United States Department of Commerce

Technology Administration

National Institute of Standards and Technol

NAT L INST. OF STAND & TECH R.I.C.

NIST Special Pumcation 879

Ceramic Powders Characterization:

Results of an International

Laboratory Study

S. G. Malghan and S. M. Hsu, Editors

QC

100

.U57

NO. 879

1995
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'At Boulder, CO 80303. ^Some elements at Boulder, CO 80303.
NIST Special Publication 879

Ceramic Powders Characterization:

Results of an International

Laboratory Study

S. G. Malghan and S. M. Hsu, Editors

Materials Science and Engineering Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

Contributors:

R. Munro and L.-S. H. Lum, NIST

A. L. Dragoo, DOE

H. Hausner, TUB, Germany

R. Pompe, SCI, Sweden

July 1995

U.S. Department of Commerce

Ronald H. Brown, Secretary

Technology Administration

Mary L. Good, Under Secretary for Technology

National Institute of Standards and Technology

Arati Prabhakar, Director
National Institute of Standards

and Technology

Special Publication 879

Natl. Inst. Stand. Technol.

U.S. Government Printing Office

Washington: 1995

For sale by the Superintendent

of Documents

U.S. Government Printing Office

Washington, DC 20402

Spec. Publ. 879

510 pages (July 1995)

CODEN: NSPUE2

This report is the result of a cooperative program on ceramics for Heat Engines and other conservation applications by the

Department of Energy. The research was partly sponsored by the U.S. Department of Energy, Assistant Secretary for Energy

Efficiency and Renewable Energy, Office of Transportation Technologies, as part of the Ceramic Technology Project of the

Propulsion System Materials Program, under contract DE-AC05-84OR21400 with Martin Marietta Energy Systems, Inc.
FORWARD

Reproducible manufacturing of high quality advanced ceramics components

requires the use of powders having high purity, and consistent physical and

chemical properties. The development and use of technically sound powder

characterization methods is one of the ways to accomplish reproducibility in

manufacturing. In addition, rapid commercialization of the advanced ceramics

can be accomplished by reaching a consensus on the measurement methods on an

international -scale since the raw materials and their processing to

manufacture ceramic components is carried out in different countries. Instead

of carrying out the required research in individual countries , the United

States, Germany and Sweden joined hands in 1979 under the auspices of the

International Energy Agency to initiate a collaborative research program on

advanced ceramics for high performance engines and other energy conservation

applications

In 1984, under the far-sighted leadership of Messers Al Chesnes , and Robert

Schulz, Office of Transportation Systems in DoE, Mr. Ed Lenoe of the U.S. Army

Materials Command in Watertown, MA, an international cooperative study on

advanced ceramics was launched. With the inputs of the U.S. industries, an

agreement was formulated under the auspices of the International Energy

Agency, lEA, and the countries involved were the United States, Germany, and

Sweden.

The agreement is called "Implementing agreement for a program of research and

development of high temperature materials for automotive engines". The U.S.

Department of Energy is the Operating Agent for the agreement, with the

Kernforschunganlage Julich GmbH in the Federal Republic of Germany, and the

Swedish National Board for Technical Development as the counterparts for the

agreement. The initial technical management was carried out by the U.S. Army

Materials Command under contract to DoE. This was changed to the Oak Ridge

National Laboratory in 1987.

The research in this report was conducted under the lEA Annex II Subtask 2

agreement. The objective of this task was to study the various

characterization methods on ceramic powders. The study was coordinated by the

National Institute of Standards and Technology in cooperation with U.S.

Department of Energy. This report represents the combined efforts of many

people in 25 organizations who participated in the ceramic powders

interlaboratory comparison project. It also represents a landmark for

international cooperation in the fast growing technology. We would like to

express our sincere thanks to all who participated in the project, especially

the national technical leaders: Dr. Alan Dragoo of the United States, Prof.

Hausner of Germany, and Dr. Robert Pompe of Sweden.

To the readers of this report, this document is the first of its kind, and is

the most comprehensive compilation of fine ceramic powder properties to date.

In the future, we plan to prepare reports on the subsequent Subtasks 6 and 8.

Stephen M. Hsu Subhas G . Malghan
PARTICIPANTS*

Chairman, Subtask 2

Technical Leader for the United States

Technical Leader for Federal Republic of Germany

Technical Leader for Sweden

Stephen M. Hsu

Alan L. Dragoo

Hans Hausner

Robert Pompe

Participants from the United States

Richard R. Hengst AC

Elise Hersenhart, Nancy Fitzgerald

Bernard J . Busovne

Wolfgang Boecker

Lawrence P. Boesch, Jo Meglen

H. Fred Linebarger

Gary M. Crosbie

Samuel Natansohn, Francis X. Pink

Marc Freedman

Alan L. Dragoo, Subhas G. Malghan, Stephen M. Hsu

William Andruchow, Param Tewari, Kamal E. Amin

Mark A. Janney

Theresa M. Resetar, James W. McCauley

Spark Plug Division of General Motors

Alcoa Technical Center

Allied- Signal Aerospace Company

Carborundum Company

Engineering and Economics Research

Elkem Materials

Ford Motor Company

GTE Laboratories

NASA Lewis Research Center

NIST

Norton Company

Oak Ridge National Laboratory

U.S. Army Materials

Technology Laboratory

Participants from the Federal Republic of Germany

Gerhard Franz

W. Kraft

Gangolf W. Kriechbaum

Gerhard Rehfeld

Schwetz, Peter Matje

Rolf Priimmer

Jiirgen Heinrich

A. Naoumidis

Albert Kerber

G. Schwier

Hans Hausner, Wolfgang Genthe

3. Participants from Sweden

Michael Hatcher KemaNord Indus trikemi AB

Robert Pompe Swedish Ceramic Institute

^Affiliation of participants was during the period in which this Subtask was

implemented.

Bayer AG

Robert Bosch GmbH

Degussa AG

Dynamit Nobel

Electroschmelzwerk Kempten GmbH

Fraunhofer- Inst i tut fur Werkstoffmechanik

Hochst CeramTec AG

KFA Julich GmbH

Lonza Werke GmbH

Hermann C. Starck Berlin GmbH

Technische Universitat Berlin

iv
EXECUTIVE SUMMARY

The application of advanced ceramics In engines depends on developing reliable

and cost-effective ceramics that will withstand harsh engine environments.

Improvement in the characterization of ceramic starting powders is a critical

factor in the control of reliability. Ceramic powders used by manufacturers

of components are increasingly obtained from producers throughout the world.

Consequently, the need for internationally agreed upon measurement procedures

is becoming increasingly critical.

This report contains the results of an international interlaboratory

comparison program ( "round- robin" ) of powder characterization under the

auspices of International Energy Agency (lEA). The results include the

contributions of 25 industrial, university and governmental laboratories in

the Federal Republic of Germany, Sweden and the United States. These

laboratories surveyed a variety of methods for the characterization of

physical properties and chemical characteristics of ceramic starting powders.

For the first time, data from various measurement methods are available for

critical comparison. Results of the same method from different laboratories

are also provided. This represents an important milestone towards

international consensus on powder measurement methodology in advanced

ceramics

.

The selected fine powders of silicon nitride, silicon, silicon carbide, and

zirconia were representative of different methods of production and various

types and stages of ceramic component manufacture. Careful preparation of the

samples of the selected powders was carried out by the National Institute of

Standards and Technology (NIST) to assure sample- to -sample homogeneity.

Measurements were carried out by each laboratory according to its customary

procedures. All results and descriptions of methods were reported to NIST.

Data compilation and statistical analysis were performed by NIST personnel.

The three technical leaders then performed analyses and drew conclusions.

These conclusions were sent to individual participants for comments.

This report presents the final results and summarizes the data obtained and

the methods studied under the auspices of lEA/Annex II, Subtask 2, Powder

Characterization. Recommendations for future studies are drawn from results

of the present round- robin. The data obtained in Annex II will no doubt serve

as the basis for designing and conducting future studies as well as for the

development of standard procedures needed in the international arena of

advanced ceramic materials

.

Technical Program Description

Samples of the following five powders: silicon nitride (reference), silicon

nitride (test), silicon, silicon carbide and zirconia, were prepared and sent

to the participating laboratories. Each laboratory performed a core group of

analyses using standard methods employed in their respective laboratories. A

summary of properties and methods is presented below.

V
I. Physical Properties

Density

Bulk density (helium pycnometer)

Tap density

Specific surface area

Single point BET

Multi -point BET

Particle size and size distributions

Gravitational sedimentation

Centrifugal sedimentation

Light scattering

Fisher sub -sieve

Photon correlation spectroscopy

Electrical sensing zone

Particle Morphology

Scanning Electron Microscopy

Transmission Electron Microscopy

Phase Composition

X-ray diffraction

II. Chemical Properties

Major Methods

X-ray fluorescence (XRF)

Atomic absorption (AA)

Inductively coupled plasma (ICP)

Direct current plasma (DCP)

Gravimetry

Major Non-Metallic Impurities

Total carbon in SisN^, SiC (Combustion)

Free carbon in SiC (Combustion)

Total carbon in Zr02 (Combustion)

Nitrogen in SiC, Si, SisNz, (Combustion)

Oxygen in SisN^, SiC, Si (Fast Neutron Activation Analysis)

Sulfur in SisN^ (Combustion)

Fluorine in SigN^, SiC (Ion Chromatography and

Electrochemical Method)

Chlorine in Si, SiC (Ion Chromatography)

Sulfur in Zr02 (Inductively Coupled Plasma)

(Combustion)

(Mass Spectrometry)

(Ion Chromatography)

v.i
Chlorine in Zr02 (Ion Chromatography,

Neutron Activation and

Argentometric Titration)

Major Metallic Impurities

Free Si in SijN^ (Electrochemical Titration)

(Volumetric Analysis)

Al.Fe.Ca in SigN^, SiC, Si (Atomic Absorption)

(Inductively Coupled Plasma)

(Direct Current Plasma)

(X-ray Fluorescence)

(Mass Spectrometry)

Minor Impurities

S,F,Cl,Na,Mg,K,Ti,Cr,Mn

Ni.W.B in SigN^, Si (Inductively Coupled Plasma)

(Atomic Absorption)

(Mass Spectrometry)

(Direct Current Plasma)

Results and data collected from the participants were analyzed statistically

at NIST by Dr. R. Munro to identify outliers and the primary sources of

variance. Binary comparisons of data and methods were also performed.

Conclusions

Average particle size, density, and surface area are in good agreement not

only among different laboratories but also among the various methods used.

This is somewhat contrary to the previous experience on ceramic powder

interlaboratory comparison. The major difference this time is the

extraordinary care taken in sample preparation and packaging. This resulted

in a minimum sampling error.

Particle size distributions from six methods showed a wide range of variation.

The cause of the variation had been determined to be mainly from the following

three sources: sample pretreatment method and severity, different sensitivity

ranges from various instruments, and different measurement principles.

The chemical analysis of major elements and minor trace impurities presented a

higher than normal deviation. The source of error can be traced to: the lack

of standard reference materials for calibration; different sample pretreatment

methodology associated with different instruments; the choice of instruments

and methods

.

vii
Specific conclusions are as follows:

1. Sample preparation methods influence the results of particle size

measurements. Consequently for a set of methods to be compared, a

universal prescription for sample preparation is required so that a stock

slurry is obtained which satisfies (1) the volume requirement of the

method with the largest volume requirement and (2) the concentration

requirement of the method with the most concentrated suspension. Volumes

and concentrations for other methods to be compared would be obtained by

taking suitable aliquots and by making the appropriate dilutions.

2. A bias between specific surface areas determined by single point and

multipoint BET measurements was apparent. However, accurate evaluation

of this bias was obscured by the variability in the data. One source of

variability was the use of different outgassing times and temperatures.

Establishment of a common preparation procedure is recommended.

3. A limited amount of quantitative x-ray diffraction data for phase content

determination was obtained. Several methods for analysis of the data

were used by the laboratories. Concentration (in percent) of secondary

phases typically varied by about 2%. Some of the methods used were

outdated or contained measurement biases. A wider base of test data for

methods based on the best measurement assumptions and protocols is

needed. The use of silicon nitride as the initial test powder is

suggested,

4. Results showed low precision (relative standard deviation > 25 %) for the

analysis by AAS , ICP and DCP of the major metallic impurities Al , Ca and

Fe in SigN^ and SiC. Better interlaboratory agreement (i.e.,

reproducibility) and intermethod consistency were obtained with acid

digestion rather than with flux dissolution of SigN^ and SiC. More

problems were evident in the analysis of SiC than of SisN^. Withinlaboratory uncertainty (i.e., repeatability) was improved by the use of

an internal standard, such as Sc for ICP, and by the use of synthetic

calibrating solutions.

5. Limited data on halide impurities in SigN^, and SiC were obtained. Two

sample preparation methods were used for extraction of halides: hot-water

leaching and flux decomposition. Leaching methods were employed in a

limited manner, mostly for F and CI impurities. Both hot water and

boiling water leaching were used. However, insufficient data were

obtained for detailed analyses. Principal detection methods used were:

ion chromatography, specific ion electrode, argentometric titration for

CI" and potentiometric titration. Concentrations determined after

leaching were somewhat less than those obtained after decomposition.

6. Oxygen in SigN^ and SiC was determined by combustion/decomposition using

either thermal conductivity or IR absorption detection. The results of

most laboratories were in agreement with results from fast neutron

activation analysis; however, some results for 0 in SisN/, (both reference

and test samples) were inexplicably high.

viii
7. Results for total C in SiC showed low precision (relative standard

deviation > 3 %) and a possible negative bias of about 2%. Carbon

analysis by combustion/decomposition may be improved by the development

of better calibration standards.

8. Kjeldahl analysis of N in SisN^, and Coulometric titration of C in SiC were

each tested by three laboratories. Both methods require decomposition of

the sample followed by recovery of the element in an evolved gaseous

compound and then by analytical determination. The overall precision was

good in both cases, and the development of reference methods based on

these two approaches appears to be promising. However, specific

procedures need to be developed and tested in more laboratories.

Recommendations . Recommendations for further comparisons of powder

characterization measurements are discussed at length in the report. The

recommendations were developed by the task leaders in their analysis of the

data, through further discussions between themselves and in consultation with

participants . The recommendations may be summarized as follows

:

1. Further interlaboratory testing is required to improve the analysis

by AAS, ICP and DCP of Al , Ca and Fe in SigN^ and SiC.

2. Further interlaboratory testing of an analysis procedure for halides

is required to develop sufficient data for an accurate evaluation by

leaching or decomposition analysis.

3. Develop and evaluate procedures for analysis of C and 0 in SigN^ and

SiC by combustion/decomposition.

4. Develop and evaluate a potential reference method for one of the

following analyses:

a. Determination of N in SigN^ by the Kjeldahl method;

b. Determination of C in SiC by Coulometric titration.

5. Develop and evaluate a method for analysis of free -carbon in SiC,

similar to DIN 51075 (in FRG) which was Intended for coarse-grain

SiC.

6. Test one or more methods for the analysis of discrete Impurities.

7. Develop and test a methodology for sample preparation which enables

two or more methods to be compared. SEM analysis of deposited

particles is suggested as a method for evaluation of agglomeration

conditions in the slurry.

8 . Develop a sample preparation procedure for BET measurements and

evaluate the bias between single point and multipoint methods.

9. Compare thermal weight loss measurements for a selected powder.

ix
10. Evaluate one or more methods for spectroscopic analysis of powder

surface chemistry.

11. Evaluate and compare methods based on current laboratory practice

for determination of surface charge related properties using such

methods as electrokinetic measurements and acoustophoresis

12 . Devise and evaluate a procedure for quantitative phase determination

by x-ray diffraction.

Subsequent to the completion of the Subtask 2 work, the participants voted to

continue the powder characterization task under Subtask 6

The contributions from all participants in the round robin are gratefully

acknowledged

X
ACKNOWLEDGMENTS

The research described in this report and conducted under the terms of the

International Energy Agency (lEA) Annex II agreement entitled, "Implementing

Agreement for a Programme of Research and Development of High Temperature

Materials for Automotive Engines," was performed by participating laboratories

in the United States, the Federal Republic of Germany, and Sweden. The

research in this report is identified within the Agreement as Subtask 2,

Powder Characterization.

The organization in each country responsible for the research was the

Department of Energy in the United States, the Kernforschungsanlage Jiilich

GmbH (KFA-PLR) in the Federal Republic of Germany, and the Swedish National

Board for Technical Development (STU) in Sweden. The person in each country

responsible for organization and overseeing the research was A. L. Dragoo at

National Institute of Standards and Technology (NIST) in the United States; H.

Hausner, Technical University of Berlin, Federal Republic of Germany; and R.

Pompe , Swedish Ceramic Institute, Sweden. Mssrs. Dragoo, Hausner, and Pompe

also were responsible for conducting the technical analysis of the data. A.

L. Dragoo provided extensive preparation and editorial work on this report,

and brought together the individual contributions. S. G. Malghan provided

descriptions of many of the methods and made a major contribution in the

preparation of the report. L.-S. H. Lum and R. Munro provided invaluable help

in statistical analysis of the data. L.-S. H. Lum also prepared the final

data tables. M. Robinson was responsible for typing the report. S. M. Hsu,

Chairman, of NIST coordinated all of the research activities in Subtask 2.

V. J. Tennery, Oak Ridge National Laboratory, had overall responsibility for

this lEA Agreement research in the United States. We want to acknowledge the

support of D. R. Johnson, Project Manager, Oak Ridge National Laboratory,

under Ceramic Technology Program this work was conducted. Messers. R. B.

Schulz and A. Chesness provided an overall leadership and guidance, and a

significant financial support to NIST for this work. The Department of

Energy, through the Heat Engine Propulsion Division, Office of Transportation

Systems, provided partial financial support (the Ceramic Technology for

Advanced Heat Engines Project of the Advanced Materials Development Program,

under Contract DE-AC05 - 840R21400 , with Martin Marietta Energy Systems, Inc.).

The researchers in many laboratories in the three countries who contributed

their knowledge and skills to this research which focused on the evolution of

standardized ceramic powder characterization measurements are too numerous to

name here, but their participation was critical to this international

cooperative effort.

xi

Table of Contents

FORWARD iii

PARTICIPANTS iv

EXECUTIVE SUMMARY v

ACKNOWLEDGMENTS xi

1. INTRODUCTION 1

S. G. Malghan and A. L. Dragoo

1.1 BACKGROUND 1

1.2 PURPOSE OF SUBTASK 2 2

1.3 TECHNICAL BACKGROUND 3

1.4 MEASUREMENTS 6

1.5 STATISTICAL ANALYSIS 8

1.6 REFERENCES 10

2. DENSITY OF POWDERS- -METHODS , AND DATA ANALYSIS 11

H. Hausner and S. G, Malghan

2.1 METHODS 11

2.2 DATA . 13

2.3 STATISTICAL ANALYSIS 24

3. SPECIFIC SURFACE AREA. 29

R. Pompe and S. G. Malghan

3.1 MEASUREMENT METHODS 29

3.2 DATA 43

3.3 STATISTICAL ANALYSIS 57

4. PARTICLE SIZE AND PARTICLE SIZE DISTRIBUTION (PS & PSD) 65

H. Hausner and S. G, Malghan

4.1 MEASUREMENT METHODS 65

4.2 DATA 80

4.3 STATISTICAL ANALYSIS 131

xiii
5. PARTICLE MORPHOLOGY 132

R. Pompe and A. L. Dragoo

5.1 MEASUREMENT METHODS 132

5.2 SEM AND TEM MICROGRAPHS 137

5.3 PARTICLE MORPHOLOGY - QUANTITATIVE DATA 158

5.4 REFERENCES 164

6. CHEMICAL COMPOSITION OF POWDERS 165

A. L. Dragoo and S. G. Malghan

7. MAJOR CHEMICAL COMPONENTS 168

A. L. Dragoo, S. G. Malghan, R. G. Munro and S. M. Hsu

7.1 METHODS FOR SILICON IN SILICON NITRIDE, SILICON

CARBIDE AND SILICON 168

7.2 METHODS FOR NITROGEN IN SILICON NITRIDE 175

7.3 METHODS FOR TOTAL CARBON IN SILICON CARBIDE 180

7.4 METHODS FOR ZIRCONIUM IN YTTRIA-ZIRCONIA 182

7.5 METHODS FOR YTTRIUM IN YTTRIA-ZIRCONIA 183

7.6 DATA 185

7.7 STATISTICAL ANALYSIS 205

7.8 REFERENCES 208

8. MAJOR NONMETALLIC IMPURITIES 209

A. L. Dragoo, S. G. Malghan, R. G. Munro and S. M. Hsu

8.1 METHODS FOR TOTAL CARBON IN SILICON NITRIDE AND

SILICON 209

8.2 METHODS FOR FREE CARBON IN SILICON CARBIDE 211

8.3 METHODS FOR TOTAL CARBON IN YTTRIA-ZIRCONIA 211

8.4 METHODS FOR NITROGEN IN SiC, SILICON AND

YTTRIA-ZIRCONIA 212

8.5 METHODS FOR OXYGEN IN SILICON NITRIDE, SILICON

CARBIDE AND SILICON 212

8.6 METHODS FOR FLUORINE IN SILICON NITRIDE AND

SILICON CARBIDE 216

xiv
8.7 METHODS FOR CHLORINE IN SILICON CARBIDE AND SILICON .... 217

8.8 METHODS FOR SULFUR IN YTTRIA-ZIRCONIA 217

8.9 METHODS FOR CHLORINE IN YTTRIA-ZIRCONIA 218

8.10 STATISTICAL ANALYSIS 218

9. MAJOR METALLIC IMPURITIES 247

A. L. Dragoo, S. G. Malghan, R. G. Munro and S. M. Hsu

9.1 METHODS FOR FREE SILICON IN SILICON NITRIDE 247

9.2 METHODS FOR ALUMINUM, CALCIUM AND IRON 247

9.3 METHODS FOR OTHER MAJOR METALLIC IMPURITIES

IN YTTRIA-ZIRCONIA (Si, Ti, Hf, Sn, Nd, Ho) 255

9.4 DATA ON MAJOR METALLIC IMPURITIES 256

10. MINOR NONMETAIilC AND METALLIC IMPURITIES 315

A. L. Dragoo, S. G. Malghan, S. M. Hsu and R. G, Munro

10.1 METHODS FOR MINOR NONMETALLIC AND METALLIC

IMPURITIES 315

10.2 NONMETALLIC IMPURITIES (S, F, Cl) IN SILICON NITRIDE

SILICON CARBIDE AND SILICON 315

10.3 METALLIC IMPURITIES IN SILICON NITRIDE, SILICON CARBIDE

AND SILICON (Na, Mg, K, Ti, Cr, Mn, Ni, W, B) 316

10.4 METALLIC IMPURITIES IN YTTRIA-ZIRCONIA

(Na, Mg, K, Ga, Ba) 320

10.5 SULFUR IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 320

10.6 FLUORINE IN SILICON 322

10.7 CHLORINE IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 323

10.8 SODIUM IN ALL POWDERS 327

10.9 MAGNESIUM IN ALL POWDERS 334

10.10 POTASSIUM IN ALL POWDERS 341

10.11 TITANIUM IN SILICON NITRIDE, SILICON CARBIDE

AND SILICON 344

XV
10.12 CHROMIUM IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 349

10.13 MANGANESE IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 352

10.14 NICKEL IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 355

10.15 TUNGSTEN IN SILICON NITRIDE 359

10.16 BORON IN SILICON NITRIDE, SILICON CARBIDE AND

SILICON 359

10.17 GALLIUM IN YTTRIA-ZIRCONIA 362

10.18 BARIUM IN YTTRIA-ZIRCONIA 362

10.19 STATISTICAL ANALYSIS 362

11. PHASE COMPOSITION ANALYSIS 368

A. L. Dragoo

11.1 METHODS FOR X-RAY DIFFRACTION 368

11.2 DATA 374

11.3 REFERENCES 384

12. THERMAL ANALYSIS 385

A. L. Dragoo and S. G. Malghan

APPENDIX I: Physical Properties 386

APPENDIX II: Particle Size and Morphology 414

APPENDIX III: Chemical Composition 441

APPENDIX IV: Phase Composition 489

XVi
1 . INTRODUCTION

S. G. Malghan and A. L. Dragoo

National Institute for Standards and Technology

1.1. BACKGROUND

Purpose of lEA/Aimex II

The lEA/Annex II program was directed toward generic research in hightemperature structural ceramics for advanced engines and other energy

conservation applications. The major objective was the evolution of

internationally accepted standardized testing and characterization methods for

structural ceramics and for starting powders used in the fabrication of

structural ceramics

.

Program

The Annex II program set up three major experimental tasks to achieve its

objective. These tasks were:

• characterization of ceramic powders (Subtask 2)

• characterization of structural ceramics (Subtask 3)

• measurement of fracture strength (Subtask 4)

Annex II was developed on the basis of work completed in Annex I which

emphasized ceramic component development for gas turbines. Industry and

government laboratories worked closely in both activities to define the

technical scope of work, to carry out the measurements and to discuss and to

evaluate the results. Industrial participants in each country cost- shared a

portion of the research.

During its formative stage, Subtask 2 was under the chairmanship of Dr. J. W.

McCauley, U.S. Army Materials Technology Laboratory. During this stage, NIST

provided technical support through the preparation and distribution of

samples. During the second stage of Subtask 2 which required the compilation,

distribution of results to participants and data analysis. Dr. S. M. Hsu,

NIST, served as the chairman.

Importance of Advanced Ceramics for Heat Engines

Ceramics have been successfully employed in engines on a demonstration basis.

The successful manufacture and use of ceramics in advanced engines depends on

the development of reliable materials that will withstand high, rapidly

varying stress loads. Improvements in the characterization of ceramic

starting powders is a critical factor in achieving reliable ceramic materials

for engine applications.

1
1.2. PURPOSE OF SUBTASK 2

Objectives

The overall objective of the powder characterization effort was the

enhancement of the quality, reproducibility and reliability of powder

characterization measurements and, consequently, of ceramic powders.

Through a program of interlaboratory comparison of measurements , the

participants in Sub task 2 sought the following:

• survey methods currently in use for characterization of ceramic

starting powders,

establish a base of data and experience which would identify unique

sets of properties and methods useful for powder evaluation and

comparison,

• determine the extent of agreement between laboratories,

identify areas for further measurement research, and

• recommend useful standards which would aid international commerce.

Participants were encouraged to report results of measurements which they

believed represented the "true" values of the material characteristics.

Importance of Powder Characterization

Physical and chemical characteristics of powders strongly influence their

behavior during ceramic processing and, thus, impact ultimately upon the

microstructure and performance of ceramic components produced from them. The

ceramic process cannot be adequately controlled for large scale production of

high-quality technological components without detailed information on the

powder characteristics. Moreover, as identified by the NIST study conducted

by Charles River Associates^ (CRA) , the key issues in the commercialization

of ceramic materials for advanced technological applications are production

cost, reliability in service and reproducibility in manufacture. For the case

of ceramic heat engines, CRA saw reliability as a major technological barrier,

and improved characterization of ceramic powders as providing "important

leverage in overcoming the reliability and reproducibility problems."

Improved characterization of ceramic powders requires not only improved

measurements but also improved understanding of how powder characteristics are

related to properties and performance of resulting ceramic materials.

In view of the many applications of structural ceramics, as heat engine

components as well as in other areas of use, the analysis of powder

characteristics includes particle size distribution, particle morphology, bulk

elemental composition, surface chemistry, crystalline/noncrystalline phases,

surface area, density, porosity, and grain or primary particle size.

Different applications emphasize different combinations of these

characteristics.

2
Importance to Industry and Commerce

Powders used in the fabrication of advanced structural ceramic components are

manufactured in a number of the major industrial countries of the world. A

manufacturer of ceramic components may obtain powders from a number of these

sources. However, few standard methods and certified reference materials are

available for the evaluation of these powders in the international

marketplace. Moreover, a set of data obtained from characterization of a

large number of homogeneous samples by several laboratories was not available,

prior to this study, to assist in the development of standard methods and

reference materials

.

A key part of Subtask 2 was the participation of companies from the three

countries. Powders (See Section 2.1.1, below) were obtained from different

sources. Current characterization instruments and procedures were compared.

Finally, a forum was provided in which measurement methods and problems were

discussed.

1.3. TECHNICAL BACKGROUND

Issues in powder characterization are what to measure, how to measure and how

to ensure quality in analytical measurements. "What to measure" involves

understanding the relationships between powder characteristics and ceramic

microstructures . "How to measure" requires the development of measurement

methods and the determination of repeatability and reproducibility. A

thorough analysis of repeatability and reproducibility requires breaking a

method down into a series of procedural steps and determining the influence of

each step on the precision and, if possible, on the accuracy of the

measurement. Standard (or certified) reference materials are required to

assure the quality of the measurements and comparability of measurements

between different laboratories and techniques or equipment.

A foremost requirement to achieve these objectives is the selection and

preparation of powder samples. Repeatability and reproducibility of ceramic

powder characteristics are assured only when the powder samples are prepared

according to well-established statistical procedures.

Powders

The powders were selected on the basis of extensive discussion and consensus

among the participants. Several factors were considered in these discussions:

(1) production in one of the participating countries, (2) use by one or more

companies in the manufacture of structural ceramics, and (3) use in the

fabrication of samples for Subtasks 3 and 4. The powders selected for the

program, along with the abbreviations used for them in this report were:

3
Silicon nitride, LC-IO^^', H.C. Starck (SNR)

Silicon nitride, SNE-10, Ube Industries (SNT)

Silicon, IV-D, Kemanord (Si)

Silicon carbide (< 5 fim) , H.C. Starck (SiC)

Yttria-zirconia, *ToyoSoda (YSZ)

The LC-10 silicon nitride powder was selected by the participants to serve as

an internal reference material for the purposes of the round- robin.

*Since completion of this work ToyoSoda has changed company trade name to

TOSOH

The powder lots were obtained by Oak Ridge National Laboratory and delivered

to NIST for sampling, distribution and archiving.

Sample Preparation : Summary of Procedure for Subdivision of Powders.

Sample preparation required:

(1) the division of a bulk lot of powder into representative samples,

(2) the avoidance of contamination, and

(3) packaging in a manner which would assure long-term sample

integrity.

Division of the powder by means of spinning rifflers was used to minimize

sample- to -sample variance. Contamination was avoided by processing one powder

at a time and by operating the rifflers in an isolated laboratory which was

serviced by a filtered air supply. Powders were stored under an inert gas.

Sample vials were hermetically packaged with a dry argon ambient in the free

space of the vials and surrounding envelope.

Powder samples were prepared from 25 kg bulk lots of powder, with the

exception of the LC-10 silicon nitride which was received in a 100 kg lot.

Sample preparation consisted of cone blending of the total lot, followed by

manual division by small increments into several plastic lined metal

containers to obtain units containing about 2 to 3 kg each, depending upon the

packing density of the powder. Thus, a 25 kg lot was split into 8 or 12

smaller lots. Due to the fluffiness of the LC-10 powder, it was split into 48

smaller lots. These units were vacuum dried and the containers were

backfilled with dry argon.

Two subsequent divisions were carried out using spinning rifflers, such as the

one shown in Figure 1. A third riffling was performed using a smaller

Certain commercial equipment, vendors, instruments, or materials are

identified in this report in order to adequately describe experimental

requirements. In no case does such identification imply recommendation or

endorsement by the International Energy Agency, nor by any of the

participants in lEA/Annex II, nor does it imply that the vendor material or

equipment identified is necessarily the best available.

4
Figure 1. Laboratory spinning riffler

5
riffler. Samples were vacuum dried and backfilled with dry argon after each

operation. The final riffling was carried out entirely in an ambient of dry

argon, and the samples were collected directly in sample vials which were

closed with plastic caps; see the inner sample vial shown in Figure 2. The

samples which were obtained from the final operation were about 4 g in weight

for the silicon nitride, silicon carbide and silicon samples and 12 g in

weight for the yttria-zirconia samples. These samples were hermetically

sealed immediately in foil laminate pouches to preserve an atmosphere of dry

argon around the vials. For the yttria-zirconia powder and the two silicon

nitride powders , sample vials were subsequently inserted individually into an

outer glass envelope which was flame -sealed. A schematic of a flame -sealed

sample is illustrated in Figure 2. A major equipment failure with the flame

sealer prevented the use of this encapsulation method for the silicon and

silicon carbide samples.

Sample -to -Sample Homogeneity

Sample- to -sample homogeneity was maintained (1) by the use of spinning

rifflers, (2) by probability sampling at all stages and (3) by blending

randomly selected pairs of samples prior to riffling. Verification of

homogeneity was carried out by testing randomly selected samples and by

maintaining traceability of samples. Traceability required maintaining

a lineage record for each sample so that sample numbers associated with

anomalous measurement values could be compared.

1.4. MEASUREMENTS

The major intent of this round-robin was the survey of a variety of methods

which provide characterization of the powder chemistry (i.e., elemental

constituents and phases), microstructure , particle size, other physical

properties and processing defects. For the purpose of the most complete

statistical analysis of the data it was desirable for each participant to

contribute sufficient characterization of as many selected properties as

possible. However, the analyses selected and the extent of the effort of each

participant depended on their interest, experience and resources. The degree

to which a single method was replicated by a single laboratory or used by

several laboratories varied widely in this study. Although an attempt was

made to have at least four laboratories using the same method, this was not

always realized in the final results. In some cases in the following report,

results contributed by one or two laboratories are considered and compared

with results obtained by other methods because the precision of the

measurement, possible accuracy of the method, or because degree of agreement

with another method suggests that a more extensive study may be warranted in

the future

Each laboratory was instructed to follow their customary procedure for a

method and to report what they considered to be the "true" value given by a

measurement. Laboratories were requested to provide the individual results of

replicate measurements and to provide documentation for the measurement

procedure followed.

6
fiberglass

pad

E

E

05

sample in

inner vial

flame-sealed

outer vial

colored

polyethylene

snap-cap

80 mm

Figure 2. Illustration of flame-sealed sample.

7
Structure of the Report

The report is divided into several chapters, and each chapter is devoted to a particular property of the powder. In each chapter, the technical material is

organized as follows:

• Methods used for making measurements.

• Statistical data in the form of tables and plots.

• Tabulated data from all participants.

Reporting of Results

For the purposes of comparison of the large volume of data in this report, as

well as to reduce a large volume data to a tractable quantity for publication,

it was necessary in most instances to report the results of a measurement by

one or two numbers. In cases where an averaged bulk property is obtained by a

measurement, no information is lost. However, for measurements of particle

size distributions, in particular, this meant a representation of the

distribution by a mean value, usually the median (D50) , and a measure of the

spread, i.e., the difference of the size at 90% finer and 10% finer divided by

D50, or

(Dgo - Dio)/D5o

Although such a representation was in most cases an oversimplification and

meant that the full details of the distribution were not reported here, the

use of the central tendency and the spread may serve for an adequate

comparison of measurements by different laboratories.

In addition, each laboratory was encouraged to run the H. C. Starck LC-10

silicon nitride as an internal reference material. Further comparison between

laboratories can be made by first normalizing their results to their

respective results obtained for the reference silicon nitride powder. A large

body of data on this powder was collected by the participants.

Since most laboratories also provided selected information about the

experimental procedures which they used, a limited number of analyses of the

effects of analyte processing on measurements was possible. These analyses

are presented as part of the technical analyses in each chapter.

1.5. STATISTICAL ANALYSIS''

There were 39 different properties that could be reported for each of the

approximately 700 lEA samples. Each participating laboratory performed a

selected subset of these tests, consistent with the measurements normally

performed by that laboratory. As a result, laboratories performing physical

measurements often reported particle size results, while laboratories

conducting elemental analyses usually reported results for a selected set of

chemical elements.

8
The data obtained in this study, therefore, are useful for identifying

overall, or pooled, sources of variance, but not individual contributions from

distinct sources such as sampling technique, specimen preparation, apparatus,

and operator performance. That level of detail will be addressed in the

future when specific measurement procedures are studied. For the present

purposes, it is adequate to consider only effective measures of repeatability

and reproducibility.

The variability in the property values determined by a given laboratory using

a specified technique can be estimated by computing the standard deviation of

the replicated measurements, i.e., the estimate of repeatability is based on

the within - laboratory variance. An estimate of the reproducibility of a

measurement can be made by computing the standard deviation of the means

obtained from different laboratories using what is nominally the same

technique; i.e., the estimate of reproducibility is based on the betweenlaboratory variance. It should be emphasized that this estimate in particular

neglects differences in specimen preparation and detailed measurement

procedures. When two or more methods are used to determine a property value,

an overall mean can be computed for each method; then, an estimate of the

robustness of a property measurement can be made by computing the standard

deviation of the overall means obtained from each of the different methods.

Throughout this report, the terms "average value" (A) and "standard deviation"

(S) for a set of N observations, {x^, X2 %) > ^"^^ defined as follows:

A = (Xi + X2 + ... + Xn)/N

S2 = [(xi-A)2 + (X2-A)2 +... + (xn-A)2]/(N-1).

These terms are used particularly in all of the tables of summary statistics

in the following chapters . Each summary table has an identifying header and

six columns of data. Each column has a column header which is selfexplanatory, except perhaps for the first column. The first column, LAB #,

identifies the sources of data for each row of the table. The source of the

data for each row is a participating laboratory, except for the last row of

the table which is separated from the primary rows of the table by a solid

horizontal line. The entry for the LAB in the last row of the table is

always the word "Means". The source of data for this row is the column

labeled "Average Value" in the primary rows of the table. Thus, the value of

the standard deviation given in each primary row of the table is related to

the repeatability of the measurement performed by one laboratory, while the

value of the standard deviation in the row labeled "Means" is related to the

reproducibility of the specified measurement across all of the laboratories

Representative examples of the measures of precision, reproducibility, and

robustness are presented here for both physical and chemical powder

characterization measurements. Bulk density, tap density, mean particle size,

and specific surface area are discussed as physical characterization

measurements. For chemical characterizations, three illustrative cases of

quantitative elemental analysis are discussed: measurements of a major

constituent (nitrogen in silicon nitride) , a nonmetallic impurity (oxygen in

all of the powders except zirconia) , and a metallic impurity (iron in all of

9
the powders)

Overall, the most persistent trend in the results is that the betweenlaboratory variance is greater than either the within- laboratory or betweenmethods variances. This trend bodes well for the effort to achieve

standardization in powder characterization and indicates that the careful

attention given to the primary sample preparation was successful. With the

sampling error reduced, it appears that good precision can be attained within

individual laboratories for each of the measured properties using a variety of

measurement procedures. Further examination of the descriptive information

supplied by the participants suggests that the quantitative differences among

the values measured by different laboratories arose from the varying sample

pretreatments , as well as from differences in instrumentation. These sources

of variance can be reduced by standardized measurement procedures and will

provide a focus for the next lEA round- robin program.

1.6. REFERENCES

1. Resetar, T. M. ; Schaefer, G. E. ; McCauley, J. W. ; Dragoo, A. L. ; Hsu, S.

M. ; Johnson, D. R. ; Hausner, H. ; Pompe , R. , lEA-Annex II Powder

Characterization Cooperative Program. Ceramic Powder Science, Vol. 1. Ed.

by Messing, G. L. et al . Columbus, OH: Am. Ceram. Soc; 1987. p. 304.

2. Charles River Associates, Inc. Technological and Economic Assessment of

Advanced Ceramic Materials, Vol. 1. Planning Report 19, NBS GCR 84-470-1,

National Bureau of Standards, August 1984.

3. Dragoo, A. L. ; Robbins, C. R. ; Hsu, S. M., A Critical Assessment of

Requirements for Ceramic Powder Characterization. Advances in Ceramics,

Vol. 21. Columbus, OH: Am. Ceram. Soc; 1987. pp. 711-20.

4. Munro, R. G. ; Malghan, S. G.; and Hsu, S. M. , Variances in the Measurement

of Ceramic Powder Properties, J. Res. NIST (1995),

10
2. DENSITY OF POWDERS- -METHODS AND DATA ANALYSIS

H. Hausner, Technische Universitat Berlin; S. G. Malghan, NIST

2.1. METHODS

2.1.1. Bulk Density

Use and Significance

Bulk density of powders is a measure of the true (or skeletal) density plus

closed internal porosity. This measurement is required for the application of

several methods in particle size analysis.

The helium pycnometer is the most commonly used instrument for measuring the

volume of bulk powders since helium will penetrate all of the open porosity.

The volume of the powder is determined by the volume of gas displaced by the

sample

.

Instrximent and Experimental Parameters

It is desirable to use as large a sample as possible to maximize the volume of

gas displaced. Prior to the measurement, the sample is placed in a scalable

sample holder and is degassed by heating the powder to 100 - 200 °C under

vacuum for a predetermined length of time. Following degassing, the sample is

cooled in a vacuum desiccator. The cooled sample and sample holder are

weighed and then transferred to the helium pycnometer. Volume measurements

are carried out according to the procedure required for the particular

instrument

.

Calibration and Standards

Frequent calibration of the pycnometer is desirable to establish close

experimental control of the instrument. This can be done using a steel ball

which is provided as a reference for the instrument or by using a standard

powder. The standard procedure, ASTM D854-83, "Standard Test Method for

Specific Gravity of Soils," may be consulted for guidance in the determination

of the specific gravity of ceramic powders.

Results and Discussion

Data are summarized in Section 2.3.

The bulk density measurements showed an excellent agreement, as can be seen in

Table 2.1.1. This is certainly due to the fact that the same method, or even

the same instrument type, was used and that in the latter case a wellspecified procedure was followed.

Principle

11
Table 2.1.1. Range of Bulk Density Measurements (He-Pycnometer)

Number Number Density (g/cm^) Calc

Material of labs of Determ. Min

Max

Data Ref

Si 2 57 2.30 2.35 2.33 1

SiC 2 54 3.08 3.19 3.21 2

SNR 2 34 3.12 3.18 3.18 3,4

SNT 2 51 3.13 3.20 3.18 3,4

Conclusions

The results of the bulk density measurements are in excellent agreement, but

it has to be taken into consideration that only two laboratories using the

same method reported results.

2.1.2. Tap Density

Use and Significance

The powder tap density gives an indication about the compaction behavior of

the powder. The tap density of a dry powder is affected by the relative

movement of individual particles to fill voids within the powder mass. This

relative movement will be affected by the degree of agglomeration or

dispersion of the particles. This property is also useful for comparing the

flow properties of various powders in bins, chutes and conveyor belts.

Principle

The tap density is a relative measure of the fill density and is measured by

dividing the weight of the powder by its volume after a specified number of

taps at the bottom of the receptacle containing the powder.

Instrument and Experimental Parameters

A known weight of powder (e.g., 100.00±0.02 g) is poured into a graduated

cylinder which is located in a tapping device for which the number of taps are

preset. The measured tap density is strongly dependent on the manner in which

the powder is loaded, number of taps, force imparted with each tap and wall

effects of the graduated cylinder. The experimental conditions (e.g., the

number of taps) vary significantly among different laboratories, rendering the

comparison of results difficult.

Calibration and Standards

For guidance in conducting tap density measurements on ceramic powders, the

following standard procedure may be consulted.

12
ASTM D3347-86. Flow rate and tap density of electrical grade

magnesium oxide for use in sheated-type electric

heating elements.

Results and Discussion

Data are summarized in Section 2.3. The results of five powders are compared

in Table 2.1.2.

The values for the tap density show a large scatter which appears to be due

largely to the number of taps used by different investigators.

Table 2.1.2. Range of Tap Density Measurements

Number Number Density (g/cm3)

Material of labs of Determ. Min. Max.

Si 3 3 0.78 1.08

SiC 5 5 0.68 0.83

SNR 7 7 0.74 0.87

SNT 9 9 0.66 0.78

YSZ 2 2 1.49 1.51

Conclusion

Tap density values show a large scatter due most likely to different

experimental procedures used by the participating laboratories.

2.2. DATA

2.2.1. Laboratories Making Density Measurements

Three types of density measurements were reported: bulk density, tap density

and liquid density (Archimedes' method). The identification numbers of the

laboratories making measurements are given in Table 2.2.1 for bulk and tap

density

.

13
Table 2.2.1. Laboratories Making Bulk and Tap Density Measurements

BULK TAP

Powder Type Lab No. Lab. No.

Silicon 17, 23 6, 15, 18

Silicon Carbide 17, 23 6, 10, 15, 18, 21, 25

Silicon Nitride, R 17, 23 5, 6, 18, 21, 25

Silicon Nitride, T 17, 23 14, 15, 18, 21, 25

Zirconia 17, 18 6, 14, 18

For method codes, see Table 2.3.1.

2.2.2. Bulk. Tap and Liquid Density of Silicon Nitride Reference Powder

Table 2.2.2.1 Bulk Density by He Pycnometer

Material: Silicon Nitride, Reference Powder

Property: BULK

Method: 4

// of Minimum Maximum Average Standard

Lab # Values Value Value Value Deviation

17 25 3.1200 3.1800 3.1386 0.0193

23 7 3.1310 3.1570 3.1421 0.0100

Means 2 3.1386 3.1421 3.1404 0.0025

Table 2.2.2.2 Tap Density

Material: Silicon Nitride,

Property: TAP

Method: 3

Reference Powder (Figure 3)

Minimum Maximum Standard

LAB # Values Value Value Value Deviation

5 2 0.74 0.78 0.76 0.028

6 1 0.87 0.87 0.87 0.000

15 2 0.77 0.77 0.77 0.000

17 3 1.46 1.48 1.47 0.010

18 1 0.74 0.74 0.74 0.000

21 1 0.71 0.71 0.71 0.000

25 1 0.79 0.79 0.79 0.000

Means 0.71 1.47 0.87 0.268

14
E

_Q

O

4-) c

o

,13 N

•i-i t3 >-i 0) o u

O 0) ax

u

u

0)

o

o

c

>

bO

• a>

t4-l >^ w COu

1-1 a u B

•H

= 1

o

o

•H^ w

u cd

«4-l O bO

C

>^ T-i P 4J

CO a

<u u

1-1

a.

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CO

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(0

Luo/5 *A:^jsuaa
Table 2.2.2.3 Liquid Density in Hydrocarbon, Archimedes Method

Material: Silicon Nitride, Reference Powder

Property: LIQUID

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

21 1 0.56 0.56 0.56 0.00

25 1 0.48 0.48 0.48 0.00

Means 2 0.48 0.56 0.52 0.05

2.2.3. Bulk. Tap and Liquid Density of Silicon Nitride Test Powder

Table 2.2.3.1 Bulk Density by He Pycnometer

Material: Silicon Nitride, Test Powder

Property: BULK

Method: 4

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 43 3.1300 3.2000 3.1619 0.0148

23 7 3.1360 3.1700 3.1497 0.0130

Means 2 3.1497 3.1619 3.1558 0.0086

Table 2.2.3.2 Tap Density

Material: Silicon Nitride, Test Powder (Figure 4)

Property: TAP

Method: 3

# of Minimum Maximvxm Average Standard

LAB # Values Value Value Value Deviation

6 1 0,.76 0,,76 0,,76 0,.00

14 2 0,.65 0.,67 0.,66 0,,01

15 1 0..66 0,,66 0,,66 0,.00

18 1 0,.71 0,,71 0,,71 0,.00

21 1 0,.66 0,,66 0,,66 0,,00

25 1 0,.71 0.,71 0,,71 0.,00

Means 6 0.,66 0.,76 0.,69 0.,04

16
•o

0) 4JUOu

0)o

(X

4-1 0) H

1-1

4JcOU

•H • ^ W O e»0 C

(Uu

•O T-l

cd cd u

17
Table 2.2.3.3 Liquid Density in Hydrocarbon, Archimedes Method

Material: Silicon Nitride, Test Powder

Property: Liquid Density

Method: 6

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

25 1 0.43 0.43 0.43 0.00

Means 1 0.43 0.43 0.43 0.00

2.2.4. Bulk. Tap and Liquid Density of Silicon Carbide Powder

Table 2.2.4.1 Bulk Density by He Pycnometer

Material: Silicon Carbide

Property: Bulk Density

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 36 3.08 3.19 3.1459 0.0238

23 18 3.12 3.16 3.1468 0.0113

Means 2 3.15 3.15 3.1464 0.0006

18
Table 2.2.4.2 Tap Density

Material: Silicon Carbide (Figure 5)

Property: Tap Density

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0 83 0 83 0 83 0 00

10 16 0 71 1 80 1 69 0 26

15 1 0 77 0 77 0 77 0 00

18 1 0 68 0 68 0 68 0 00

21 3 0 75 0 76 0 75 0 01

25 1 0 78 0 78 0 78 0 00

Means 6 0 68 1 69 0 92 0 38

Table 2.2.4.3 Liquid Density in Hydrocarbon, Archimedes Method

Material: Silicon Carbide

Property: Liquid Density

Method: 6

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 i 0.40 0.40 0.40 0.00

Means 1 0.40 0.40 0.40 0.00

19
0)oocoo

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E

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o\ 00

ro• CM o O• il O •

ii >Q cD •

CO

o

CVJ

lO

o

CO

(N

(N

(N

CNJ O

(N

00

CO

CMO

00

CO

-- ^

(NO

LOo

ED

tj

<uuo

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•Oo

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20
2.2.5. Bulk and Tap Density of Silicon Powder

Table 2.2.5.1 Bulk Density by He Pycnometer

Material: Silicon

Property: Bulk Density

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 40 2.300 2.350 2.3261 0.0142

23 17 2.328 2.344 2.3328 0.0049

Means 2 2.326 2.333 2.3295 0.0048

Table 2.2.5.2 Tap Density

Material: Silicon (Figure 6)

Property: Tap Density

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 1 08 1 08 1 08 0 00

15 1 1 03 1 03 1 03 0 00

17 3 1 46 1 48 1 47 0 01

18 1 0 78 0 78 0 78 0 00

Means 4 0 78 1 47 1 09 0 28

21
C

•tA 4J

(d

•Ho

•l-l 4-) U

cd

•o

4Joa0)

a>o

(Xcoo

01ou

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U) «

a. j3

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•r-l

22
I

2.2.6. Bulk. Tap and Liquid Density of Yttria-Zirconia Powder

Table 2.2.6.1 Bulk Density by He Pycnometer

Material: Zirconia

Property: Bulk Density

Method: 4

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

17 14 5.6060 5.8100 5.6870 0.0564

18 4 5.9030 6.0010 5.9480 0.0489

Means 2 5.6870 5.9480 5.8175 0.1846

Table 2.2.6.2 Bulk Density by Mercury Porosimeter

Material: Zirconia

Property: Bulk Density

Method: 13

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 6 6.0200 7.5660 6.7452 0.6493

Means 1 6.7452 6.7452 6.7452 0.0000

23
Table 2.2.6.3 Tap Density

Material: Zirconia (Figure 7)

Property: Tap Density

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6

14

15

18

1

2

1

3

1.5200

1.5000

1.4900

1.4600

1.5200

1.5000

1.4900

1.4800

1,

1,

1,

1,

5200

5000

4900

4700

0.0000

0.0000

0.0000

0.0100

Means 1.4700 1.5200 1.4950 0.0208

Table 2.2.6.4 Liquid Density in Hydrocarbon, Archimedes Method

Material: Zirconia

Property: Liquid Density

Method: 6

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 1.2200 1.2400 1.2300 0.0141

Means 1 1.2300 1.2300 1.2300 0.0000

2.3. STATISTICAL ANALYSIS . R. Munro , NIST

The bulk density of a powder refers to the average mass per unit of actual

volume of the particles in the powder. The total mass of a powder specimen

can be measured with high accuracy using a microbalance . The helium

pycnometer technique is most commonly used to determine the actual volume of

the particles in the powder. The helium gas penetrates into the open pores

and interparticle regions so that the volume of the gas displaced by the

specimen is the sum of the volumes of the individual particles including

contributions from regions of closed porosity. While only two laboratories

reported measurement results, the method appears to be among the more precise

and reproducible measurements made in this study, except for its application

to zirconia. The results in Figure 8 indicate an unusually good agreement

among laboratories.

24
In contrast, the tap density measurements, Figure 9, exhibit a large variance

between laboratories, as well as being less precise. This result is not

surprising considering the extent to which the procedural details in this

technique can influence the measured value. The tap density refers to the

average mass per unit of occupied volume and is determined by dividing the

total mass of the specimen by the volume occupied by the powder in a graduate

cylinder after being mechanically tapped a given number of times. The powder

settles or compacts as the cylinder is tapped but retains a significant pore

volume. The amount of interparticle pore volume varies with both the

magnitude of the impact imparted by the tapping and the frequency of the

tapping.

25
Xi

•O

0) 4Juo

0)V4U

9)

(0oou

•HNIcd

>-l •

4-> (0 4J ^ O bO

1-1 cd n o< C 1-1 <u u

•O iH

Q) CO

4)

26
0.20

a M 0.05

09 91 n

• « « • •

m m n m

Figure 8. Within lab and between lab standard deviations in the

measurements of bulk density for five powders as measured by

various laboratories using the helium pycnometer method.

27
0.40

.2 O

0.30 -

0.20 '

•

0.10 -

0.00

Tap Density

SiC

Si3N4

. (Bet ) Si

(Test) ZrOg

1 . . , 1 1 1 n n

S 1 1

• • •

n n m n

B9

3

Figure 9. Within lab and between lab standard deviations in the

measurements of tap density for five powders as measured by

various laboratories using tap method.

28
3. SPECIFIC SURFACE AREA

R. Pompe, Swedish Ceramic Institute; S. G, Malghan, NIST

3.1. MEASUREMENT METHODS

3.1.1. Brunauer-Emmett- Teller (BET) Method

Use and Significance

The specific surface area of powders composed of deagglomerated, compact

particles with a regular size and narrow size distribution will be closely

related to the mean particle size. For other powders, the measured specific

surface area will include factors such as shape factor, degree of

agglomeration and internal porosity of the particles. Significant indication

of particle regularity, internal porosity and agglomeration may be gained by

combining surface area data with results of measurements of particle size.

The specific surface area measurement is usually based on the well-known BET

theory which describes the multilayer adsorption of a gas upon a clean and

uniform surface. The BET theory generalizes an older Langmuir monolayer

theory by assuming that a layer of adsorbed molecules provides the sites for

the adsorption of the next layer and that only local forces exist between the

layers

.

Instrument and Experimental Parameters

The experimental parameters which can influence the measurement are;

• sample handling

• sample quantity

• degassing temperature

• degassing time

• adsorbate gas

• other factors, such as standards, reference materials.

To avoid biased measurements, the powder to be analyzed should be sampled at

many locations within the material. This is best done with a small spinning

riffler. If a riffler is not available, the powder can be poured into a shallow pile or a long row and sampled at many points. Grab samples from a

single location in the powder should not be used.

Typical amounts of powder used for samples were in the range of 1-5 grams.

Some laboratories used amounts down to 0.1-0.5 grams and still obtained

precision in specific surface area values within the range of data obtained by

other labs

.

Degassing depends on the pressure, temperature and duration at which the

surface is conditioned. Degassing conditions differed depending on the powder

Principle

29
and laboratory practice. One lab (No. 22) also carefully checked outgas rate.

Degassing conditions are sunmiarized in Table 3.1.1.

Table 3.1.1. Summary of Instrumental and Experimental Conditions in the

Single(s) and Multi-Point(M) BET Measurements

Lab BET Degass Adsorbate Instrument

No. Meas . time (h) T(°C) gas type -/ ST

1 M/S 4 150/vac N2 Micromeritics

,

2 M N2 Digisorb 2600

3 M/S 4-8 110 (+RT/vac) N2

4 S 1-3 /vac N2 Quantachrome

,

Monosorb

5 M 2 215/vac N2 Quantachrome

6 S RT-288 N2 Quantachrome

7 M/S 20 min 215 N2 Flowsorb II 2300,

8 M 17 200 N2

10 M 18 220 N2/Kr Digisorb 2500

(1-2) (-300)

11 S 350 N2/Kr Quantas orb.

+ Accusorb

.

12 M N2 Digisorb 2600

13* S 40 min (air) 300 N2 Stroehlein AREA

meter II (DIN 66132)

14 S 15/20 min 100/150-200 N2 a) - " -

S 15/1 100/200/vac N2 b) Micromer. 2400

J * 1 00 /1 SO- 900 CN N

16 S N2 - " - , DIN 66132

17 S 2-3 150 N2 Sorpty 1750,

C Erba Inst.

18 s 0.5-4 350 N2 Microm. 2200

+ Desorb 2300 A

19 s 1 200-300 N2 Desorb 2300

20 S/M 140 N2 (N2/He dynamic flow)

21 S 2 250 N2 Quantasorb

,

Quantachr

.

22 S N2 Flowsorb 2300

23 M N2 Monosorb, Quantachrome

24 M 2 250 N2 Quantasorb

>tZr02: 110 °C/16 h, heating in air

The measurements are accomplished either by a simplified singlepoint run at

the saturation vapor pressure of the liquified adsorbent gas or by the more

detailed multipoint technique. In the latter case, runs are made at different

adsorption pressures, and the specific surface area is calculated from the

slope and intercept of a straight line usually obtained from a BET plot of

30
adsorption-to-saturation pressure ratio in the range 0.05-0.25. In most cases

three runs are used to determine the specific surface area. The measurements

are performed either under static or dynamic gas flow conditions. For

example , flowing N2/He gas mixtures are frequently used for dynamic

conditions. Two labs (No. 8, 22) used Kr gas as an adsorbate which gave lower

values as compared to the results with N2 adsorbate gas.

Computer automation of the measurement enables a determination of the

adsorption isotherm.

Calibration and Standards

The use of the manufacturer's recommended procedure generally yields highly

reproducible data. However, calibration of apparatus against standard

equipment at regular intervals and/or calibration with standard powders should

decrease disparities.

A recommended general procedure is given by ASTM C1069-86, Standard Test

Method for Specific Surface Area of Alumina or Quartz by Nitrogen Adsorption.

For single point determinations consult:

DIN 66132. Determination of specific surface area by absorption of

nitrogen according to the single-point differential method

of Haul and Dumb gen.

Alpha alumina powders certified by the National Physical Laboratory,

Teddington, U.K. , and meeting the ISO conditions for certified standard

powders are available from the Community Bureau of Reference of the European

Economic Community or, in the United States from the National Institute of

Standards and Technology as Standard Reference Materials (SRM's) 8005 to 8008.

These references cover the range 0.1 to 2.1 mVg- NIST also offers SRM 8570,

a calcined kaolin, produced in conjunction with the ASTM, with a specific

surface area of 10.89 mVgDespite the availability of external standards, only a few laboratories in

this study reported the use of standards. In some cases the reported

standards were those internal to the practices of that laboratory or those

furnished by the manufacturer; for example, lab No. 22 reported the use of two

Ti02 standards with specific surface areas of 24.3 ± 0.6 and 10.3 ± 0.3 m^/g.

Instrumental Effects

The instrument information has been taken from Table 3.1.1 which is based on

primary data as provided by all labs. Several labs did not give sufficient

information on their instruments. The instruments selected include only those

used by two or more laboratories for three or more types of powders

.

The instruments compared for single point measurements are Quantasorb, Desorb

2300 and Stroehlein, and for multipoint measurements the instruments are

Quantasorb and Digisorb 2500/2600. The total number of data collected per

instrument varies considerably; from 50 to 100 values for Quantasorb and 1 to

31
10 for Stroehlein. The primary data base is thus not fully satisfactory for

all instruments - none the less, it seems apparent that none of the

instruments appear to give data sets which systematically diverge from each

other. Hence, the variation of the data obtained seems to depend more on

other factors than the selection of a particular instrument.

Lab. 10 noticed that by switching from stationary gas adsorption to the flowtype mode, the BET single point data for LC 10 SisN^ powder decreased by

approximately 5%.

Relatively coherent data were obtained from different laboratories even for

the low surface area Si powder. This indicates an overall high absolute

instrumental accuracy.

3.1.2. Results and Discussion

In this section, a general comparison is made with respect to the number of

laboratories providing data, number of measurements made, and the spread of

data when all the data are considered. In the ensuing subsections an attempt

is made to evaluate selected data with respect to instrumental and

experimental parameters, the internal consistency of powders and specific

features of a powder.

General Features

Most laboratories provided single point data, but several supplied both single

and multi -point values. Typically, in more than 50% of the cases the number

of measurements per sample was sufficient to permit calculation of a mean

value. Table 3.1.2 shows the number of laboratories providing data for single

and multi -point measurements, respectively, for different powders

investigated.

Several laboratories supplied only 1 or 2 data. These values are part of

their particular data population. A reliable comparison of these data with

average values of other laboratories cannot be made because the precision of

such data cannot be estimated. However, it still may be of interest to

include these data in a graphical representation (see Figures 9-18)

32
I

Table 3.1.2. Number of Laboratories Single and Multipoint BET

Measurements Reported Per Powder

Powder Single-point Multi-point

SigN^ ref. 14 10

Si3N^ test 12 8

SiC 11 9

Si 11 5

Zr02 10 7

The relative standard deviations for mean values calculated from all data for

both single and multi-point values were in the range of 5-10% (see Table

3.1.3). In absolute terms, the standard deviation of the mean was typically

approximately equal to less than 1 m^/g. The results for Si gave a standard

deviation of 0.2 mVg arid almost an order of magnitude lower value for the

specific surface area. The multi-point results of one lab (No. 22) affected

strongly the mean value and standard deviation for Si. The spread of the

values of the population of all data for a powder was generally of the same

order of magnitude as that for the spread of data obtained by particular

laboratories. In some cases the variation for a powder was significantly

larger than the within laboratory variation. This will be considered later in

the analysis.

The average values for the single and multi-point results, where appropriate

with the standard deviations, are shown in Figures 9-18.

Table 3.1.3 Average Values and Standard Deviations for Single and Multipoint BET Results

Single-point Multi-point

Powder Mean Standard Deviation Mean Standard Deviation

m2/g m2/g % mVg m^/g >

Si3N, ref. 13.11 0.72 5.5 13.51 0.62 4 6

SigN, test 9.43 0.61 6.5 9.81 0.52 6 3

Sic 13.34 1.12 8.4 14.53 0.96 6 6

Si 1.92 0.2 12.0 2.27 0.61 26 9

ZrOz 16.84 1.4 8.3 18.36 0.59 3 2

Single -point vs Multi -point Data

In Table 3.1.3 it can be seen that the average multi -point values based on all

data for each powder are always higher by 2-10% than the corresponding average

single point values. However, for those laboratories which measured the

specific surface areas using both methods (Lab 14 for SNR; see Tables 3.2.1.1.

33
and 3.2.2.2; Labs 14 and 20 for SNT; see Tables 3.2.2.1 and 3.2.2.2) the

single-point values were slightly higher than the multi-point values. In the

case of Lab 14, some samples from the same vials were used for both test, with

single-point values higher than multi-point values.

The multi-point specific surface areas are determined from the BET isotherm.

A typical plot (Lab 1) of the volume of nitrogen gas adsorbed vs relative

pressure is shown in Figure 10a for silicon powder. Figure 10b shows a

corresponding BET plot of l/VA(Po/P-l) against the relative pressure (P/Pq)

for the same data.

There may be several reasons for the divergence between the single point and

multi-point results:

(a) statistical - the limited population of the participating

laboratories may be subject to a fluctuation, giving rise to a

systematic difference;

(b) experimental/instrumental - somewhat differing conditions between

the two types of measurements may have been significant;

(c) algorithm- related - the multipoint values are computed by a

regression analysis; or

(d) virtual - the multi -point values may be closer to the true surface

area

.

The correlation coefficients obtained in the multi -point analyses were

typically 0.995 and higher. Nonetheless, as indicated later in this

discussion, the multi-point values obtained by laboratories which performed a

large number of runs on one sample displayed generally larger mean deviations

compared to corresponding single- point data.

Several laboratories which measured the surface areas in the multi -point mode

also determined the Langmuir surface areas (e.g.. Lab 6). These surface areas

were typically greater than those calculation from the BET equation (e.g.. Lab

1).

For a general assessment as to which method to employ, the experimentalist

must consider which method gives the most reproducible values, and which

technique is easier to utilize from the experimental/instrumental point of

view

.

Internal Consistency of the Powder Samples

The issue of concern of this subsection is how the variation of data may have

been influenced by the riffling procedure as evidenced by variation between

different vials and as compared to variation in independent measurements made

on one vial of powder. To identify the various contributions to the variance

of the measurement requires independent analyses of replicate vials, analysis

of replicate subsamples from each vial and replication of the measurement

process. "Independent analyses" means that all aspects of the analysis of

34
0.5

0.0

0.0 0.2 0.4 0.6 0.8 1.(

Relative Pressure, (p/Pq)

Figure 10a, Plots of BET multipoint data: volume of gas adsorbed vs.

relative pressure.

0.00 0.05 0.10 0.15 0.20 0.25

Relative Pressure, (p/p^)

Figure 10b. Plots of BET multipoint data: BET transformation of

adsorption data in a.

35
separate analytical samples are carried out in the same manner. Multiple

instrumental readings on the same sample do not constitute independent

measurements, albeit they do yield an estimate of the variance assignable to

the instrumental readings. The tabulation of data in Chapter 3.3 does not

make a distinction between multiple instrumental readings and independent

measurements in which replicate subsamples of a sample were prepared and

analyzed. Furthermore, the raw data furnished by a laboratory often did not

clearly indicate whether measurements identified as replicate runs were truly

independent. In a few cases sufficient information was provided to enable

independent runs and multiple readings to be distinguished.

Most laboratories which reported more than one measurement only analyzed one

sample from a sample vial and reported only one instrumental reading. Table

3.1.4 gives the means and standard deviations for laboratories which reported

more than 10 determinations, either multiple readings or replicate subsamples,

per vial and which analyzed 2 or more vials . The powders included in Table

3.1.3 are SisN^, Ref .

, SisN^, Test and SiC. Si powder was not included because

it had a low absolute surface area;

Table, 3.1.4 Mean and Standard Deviation for Analyses with Replicate

Sample or Multiple Instrumental Measurements.

Single (s)/ Standard

Powder Lab No. Multi -point (m) Mean, Deviation

m^/g

SigN^ Ref. 4 s 13.39 0.32

17 s 12.97 0.27

22 ra 13.51 1.03

23 m 13.40 0.28

SigN^ Test 4 s 9.79 0.03

8 s 10.28 0.06

17 s 9.01 0.23

9 m 9.73 0.32

23 m 9.65 0.12

SiC 3 s 12.71 0.19

4 s 13.72 0.05

17 s 13.04 0.07

9 m 14.63 0.13

23 m 14.27 0.18

also, the data showed low variation for the few laboratories which made a

sufficient number of runs . The YSZ powder was not included because of a

degassing dependence in the measurements was apparent in the data.

With the exception of Lab 22, the standard deviation was within 0.3% - 3.3% of

the mean value. Lab 22 carried out measurements using N2 and Kr so that the

relatively large standard deviation (7.6% of the mean) includes the differing

36
effects of the two adsorbates. For the other laboratories the variances

generally contain the contributions from the preparation of the lEA samples

(riffling error; standard deviation, Sr) , from the extraction and preparation

of analytical subsamples (preparation error; standard deviation, Sp) and from

the instrumental measurement (measurement error; standard deviation, S[^) . The

total variance can be expressed as

s^ = Sr2 + Sp2 + s„2 (2.1)

For the laboratories reporting a large number of determinations of specific

surface area, the manner in which those measurements are distributed with

respect to lEA samples, subsamples and measurements is indicated in Table

3.1.5.

It is evident from Table 3.1.5 that the effect of taking subsamples was not

adequately tested. With the exception of Lab 17, the subsampling effect is

confounded with the run effect. The results for the SNR powder provided by

Lab 23 could not be evaluated due to a large uncertainty in measurements for

one of the two subsamples from lEA sample SNR 1471. An analysis of variance

of the results of Lab 17 for SNR, SNT and SiC powders is given in Table 3.1.6.

37
Table 3.1.5 Distribution of Measurements with respect to Samples

,

Subsamples and Runs

.

No. of

No . Method Data

No. of

Samples

No. of

Subsamples

per Sample

No . of Lab

Runs per

Subsample

SNR

4

17

18

23

SNT

17

18

9

23

SiC

17

S

M

15

80

9

24

38

S 9

M 20

M 24

33

16 #582, 2

#1381, 3

All others , 1

#1471, 2

All others , 1

#312, 2

#938, 2

#1419, 2

All others , 1

1?

#116, 2

All others, 1

#154, 3

All others, 1

2-4

4-5

3

3

4-5

3

4

3

4-5

18

38
Table 3.1.6 Estimates of the Standard Deviation and Its Components for

the Results of Lab 17. Units are mVgPowder

SNR

Data Used in

the Analysis (1)

0.3196

Standard Deviation

(2) (3) (4) (5)

SNT

SiC

All data

Subsample av. 0.3260

and s . d

.

#582, #1381

subsample av.

Estimate, using

Col. (2) and (4)

All data 0.2304

Subsample av. 0.2349

and s . d

.

#312, #938, #1419

subsample av.

Estimate, using

Col. (2) and (4)

All data 0.1989

0.0876

0.0701 0.0900

0.300

0.0694

0.0364

0.232

Subsample av. 0.1697 0.1381

Insufficient data for reliable estimate of Sp and s^.

and s . d

.

Standard Deviation Columns above

Col. (1) Total standard deviation, s.

Col. (2) [Sr2 + Sp2]i/2

Col. (3) s^, run standard deviations pooled over all subsamples

Col. (4) Sp.

Col. (5) Sr.

39
The estimates for Sr are 0.30 m^/g for the SNR powder and 0.23 m^/g for the

SNT powder. The SiC value could not be estimated. Although s^ cannot be

estimated for the other laboratories and for the SiC powder, the sum

Ss2 = [sr2 + Sp2] (2.2)

of the variances can be estimated. For other laboratories, values of the

standard deviation, Sg, were in the range 0.17 to 0.35; for the SNR powder,

0.09 to 0.17, for the SNT powder. For the SiC powder, for which only data

from Lab 17 were available, Ss was 0.065. Using the formula

2[ssV2as + SpV2ap]i/2

where is the number of degrees of freedom in estimating combined variance

and ap is the number of degrees of freedom in estimating Sp^, the approximate

confidence range of Sr obtained from the results of Lab 17 can be estimated.

For the SNR powder, the range is approximately 0.15 to 0.45; and for the SNT

powder, 0.11 to 0.35. Thus, the values of Sr as suggested by the results for

Sg for all laboratories are consistent with the estimate obtained from Lab 17

in the case of the SNR powder, but possibly lower than the estimate in the

case of the SNT powder.

The range of estimated relative sample error due to riffling is 1.0 to 3.5%

for the two SigN^ powders. This range can be compared with the estimated

maximum error of 0.42% obtained for sampling of a 60:40 coarse: fine sand

mixture.^ The source of the increased error for the SigN^ cannot be

definitely established; however, the poor flow characteristics of these

powders is suspected. Furthermore, it is to be noted that the surface area

values are roughly uniformly distributed with no significant outliers

apparent

.

The measurement error for the multi -point determinations appears to be about

twice that for the single-point determinations. The riffling error may be

comparable to the measurement error obtained by the multi -point method. Based

on the results of Lab 17, which riffled the lEA sample to obtain subsamples,

the sample preparation error for the SigN^ may be small. These statements are

at best tentative since the replication of samples, subsamples and

measurements was inadequate for the calculation of accurate estimates.

Specific Features of the Data

SNR and SNT

See above discussion of internal consistency of the powders. (Figures 11-14)

SiC

Lab 1 stressed that samples had to be mixed thoroughly to obtain reproducible

results - i.e., the samples were not homogeneous. The SiC data show the

relatively largest mean deviation (both relative and absolute values)

.

Unfortunately, only Laboratories 9 and 23 (multi-point) and Labs 3, 4, 17 and

18 provided sufficient amounts of data for computing reasonable, within

40
laboratory, mean values. These mean values show a relatively narrow spread

(see Figures 15-16).

Si

A relatively narrow spread of data was obtained in spite of the low BET

surface area of this powder (see Figures 17-18). Values within the deviation

range were obtained even when small amounts of powder were used; e.g., Lab 23

used 0.17 to 0.40 g of powder. Regarding the large spread for the multi -point

data reported by Lab 22, the data contain measurements by N2 and by Kr

adsorbate gases. Surprisingly, the BET areas obtained with N2 were about

twice thos3 obtained with Kr

.

YSZ

SEM and TGA indicated that the powder was spray dried and, thus, contained

traces of a binder which was removable only at high degassing temperatures or

long times. In addition, this material is known to be fairly hygroscopic.

Lab 18 demonstrated a considerable effect of degassing temperature on the BET

area (multi-point)

:

Effect of Degassing Temperature on Specific Surface Area

1st Run 2nd Run

Room 16.2 17.1 mVg

Temp

.

55°C 17.4 18.3

288°C 18.9 19.8

Lab 4 showed that the BET area (single-point) increased as the degas time at

350°C increased from 0.5 to 4 hours. The data shown in Figure 19 seem to fall

into two groups consistent with the extent of degassing. Those data provided

by Labs 4, 16 and 18 were obtained at high degas temperatures and at times

typically not less than 2 hours. The multi -point data are shown in Figure 20.

Conclusions

The relative standard deviation for the average value for each powder,

calculated using all data, was in the range of 5-10%, except for Si which had

a low surface area.

The multi-point average values were higher by 3-10% than the corresponding

single- point values. From the available data, it was not possible to deduce

whether this difference is real. Two of the laboratories which performed

measurements by both methods obtained higher single -point data.

41
For the SNR, SNT and SiC powders an average value obtained within an

uncertainty band of ±1 m^/g around the average values shown in Table 3.1.3 can

be expected to be acceptable. For the Si powder the band may be set at +0.5

mVg.

No significant difference in average values or spread of data was found when

comparing laboratories which used different types of instruments. The

relatively small spread of absolute values for the Si powder with low specific

surface area indicated a good instrument- to- instrument measurement capability.

The vial-to-vial spread of average values was significantly higher, in

particular for SisN^ Ref. and SiC, than for runs on several samples from one

vial. The variation within one vial was on the same order of magnitude as

that for several runs in which each run used a single sample from a single

vial. Estimates of the riffling error are in the approximate range of 1.0 to

3.5% for the two SisN^ powders. However, part of the apparent riffling error

may be due to vial -to -vial variation in apparent surface area due to formation

of closed pore agglomerates. The presence of closed pore agglomerates may

also account for the observed vial -to -vial density variation for these

powders

.

For measurements performed several times on a single sample, the standard

deviation for the multi -point measurements was frequently larger than for

corresponding single-point measurements.

The measurement of specific surface area for the Zr02 powder was suggested to

be considerably dependent on the degassing conditions.

Suggested future activities:

• Zr02 - interlaboratory measurements using a fixed degassing temperature and

time

;

• A statistically balanced set of interlaboratory measurements should be

performed on one powder, such as the SisN^^ powder, with each laboratory

using multiple subsamples of each vial and multiple independent

instrumental measurements on each subsample;

• Measurement of density, BET area, particle size distribution (plus SEM

examination) should be carried out on one sample taken from each vial

exhibiting large data variation.

42
3.2. STATISTICAL DATA

3.2.1. Silicon Nitride Reference (SNR) Powder

Table 3.2.1.1 Single-Point Determination

Material: Silicon Nitride, Reference Powder

Property: SINGLEPT

Method: 1

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

2 1 13 20 13 20 13 .20 0 00

3 3 11 60 11 80 11 .67 0 11

4 15 13 10 13 90 13 .39 0 32

5 1 12 40 12 40 12 .40 0 00

8 4 14 00 14 04 14 .02 0 02

11 1 13 70 13 70 13 .70 0 00

14 5 13 60 14 80 14 .18 0 44

15 2 12 90 13 10 13 .00 0 14

16 7 13 60 14 00 13 .76 0 14

17 80 12 44 13 71 12 .97 0 27

18 9 12 45 13 04 12 .87 0 19

24 5 12 00 12 60 12 .22 0 23

25 3 13 10 13 20 13 .13 0 06

leans 13 11 66 14 18 13 .12 0 72

43
Table 3.2.1.2 Multi-point Determination

Material: Silicon Nitride, Reference Powder

Property: MULTIPT

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 14,,20 14,,51 14,,35 0,,21

5 1 13,.20 13,,20 13,,20 0,,00

6 1 12..93 12,,93 12,,93 0,,00

7 2 13.,47 13,,56 13,,51 0,,06

9 5 13.,72 15,,35 14,,72 0,,65

13 10 11.,29 14,,61 12,,95 0,,82

14 4 12.,30 13,,10 12,,72 0,,38

20 7 12.,92 13,,48 13,,21 0,,21

21 2 13.,59 13,,61 13,,60 0,,01

22 14 12.,07 15,,53 13,,51 1,,03

23 21 12.,75 13,,89 13,,40 0,,28

Means 11 12.72 14.72 13.46 0.60

44
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a) eH

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4J

E

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O C

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CO CO

0) cd O

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0)

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46
3.2.2 Silicon Nitride Test (SNT) Powder

Table 3.2.2.1 Single-Point Determination

Material: Silicon Nitride, Test Powder

Property: SINGLEPT

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 2 9,,10 9,,10 9,.10 0..00

3 2 8,,44 8,,49 8,,46 0,,03

4 12 9,,72 9,,83 9,.79 0,,03

5 4 9,,10 9.,20 9,,15 0,,05

8 10 10..21 10,,43 10,,28 0.,06

14 3 9..00 11,,00 10,,33 1,,15

15 1 8,.70 8,,70 8,,70 0,,00

16 6 8.,88 9,,29 9,,10 0,,18

17 38 8,.62 9,,48 9,,01 0,,23

18 9 9,.21 9,,83 9.,49 0,,17

20 2 10..00 10,.15 10,,07 0,,10

25 2 9.,53 9,.55 9.,54 0,,01

Means 12 8..46 10,, 33 9,,42 0.,60

Table 3.2.2.2 Multi -point Determination

Material: Silicon Nitride, Test Powder

Property: MULTIPT

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

6 1 9,.31 9,.31 9.,31 0,.00

7 6 9,.83 10,.63 10,, 33 0,. 36

9 20 8,,97 10,.09 9,,73 0,.32

14 4 8,,80 9 ,. 50 9,,25 0,. 33

20 1 10,,00 10,.00 10.,00 0..00

21 3 9,,77 10,.03 9.,88 0..13

22 8 9,,81 10..21 9.,99 0..12

23 18 9.,46 9..90 9.,65 0.,12

Means 8 9,,25 10..33 9.,77 0.,36

47
E

3

O

o

0) ^ 4-) 4J o a

0) H

ui c

l-l -H

0) O

?

o <u H C

M 0]

(4-1 bO o C

ca u

(uu

(d u

o ^

14^ bO

u a

u

•H >t-l O 4-> 9) U

Cd M p.

en

(0u

bO

5y^iu 'oajy ^oopng

48
0) U

o

o

0)

0) H

CO U

u -u

•O '1-1 > O

O 04

&, -H

4J H -H ^w 2

S

iH bO

O C

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Vj C

3 -H U 4J

Cd o ex

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cu cd

5 'DdJV ^oopns

A9
3.2.3. Silicon Carbide (SiC) Powder

Table 3.2.3.1 Single-Point Determination

Material: Silicon Carbide

Property: SINGLEPT

Method: 1

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 4 12,. 36 12,.53 12,.44 0,.08

2 1 12 .80 12,.80 12,.80 0,.00

3 12 12,.30 12,.90 12,.71 0,.19

4 12 13,.63 13,.79 13,.72 0,.05

8 6 15,.41 16,.79 16,.05 0,.66

15 1 11..92 11..92 11,,92 0,.00

16 3 12,.60 12,.90 12,.70 0,.17

17 33 12,.94 13,.20 13..04 0,.07

18 9 12,,36 14,.05 13.,37 0,.52

20 1 14,,31 14,,31 14.,31 0..00

25 1 13,,70 13,,70 13.,70 0,.00

Means 11 11.92 16.05 13.34 1.12

Table 3.2.3.2 Multi-point Determination

Material: Silicon Carbide

Property: MULTIPT

Method: 2

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 4 13,.58 13,.85 13,.71 0,.11

6 1 11,.67 11,.67 11,.67 0,.00

7 3 15,.92 16,.38 16,.20 0,.24

9 9 14,.42 14,.83 14,.63 0,.13

10 3 15,,02 15,.43 15,.19 0,.21

13 5 13,.26 13,.84 13,,58 0,,22

21 3 14,,68 14,,94 14.,77 0.,14

22 4 14.,93 15,,67 15.,27 0. 36

23 12 13. 80 14.,51 14.,27 0. 18

Means 9 11.67 16.20 14.36 1.29

50
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52
3.2.4. Silicon (Si) Powder

Table 3.2.4.1 Single-Point Determination

Material: Silicon

Property: SINGLEPT

Method: 1

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 4 1,.63 1,.88 1,.78 0,.10

2 1 1,.80 1,,80 1,.80 0 .00

3 12 1,.80 2,.00 1,.88 0,.07

4 12 1,,79 2,.03 1,.94 0,.10

5 4 1..70 1,.90 1,.80 0,.11

8 6 2..30 2,.36 2,. 32 0,.02

15 1 1..50 1,.50 1..50 0..00

16 5 1,,96 1,.99 1..96 0..01

17 34 1..96 2,.05 2..00 0..02

18 9 1.,84 1.,99 1,.91 0,.05

20 1 2,,25 2,,25 2,.25 0,.00

Means 11 1.,50 2,,32 1.,92 0,.22

Table 3.2.4.2 Multi-point Determination

Material: Silicon

Property: MULTIPT

Method: 2

# of

LAB // Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 4 1,.78 2,.02 1,.93 0..10

6 1 1,.71 1,.71 1,.71 0..00

9 9 2,.16 2,.61 2.,27 0,,17

22 8 1,.95 5,.32 3.,32 1,,48

23 12 1..78 2,.06 1.,97 0,,07

Means 1.71 3.32 2.24 0.63

53
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55
3.2.5. Yttria-Zirconia (YSZ) Powder

Table 3.2.5.1 Single-Point Determination

Material: Zirconia

Property: SINGLEPT

Method: 1

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 2 16 .93 17,,04 16,,98 0,,07

2 2 15 .40 15,,70 15,,55 0,,21

4 24 18 ,70 19,,50 19,,05 0,,24

6 1 17,,12 17,,12 17,,12 0,,00

11 2 14,,10 16,,30 15,,20 1,,55

14 3 16,,10 17,,00 16,,53 0,.45

15 1 15,,80 15,,80 15,,80 0,.00

16 12 17,,20 19,,00 18..08 0,.68

17 18 16,,05 17,,05 16,,40 0..33

18 17 17,,60 19,,80 18,.95 0,.63

20 3 16,, 90 17,,16 17,.05 0,.13

24 3 15,,30 16,,50 15,.80 0.,62

Means 12 15,,20 19,,05 16,.87 1..27

Table 3.2.5.2 Multi-Point Determination

Material: Zirconia

Property: MULTIPT

Method: 2

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 2 17,,53 17 .67 17 ,60 0,,09

6 1 17,,62 17..62 17,.62 0.,00

8 3 18,,61 19,,09 18,,78 0,,26

9 3 18,,91 18,,99 18,,96 0,,04

14 2 18,,20 18,,40 18,, 30 0,.14

19 9 18,,03 18,,45 18,,23 0,.15

22 11 18,. 30 19,,90 19,,01 0,.60

Means 7 17.60 19.01 18.35 0.59

56
3.3. STATISTICAL ANALYSIS . R. Munro , NIST

The Brunauer-Emmett- Teller (BET) gas adsorption measurement technique was used

by the participants to measure the specific surface areas of the powders.

There were two primary implementations of the method, denoted single point BET

and multi -point BET. In the single point BET procedure, the measurement was

conducted at the saturation vapor pressure of the liquified adsorbent gas. In

the multi -point BET procedure, measurements were conducted at three or more

adsorption pressures.

In both procedures, specimen preparation can affect the BET measurement

significantly. Agglomeration of the particles and residual adsorbed gases,

for example, necessarily influence the amount of adsorption that can occur

during the test. Thus, sampling procedures, degassing conditions, and the

choice of adsorbate gas can all be expected to contribute to variations in the

results. This expectation appeared to be confirmed by the measures of

precision for both methods. Figures 21-25, which had wide variations among the

individual laboratories.

57
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tM CM

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Si3N4 (Ref.)

f—Multi—point—

{

BET

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BET

S.P.

li.P.

Within Lab { I 1 -S

. o

Figure 21. Within lab, between lab, and between methods standard

deviations in the measurement of specific surface area for

the SigN^CRef.) powder as measured by various laboratories

using a variety of methods.

60
00

a

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cd

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u

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Single Point

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M

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lf.P.

Within Lab } \—\ a

Betw. £

Labs © ©

Figure 22. Within lab, between lab, and between methods standard

deviations in the measurement of specific surface area for

the SigN^CTest) powder as measured by various laboratories

using a variety of methods.

61
00

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°

a

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S «

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1 illl

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n

Betw. ^2

Labs % 0) m9

Figure 23. Within lab, between lab, and between methods standard

deviations in the measurement of specific surface area for

the SiC powder as measured by various laboratories using a

variety of methods

62
•M CM

°

a

o

d

d

-•>> en

2.0

1.5--

o 1.0

d

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Figure 24. Within lab, between lab, and between methods standard

deviations in the measurement of specific surface area for

the Si powder as measured by various laboratories using a

variety of methods

.

63
00

HH CVl

<^ 0

d

^

o cd

2 -

•0 CO

CO

2.0

1.5

1.0"

0.5

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BET

1 1 i

M.P.

Within Lab If 1

Betw.

Labs

. o

Figure 25. Within lab, between lab, and between methods standard

deviations in the measurement of specific surface area for

the ZrOg powder as measured by various laboratories using a variety of methods

.

64
4. PARTICLE SIZE AND PARTICLE SIZE DISTRIBUTION (PS & PSD)

H. Hausner, Technische Univsersitat Berlin; S. Malghan, NIST

4.1. MEASUREMENT METHODS

4.1.1. Methods Available

in the case of zirconium oxide, silicon carbide and silicon nitride, the particle

size and size distribution has a significant influence on the densification of

these powders during sintering. The particle size of silicon is important for

its nitridation behavior during silicon nitride powder synthesis from the metal.

Properties of the Si3N^ powder will directly affect the properties of the final

ceramic product in the case of reaction bonded silicon nitride.

in particle size analysis, the method used will depend on the particle size of

the powder under investigation. The methods shown in Table 4.1.1.1 can be used

for different ranges of particle sizes.

Table 4.1.1.1 Particle Size Range and Analysis Method

Range (/xm) Method

(1) 10000 - 5 Sieving (including micromeshsieves

)

(2) 60 - 0 2 Gravitational Sedimentation

(3) 5 - 0 02 Centrifugal Sedimentation

(4) 600 - 0 1 Light Scattering

(5) 3 - 0 003 Photon Correlation Spectroscopy

(6) 800 - 0 5 Electrical Sensing Zone

(7) 5 - 0 02 Scanning Electron Microscopy

(8) 5 - 0 001 Transmission Electron Microscopy

Methods (2) through (4) were used to the greatest extent by the laboratories

which participated in this investigation. Method (1) was not used at all and

will not be considered further here. Very limited data were reported for methods

(5) and (6). In the sections which follow, methods (2) through (4) will be

discussed. Method (5) was used only by two laboratories (9 and 23) for

measurements on the YSZ powder. Method (6) was used only by Lab 16 for Si

powder. Methods (7) and (8) are discussed under Particle Morphology in Chapter

5.0.

Methods for measuring sizes and size distribution of fine powders have been

reviewed and evaluated in recent years^'^. In addition, many articles have

appeared in the particle characterization literature comparing two techniques,

such as light- scattering with the longer established gravitational sedimentation

and electrical sensing zone methods.

65
4.1.2. Gravitational Sedimentation (Sedlgraph)

Use and Significance

The Sedigraph particle size analyzer measures the sedimentation rates of

particles dispersed in a liquid, calculates the equivalent spherical diameter

(ESD) on the basis of Stoke 's law of sedimentation, and plots the data as

cumulative mass percent versus ESD. Sedigraphs using light or x-ray detection

are in use. The instrument using xray is described here. The time required to

analyze a particle size distribution is significantly decreased by continuously

changing the sedimentation cell position so as to decrease the effective

sedimentation depth. Nevertheless, the duration of an analysis for a single

specimen may be from 1 to 2 hours. Although the analytical range of the

instrument is 100 to 0.1 fxm, the actual operating range is controlled by the

rheological characteristics of the powder in liquid to be analyzed. The accuracy

of the instrument decreases for particle sizes below 1 fixa due to the increase of

diffusion effects in the liquid.

For an x-ray type Sedigraph, the intensity, I, of the transmitted x-ray beam is

proportional to the mass, C, of powder in the beam according to the absorption

law

where B is a mass absorption constant. The x-ray density is defined as

The PSD is calculated on the basis of Stoke 's law at intervals of the cell

position using the measured settling depth, powder and liquid densities, and

liquid viscosity.

Instrument and Experimental Parameters

Size distribution analysis by Sedigraph consists of two steps: (1) sample

preparation and (2) size analysis. The parameters influencing sample preparation

for particle size analysis are:

• dispersion method

• dispersion liquid

• dispersion agent

• deagglomeration

• deagglomeration time

• time elapsed before analysis

• solid- liquid ratio

• pH of suspension

• temperature of suspension

• volume of sample

Principle

I - Iq exp(-BC) (2.1)

D - logio(I/Io) (2.2)

66
Special liquids containing surfactants (e.g., SedisperseTM) are available from

instrument manufacturers; however, many common liquids for which the density and

viscosity are known over a temperature range around room temperature may be used.

A variety of surfactants (dispersion agents) are available. Their use in

practice is governed largely by empiricism and art. Deagglomeration is carried

out by use of some form of shear and impact energy - e.g., ultrasonic bath or

probe, blender, or stirrer. It is essential that the means used to deagglomerate

the powder produce disruption of all mechanically bound agglomerates and produce

a uniform suspension of all the particles. The dispersed suspension is placed

in the instrument compartment and pumped into the sample cell.

As can be seen from the compilation of experimental conditions given in Table

4.1.2.1, the experimental conditions for sample preparation differed

significantly from laboratory to laboratory.

Sample density, liquid density and liquid viscosity are used to calculate a run

parameter to which the instrument is set, or they are entered into a run file if

the instrument is computer controlled.

The x-ray Sedigraph uses a finely collimated beam of low- energy xrays to obtain

a direct measure of mass concentration at a series of accurately determined

levels in a sample cell. A scintillation detector monitors the beam which is

transmitted through the cell. With the use of the internal electronics a

continuous display of the particle size as ESD versus cumulative mass percent is

produced by an x-y plotter. Output of the instrument -response permits further

treatment of the data to be carried out, such as a plot of ESD versus mass

frequency.

Calibration and Standards

The instrument is calibrated using either manufacturer provided standard powders

or those obtained from organizations as the National Institute of Standards and

Technology and the Community Bureau of References (BCR) . At present, no

certified standard ceramic powders, especially in the range

0.1-1.0 iJ,m, axe available for calibration purposes.

The following ASTM procedure may serve as a guide in the use of the Sedigraph for

ceramic powders

67
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69
ASTM C958-81. Standard method for particle size distribution of alumina or

quartz by x-ray monitoring of gravity sedimentation.

Nomenclature and theoretical methods for representing and analyzing particle

size distributions are recommended in

DIN 66141. Darstellung von Korn- (Teilchen)groBenverteilgungen; Grundlagen

[Representation of particle size distribution; basic standards]

These recommended representations are relevant to all of the methods

considered here.

4.1.3 Centrifugal Sedimentation

Use and Significance

Since diffusional-remixing significantly interferes with gravitational

sedimentation at particle sizes less than 1 /xm, the use of centrifugal forces

is preferred for particle sizes in the range of 0.1 to 2 fim. Sedimentation in

a centrifugal field is subject to the same limitations of concentration of the

solid phase, particle shape, and electroviscosity effects as in gravity

sedimentation. In addition, analysis of centrifugal data is complicated by

the variation of the centrifugal force on a particle as a function of

distance

.

As the range of particle size to be determined decreases from 0.1 to 0.01 /Ltm, a large centrifugal force becomes essential to achieve adequate sedimentation

rates. In such cases, a centrifuge which can produce accelerations between

200,000 g and 400,000 g (g = 9.80 m/s^) , in the vicinity of 60,000 rpm, may be

required. At these speeds and particle sizes, the effect of Brownian motion

(i.e., diffusion) may still have an influence on sedimentation rates.

Principle

Two instrumental methods have been commercialized in recent years: (1) the

line-start method and (2) the homogeneous suspension method. Brief

descriptions of these two methods follow. Only instruments of the homogeneous

suspension type were used in this study.

In the typical line -start instrument, a thin layer of host liquid is spread

over a rapidly spinning disk; then a small amount of suspension is injected as

a thin inner annular ring. Suspended particles are detected at an outer point

in the host liquid by a photodiode with the heavier particles travelling past

the detection point before the lighter particles. Mathematical extraction of

the particle size distribution data from the intensity time data is not

greatly encumbered by approximations to integral solutions. However,

significant experimental errors may be encountered for large particle sizes (>

2 /im) since these particles may be swept out of the suspension rapidly for an

accurate resolution of the size distribution. Experimentally, errors may

arise from hydrodynamic streaming of the suspension through the host liquid.

70
In the typical homogeneous suspension instrument, a cell containing a

homogeneous suspension of the sample is placed with the axis of the cell along

a radial direction of a high-speed centrifuge. The centrifuge is accelerated

quickly or in a programmed manner to a stable rotational velocity and the

particle density at one location in the cell is measured as a function of time

with a photodiode. Since this method measures the light absorption by the

total time -dependent population of particles in a small detection volume,

mathematical analysis of the time intensity data must treat the total timedependent particle size distribution. This requires the use of approximations

of an integral equation. The algorithms used by instrument manufacturers are

usually proprietary so that these instruments typically perform as a "black

box." In application, homogeneous suspension instruments are usually somewhat

easier and convenient to use than are the line-start instruments. In

addition, the homogeneous suspension instruments usually provide for

determination of sedimentation of large sizes (> 1 fj.ni) by a gravitational

settling determination.

Instrument and Experimental Parameters

A single method cannot be described which is applicable to all instruments;

however, a general method is described here which may be more-or-less typical

for homogeneous suspension instruments. The powder which is dispersed in an

appropriate liquid medium containing a dispersant is transferred into a sedimentation cell. A reference cell filled with a clear sample of the

dispersant liquid (blank) is used to balance the centrifuge mechanically and

to provide an optical reference. The centrifuge is typically spun at speeds

up to 10,000 rpm, producing centrifugal force up to 9000 g. This may permit

particle sizes down to 0.01 ^m to be determined; the lower limit depends upon

particle density. The particle size is calculated from the change in optical

absorbance of the suspension as a function of time. Instruments may have a built-in correction for absorbance coefficient which minimizes any measurement

error caused by differences in light attenuation efficiencies of particles

with different diameters. A large number of different data presentation

systems and formats are available with these instruments.

Sample preparation considerations are similar to those outlined in Section

4.1.2., above. The experimental conditions used in this study are summarized

in Table 4.1.3.1.

Calibration and Standards

No specific standards based on ceramic powders are available for centrifugal

instruments. A standard procedure was developed by ASTM for centrifugal

sedimentation, but the procedure was based on instrumentation which is no

longer commercially available. However, this procedure may be consulted for

guidance

ASTM C678-75 (Reapproved 1985). "Standard Method for

Particle Size Distribution of Alumina or Quartz Using

Centrifugal Sedimentation."

71
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72
4.1.4. Light Scattering

Use and Significance

Of the new methods of particle size distribution analysis, light scattering

has grown the most rapidly. The application of light scattering has been

increased and refined by improvements in laser technology; computers,

especially microcomputers; and computer-based algorithms for data analysis.

In light scattering instruments, laser illumination is used. The scattered

light data are processed by a combination of mechanical, optical and

electronic means. For larger particle sizes (D > A; where D is the particle

size and A is the wavelength of light) Fraunhofer diffraction theory is used;

for smaller sizes (typically D < 2 and A = 0.6 /zm) Lorenz-Mie theory forms the

basis for data analysis.

Principle

The form of the scattering pattern for light scattered out of a well

collimated beam of light by particles depends upon the dimensions of the

particles and the wavelength of light. The relative intensity and spatial

distribution of the scattered light is well described by diffraction and

scattering theories. Accurate measurement of intensity and spatial

distributions enable particle size distributions to be determined. Detailed

discussions of Fraunhofer and Lorenz-Mie theories and methods based on them

can be found elsewhere^.

Instrument and Experimental Parameters

In a typical optical sizer a laser beam from, e.g., a He-Ne laser source, is

focused into the sizer' s detection zone or is expanded and passed through a glass sample cell in a parallel fashion. A suspension of particles which is

stirred and ultrasonicated in a separate chamber is circulated continuously by

a peristaltic pump from the chamber and through the sample cell.

The unscattered portion of the incident beam is cut off by a mask since its

intensity is so strong that it would swamp the photodetector . The scattered

light is passed through a rotating disc which contains apertures arranged in a

spiral configuration. A multi-element array detector is used in the optical

focal plane to record the light distribution. The digital output of the

photodetectors is processed by a computer.

See Section 4.1.2 above for an outline of sample preparation factors.

Experimental conditions used in this study are summarized in Table 4.1.4.1.

Calibration and Standards

Light scattering instruments commonly provide data in the form of number density

versus particle size, which can be transformed to provide data in terms of mass

density versus particle size. Calibration with standards such as latex spheres

is routinely practiced.

73
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74
The following ASTM procedure may be consulted for guidance in the practice of

laser light scattering:

ASTM C1070-86. "Determining Particle Size Distribution of Alumina or

Quartz by Laser Light Scattering."

4.4.1.5. Results and Discussion

A comparison of the results using statistical analysis is not appropriate

since in most cases not enough data are available. Therefore, the discussion

will focus on specific examples which were selected to demonstrate the

influence of different procedures which were applied for sample preparation.

In order to give an overview of the overall scatter of the data, the maximum

and minimum D50 , D90 and D^q values obtained with different instruments are

shown in Table 4.1.5.1 for the SNR powder independent of the dispersion

method. Nearly every laboratory used a different procedure for sample

preparation, see Section 4.1.2., and little information was made available,

for example, on the ultrasonic power for deagglomeration or on the

experimental set-up which was used to transfer the ultrasound to the powder

suspension.

75
Table 4.1.5.1 Particle Size Distribution for the SNR Powder for Different

Instrumental Methods

Method Den '-'50 ^90 Dm

Gravitational Min. 0.,6 1.4 0.2

Sedimentation

1MaletVA. • 1X , A 7 3 0 7

o r~\ 1~ V 1 "r 1 1 O" a T M 1 T» liJ- L L . 1 n 11 d . IL . Ct . Sedimentation

Max. 1.,7 n. a. n. a

.

Light Min. 0,,7 2.1 0.3

Scattering (1)

Max. 1,,5 10.2 0.4

(2) Min. 0,,4 2.0 0.3

Max

.

0.,9 9.6 0.3

(1) Microtrac Instrument

(2) Cilas Instrument

In Table 4.1.5.2, the ratio Dmax/Dmin is indicated based on the data from

Table 4.1.5.1. It can be seen that the ratio is the largest for the Dgg

values indicating that the influence of the dispersion method had the greatest

influence on the large particles or agglomerates

.

In the following discussion specific examples will be given to demonstrate the

influence of various factors which are mainly responsible for the scatter in

the results.

76
Table 4.1.5.2 Dmax/Dmin Ratio for SNR Powder and Different

Instrumental Methods

Method Dsomax/Djomin Dgomax/Dgoinin Dioi^^^/Dio^ii^

Gravitational 2.3 5.2 3.5

Sedimentation

Centrifugal 1.7 n.a. n.a.

Sedimentation

Light

Scattering (1) 2.1 4.9 1.3

(2) 2.3 4.8 1.0

(1) Microtrac Instrument

(2) Cilas Instrument

In Table 4.1.5.3, the influence of the ultrasonic treatment on the D-values is

demonstrated. As can be expected, lower values were obtained with a prolonged

ultrasonic treatment.

Table 4.1.5.3 Influence of Ultrasonic Treatment of D-values in Microns

Lab # lEA No. Matl. Method Procedure* D50 D90 Dio

5 1584 SNR (A) A-11, 30 min. US 0.8 3.2 0.3

5 1584 SNR (A) A-11, 90 min. US 0.7 2.5 0.2

17 42 Si (A) A-11, 20 min, US 7.5 13.7 1.9

17 42 Si (A) A-11, 40 min, US 7.4 13.6 1.9

17 42 Si (A) A-11, 60 min, US 7.0 13.0 1.8

17 232 YSZ (B) H2O, 3 min. US 2.2 8 0.4

17 232 YSZ (B) H2O, 6 min. US 1.3 9 0.3

17 232 YSZ (B) H2O, 12 min. US 1.4 9 0.3

Methods

:

(A) Gravitational sedimentation

(B) Fraunhofer-Mie light scattering

US - Ultrasonication

^A-11 is an mineral spirit based dispersion liquid in the series of

SedisperseTM manufactured by Micromeritics , Inc.

77
In the case of zirconium oxide powder, constant values of d^Q, dgQ and d^o were

obtained after a 6 minute ultrasonic treatment of the sample.

In Table 4.1.5.4, the influence of the dispersion medium on the D-values is

shown. It appears that in this case the influence is even stronger than in

the case of the dispersion time.

Table 4.1.5.4 Influence of Dispersion Medium on D-values in Microns

Lab lEA No. Powder Method Procedure D50 D90 D10

1 449 SNR (A) A-11, 1 min, US 0.8 2.8 0.2

2 667 SNR (A) Deion. water,

0.4 g/100 mL A-11

pH 10; 0.2g/150mL;

3 min, US

1.2 5.7 0.4

17 1012 Sic 0.5% butylamine

in H2O; 3.5g/50mL;

10 min, US

0.6 1.0 0.2

22 7 Sic A-11, 5 min, US 4.3 6.1 3.4

US - Ultrasonication

Conclusions

The data show a large scatter which is largely caused by the different methods

which have been used for the preparation (dispersion) of the samples. In

future interlaboratory studies, preparation methods should be standardized,

and data should be obtained in such a way that a statistical treatment of

various factors will be possible.

4.1.6 Permeametry - Fisher Sub-Sieve Size ( R . Pompe

)

Use and Significance

Permeametric determination of particle size is based on the measurement of

pressure drop of a gas penetrating a bed of packed powder. It requires a

uniformly packed, aggregate- and agglomerate-free bed to achieve homogeneous

flow of gas. The calculated average particle diameter is dependent on the bed

78
porosity. The Fisher sub-sieve sizer is a convenient type of apparatus as it

incorporates a device for compressing the bed to variable porosity levels.

Fisher sub-sieve size (FSSS) measurement may provide an experimentally easily

attained value of average particle diameter under the condition of a uniformly

packed, homogeneous powder bed.

Instrument and Experimental Parameters

Permeametry measurements to determine FSSS were reported by two laboratories,

No. 18 and No. 25. Lab 18 used Fisher Sub-sieve Sizer, Model 95, which was

calibrated with AI2O3 (Alcoa A-12). Their results are summarized in Table

4.1.6.1 below.

The Fisher sub-sieve analyzer was calibrated with the synthetic ruby standard

according to the Fisher procedure given in the instruction manual. In order

to evaluate the test procedure as reported, an AI2O3 (Alcoa A-12) sample was

examined, and steps were taken to determine the optimum porosity point.

Measurements were performed at a porosity of 0.66, and the mean particle size

was determined to be 3.1 /zm, see Table 4.1.6.2. This value compared favorably

with that of 3.5 /xm determined by using the Sedigraph.

Table 4.1.6.1 Summary of Fisher Sub -Sieve Size Results

No. of Max . /Min

.

Lab # Material Values Microns Ave

.

18 YSZ 4 8.0/0.70

25 SNR 1 0.6

25 SNT 2 1.11/0.95 1.03

25 SiC 1 0.46

Results and Discussion

The results obtained by Lab 18 and 25 are summarized in Table 4.1.6.1. The

evaluation of particle size of the YSZ powder by Lab 18 is given in Table

4.1.6.2.

For the analysis of particle size in YSZ, a maximum porosity of 0.68 was

obtained due to poor packing of fine powder. This density was not sufficient

to yield a reasonable particle size value (expected to be 0.7 /im) . It was

concluded that this test was not appropriate for this powder.

Conclusions

The use of permeametry for submicrometer sized powders, such as the YSZ

powder, was considered not to be appropriate.

79
Table 4.1.6.2 Permeametry Data for YSZ Powder

A- 12 AI2O3 Reference YSZ ZrOz

Mean Part. Mean

Porosity Size (/xm) Porosity Size (/zm)

0,.80 2,.29 0,,80 8.0

0,.75 2,.82 0,,75 4.5

0,.70 3,.42 0,,70 1.15

0,.65 3,,95 0,,68 0.70

0,.60 3,,01

0..55 2.,93

0..68 3,,23

0,.66 3.,48

0,.64 3.,38

0,.62 3,,09

0,.66 3,,12

4.2. STATISTICAL DATA

4.2.1. Mathematical Functions

Results are given for the experimental mean, usually the D50 ; 90% finer size,

D90; 10% finer size, D^q; and spread ratio, calculated as (Dgg - Dio)/D5oUnder the assumption of a lognormal distribution, the geometric standard

deviation (og) is given by

ag = yCDg./Die) , (4.2.1)

where Dg^ is the size at which 84% of the particles are finer and D^g is the

size at which 16% of the particles are finer. The geometric standard

deviation can be estimated from the spread ratio. Using the assumption of

lognormality , relationship between ag and the spread ratio is as follows:

og = exp{0. 77185. sinh-HiDgo - Dio]/2D5o)) (4.2.2)

80
4.2.2.

4.2.2.1.

Gravitational Sedimentation (Sedigraph)

Silicon Nitride Reference (SNR) Powder

Table 4.2.2.1.1 Experimental Mean, D50, /^m

Material: Silicon Nitride, Reference Powder (Figure 26)

Property: EXPTLMEAN

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 11 0 .87 1 12 0 98 0 08

3 4 1 .25 1 40 1 32 0 06

4 14 0 .42 0 86 0 68 0 13

6 2 0 .80 0 95 0 87 0 10

9 8 1 .10 1 20 1 14 0 03

15 1 1 .00 1 00 1 00 0 00

16 2 0 .77 0 78 0 77 0 00

17 6 0 .68 0 90 0 76 0 08

18 1 0 .80 0 80 0 80 0 00

23 39 0 .61 1 07 0 78 0 10

Means 10 0 .68 1 32 0 91 0 20

Table 4.2.2.1.2 Size at 90% Finer, D90 , m

Material: Silicon Nitride, Reference Powder

Property: Dgo

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 11 4 .10 7 70 5 87 1 23

3 4 3 .20 7 30 4 62 1 82

4 14 1 .70 4 10 2 47 0 65

6 2 2 .80 5 00 3 90 1 55

9 8 4 .85 6 20 5 53 0 51

15 1 5 .00 5 00 5 00 0 00

17 5 3 .05 3 50 3 28 0 19

18 1 4 .90 4 90 4 90 0 00

23 39 1 .70 6 40 3 51 0 76

Means 9 2 .47 5 87 4 34 1 12

81
Table 4.2.2.1.3 Size at 10% Finer, D^o

,

Material: Silicon Nitride, Reference Powder

Property: D^q

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 11 0,.24 0.34 0,,27 0,,03

3 4 0,,61 0.67 0.,63 0,,02

4 9 0,.24 0.37 0,,32 0,,05

6 2 0,.17 0.35 0,,26 0,,12

9 8 0..34 0. 37 0,, 34 0.,01

15 1 0,.30 0. 30 0., 30 0.,00

17 5 0,,20 0.33 0,,25 0.,05

18 1 0,.23 0.23 0.,23 0,,00

23 24 0,,18 0.36 0.,25 0,,04

Means 9 0.,23 0.63 0,,32 0,,12

Table 4.2.2.1.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon Nitride, Reference Powder

Property: (Dgo - Dio)/D5o

Method: 9

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 11 4.,38 7,,77 5.,66 0,.94

3 4 2,.07 4,,95 2.,99 1..32

4 9 2.,25 4,, 35 3,,10 0..63

6 2 3,.29 4.,89 4.,09 1,.13

9 8 4,.07 4,,86 4,,51 0,.32

15 1 4,.70 4.,70 4.,70 0,:oo

17 5 3,.56 4,, 32 3,,91 0,.33

18 1 5..84 5,,84 5,,84 0,.00

23 24 2,.37 6,,57 3,,80 0..91

:ans 9 2,.99 5.,84 4,,29 1,,00

82
(uDd^ |D)uaujuddx3)

tun 'dzis dpiViDd

0)

jQO

X>U

(U

O

CO

(4-1 o

0)N

•H

(0 • C

a> o

•U 4J ^ C

CO a> a. E

T-l c -o

0) (0 e

COC

e

COo

i-> CO 4J

1-1

CU CO U bO

\0

CM

0)U

bO

83
4.2.2. Gravitational Sedimentation (Sedigraph)

4.2.2.2 Silicon Nitride Test (SNT) Powder

Table 4.2.2.2.1 Experimental Mean, D50 , /xm

Material: Silicon Nitride, Test Powder (Figure 27)

Property: EXPTLMEAN

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0,.55 0.,58 0..56 0,.02

3 2 0,.69 0.,69 0,,69 0..00

4 5 0,.48 0,,53 0,,49 0,.02

6 1 0,.64 0.,64 0,,64 0..00

9 10 0,.62 0,,72 0,,69 0,,03

15 1 0,.42 0,,42 0,,42 0,.00

16 2 0,,42 0,,54 0,,48 0,,08

17 6 0,.54 0,,67 0.,60 0,,04

18 1 0,.27 0.,27 0.,27 0,.00

23 11 0,,35 0,,50 0,,42 0,.03

Means 10 0,.27 0,,69 0,,52 0,.13

Table 4.2.2.2.2 Size at 90% Finer, D90 , m

Material: Silicon Nitride, Test Powder

Property: D90

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0,.91 0.,98 0,.94 0,.04

3 2 1,.10 1.,15 1..12 0,.03

4 5 0,,70 0,,84 0,.74 0,.05

6 1 1.,03 1,,03 1,.03 0,.00

9 10 1,,05 1,,12 1,,09 0,.02

15 1 0,,90 0,,90 0.,90 0,.00

17 6 0,,82 1.,04 0,,93 0..08

18 1 0,,64 0,,64 0,,64 0,.00

23 11 0.,54 1.,00 0.,77 0,.13

Me ans 9 0.,64 1.,12 0.,90 0.,16

84
Table 4.2.2.2.3 Size at 10% Finer, D^q, /zm

Material: Silicon Nitride, Test Powder

Property: D^q

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0 33 0.36 0 34 0.02

3 2 0 41 0.43 0 42 0.01

4 5 0 27 0.32 0 29 0.02

6 1 0 38 0.38 0 38 0.00

9 10 0 32 0.44 0 37 0.03

15 1 0 33 0.33 0 33 0.00

17 6 0 36 0.42 0 38 0.02

23 11 0 19 0.28 0 23 0.02

Means 8 0 23 0.42 0 34 0.05

Table 4.2.2.2.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon Nitride, Test Powder

Property: (Dgo - Dio)/D5o

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 1 05 1.08 1 06 0 02

3 2 1 00 1.04 1 02 0 02

4 5 0 83 1.02 0 90 0 06

6 1 1 02 1.02 1 02 0 00

9 10 0 92 1.18 1 04 0 08

15 1 1 36 1.36 1 36 0 00

17 6 0 85 0.99 0 90 0 06

23 11 1 00 1.72 1 26 0 21

Means 8 0 90 1.36 1 07 0 16

85
jQ

E

3

jOO

(uDa^ |D)Udtuuadx3)

tun 'azjs afoiviDd

u

9)>

o

a. H

M

o

0)N

w • C

0) o

o -u •H CO U C

cd 0)

•H C T3

CO (U

0) cn e

COc

COC

o

to

a CO U bO

1^

3)

86
h.2.2.1

Gravitational Sedimentation (Sedigraph)

Silicon Carbide (SiC) Powder

Table 4.2.2.3.1 Experimental Mean, D50, /xm

Material: Silicon Carbide (Figure 28)

Property: EXPTLMEAN

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 0 75 0.76 0 75 0 00

3 13 4 00 5.00 4 41 0 31

4 3 0 49 0.65 0 57 0 08

6 1 0 82 0.82 0 82 0 00

9 7 0 52 0.59 0 56 0 02

10 1 0 90 0.90 0 90 0 00

15 1 0 55 0.55 0 55 0 00

16 2 0 46 0.53 0 49 0 04

23 21 0 55 1.03 0 74 0 13

Means 9 0.49 4.41 1.09 1.25

Table 4.2.2.3.2 Size at 90% Finer, D90 , )um

Material: Silicon Carbide

Property: Dgo

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 1 20 1.50 1 30 0.17

3 13 5 80 7.20 6 33 0.39

4 3 0 80 0.95 0 87 0.07

6 1 1 30 1.30 1 30 0.00

9 7 1 05 1.25 1 12 0.06

10 1 1 50 1.50 1 50 0.00

15 1 1 00 1.00 1 00 0.00

16 2 0 85 1.00 0 92 0.10

23 21 0 98 2.15 1 45 0.29

Means 9 0 87 6.33 1 75 1.72

87
Table 4.2.2.3.3 Size at 10% Finer, D^q , m

Material: Silicon Carbide

Property: D^q

Method: 9

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 3 0,,52 0,, 53 0,,52 0,,00

3 13 2,,80 4,,40 3,.70 0,.44

4 3 0,,36 0,,46 0,.41 0..05

6 1 0.,62 0.,62 0,,62 0.,00

9 7 0,,19 0,,21 0,,20 0,,00

15 1 0,,20 0,,20 0,,20 0,,00

16 2 0.,19 0,,20 0,,19 0,,00

23 21 0,,35 0,, 55 0,,47 0.,06

Means 8 0.,19 3,,70 0,,79 1,,18

Table 4.2.2.3.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon Carbide

Property: (Dgo - Dio)/D5o

Method: 9

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 0,.89 1,.28 1,.02 0,.22

3 13 0,.46 0,.78 0,.60 0,.10

4 3 0,.75 0..90 0,.81 0..07

6 1 0.,83 0,,83 0,.83 0..00

9 7 1,, 54 1,,80 1..62 0.,08

15 1 1.,45 1,,45 1.,45 0.,00 ^ 16 2 1,,41 1,,53 1,,47 0.,08

23 21 0., 99 1,,69 1,,32 0.,20

Means 8 0. 60 1.,62 1.,14 0.,37

88
E

3

u

o

p<

o

0)N

•HW • C

0) o ^ 1-t o w

U C

cd 0) (X a

C T)

CO 0)

0) 01 a

--H «

C0 C

4-> O

C "H

(I) 4J a <

0) >

% u

(d bO

00

0)

60

Et4

(UD9^ |D)U9UJU9dX3)

tun 'azis 9|3|viDd

89
4.2.2. Gravitational Sedimentation (Sedigraph)

4.2.2.4 Silicon (Si) Powder

Table 4.2.2.4.1 Experimental Mean, D50, /xm

Material: Silicon (Figure 29)

Property: EXPTLMEAN

Method: 9

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 6 70 6.80 6 .73 0.05

3 11 5 40 6.30 5 .81 0.21

4 6 5 40 5.90 5 .63 0.23

6 1 5 80 5.80 5 .80 0.00

9 6 6 50 6.80 6 .61 0.11

15 1 6 20 6.20 6 .20 0.00

16 2 5 58 5.65 5 .61 0.04

17 13 6 70 7.60 7 .25 0.30

18 1 5 60 5.60 5 .60 0.00

23 11 5 70 6.90 6 .32 0.33

Means 10 5 60 7.25 6 .15 0.56

Table 4.2.2.4.2 Size at 90% Finer, D90, /xm

Material: Silicon

Property: Dgo

Method: 9

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 3 12 00 12. 80 12.43 0.40

3 11 9 50 10. 80 10.45 0.34

4 6 10 10 10. 80 10.46 0.28

6 1 10 07 10. 07 10.07 0.00

9 6 11 50 12. 30 11.71 0.34

15 1 10 50 10. 50 10.50 0.00

16 2 9 52 9. 67 9.59 0.10

17 13 12 00 14. 20 13.26 0.59

18 1 10 00 10. 00 10.00 0.00

23 11 12 00 14. 20 12.94 0.67

Means 10 9 59 13. 26 11.14 1.33

90
Table 4.2.2.4.3 Size at 10% Finer, D^q , m

Material: Silicon

Property: D^g

Method: 9

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 3 1.75 1 .90 1 83 0 07

3 11 1.40 2 .30 1 85 0 26

4 6 1.01 1 .55 1 31 0 23

6 1 1.55 1 .55 1 55 0 00

9 6 2.00 2 .50 2 27 0 22

15 1 2.00 2 .00 2 00 0 00

16 2 2.03 2 .13 2 08 0 07

17 12 1.55 2 .00 1 84 0 16

18 1 1.50 1 .50 1 50 0 00

23 11 1.30 2 .30 1 73 0 34

Means 10 1.31 2 .27 1 79 0 28

Table 4.2.2.4.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon

Property: (Dgo - Dio)/D5o

Method: 9

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 3 1 51 1 61 1 57 0 05

3 11 1 30 1 57 1 47 0 07

4 6 1 57 1 72 1 62 0 06

6 1 1 47 1 47 1 47 0 00

9 6 1 37 1 49 1 42 0 04

15 1 1 37 1 37 1 37 0 00

16 2 1 32 1 35 1 33 0 02

17 12 1 52 1 63 1 57 0 03

18 1 1 52 1 52 1 52 0 00

23 11 1 46 2 25 1 78 0 20

Means 10 1 33 1. 78 1 51 0 13

91
0)

JOE3O

Uo

p. M

IMO

0)N

•HW • C

0)

o ^ tH O W

tH qj

V4

C

CO (U o. s C TJ

(d 0)

(Un

S

cd

C

4J

o

B (d •H 4-»

(U >

O. (d U

bO

92
4.2.2. Gravitational Sedimentation (Sedigraph)

4.2.2.5 Yttria-Zirconia (YSZ) Powder

Table 4.2.2.5.1 Experimental Mean, D50 , /im

Material: Zirconia (Figure 30)

Property: EXPTLMEAN

Method: 9

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

4 6 0.15 0.32 0.20 0.07

6 1 0.20 0.20 0.20 0.00

15 1 0.20 0.20 0.20 0.00

17 21 0.14 0 76 0 25 0W.J1 5f 18 5 0.15 0.50 0.22 0.15

23 2 0.15 0.18 0.16 0.02

Means 6 0.16 0.25 0.20 0.02

e 4.2.2.5.2 Size at 90% Finer

Material

Zirconia

Property D90

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

4 8 2.20 4.00 3.02 0.55

6 1 3.20 3.20 3.20 0.00

15 1 4.00 4.00 4.00 0.00

17 6 3.70 8.50 6.11 1.88

18 5 10.50 14.00 11.70 1.39

Means 5 3.02 11.70 5.60 3.62

93
Table 4.2.2.5.3 Size at 10% Finer, Djo, m

Material: Zirconia

Property: D^g

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 0.16 0.16 0.16 0.00

Means 1 0.16 0.16 0.16 0.00

Table 4.2.2.5.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Zirconia

Property: (Dgo - Dio)/D5o

Method: 9

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 20.78 20.78 20.78 0.00

Means 1 20.78 20.78 20.78 0.00

94
E3o

uo

a. N

C/3 >Ho

0)N

•iH(0

0)

o

O 4J •H (Q U U u c

CO (U a s c -o

0) CO sce Co

4J

0) >

b3 bO O

COu

95
4.2.3.

4.2.3.1

Centrifugal Sedimentation

Silicon Nitride Reference Powder

Table 4.2.3.1.1 Experimental Mean, D50 , /xm

Material: Silicon Nitride, Reference Powder (Figure 31)

Property: EXPTLMEAN

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 9 0,,91 1,,14 1,,02 0,.06

5 3 0.,67 0,,70 0,,68 0,.01

11 1 0,,57 0,,57 0,.57 0..00

13 20 1,,21 1,,67 1,,40 0..11

14 1 0,,98 0.,98 0.,98 0..00

19 1 1.,51 1.,51 1,,51 0,.00

Means 6 0.57 1.51 1.02 0.37

Table 4.2.3.2.2 Size at 90% Finer, D90 , m

Material: Silicon Nitride, Reference Powder

Property: Dgg

Method: 10

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 3 3.80 5.00 4.26 0.64

11 1 2.90 2.90 2.90 0.00

14 1 4.30 4.30 4.30 0.00

Means 3 2.90 4.30 3.82 0.79 -

96
Table 4.2.3.1.3 Size at 10% Finer, D^q, fim

Material

:

Silicon Nitride, Reference Powder

Property:

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 3 0.26 0.30 0.28 0.02

11 1 0.20 0.20 0.20 0.00 . 14 1 0.29 0.29 0.29 0.00

Means 3 0.20 0.29 0.25 U . UD

e 4.2.3.1.4 Spread Ratio of Size Distribution, (Dgg - Dio)/D5o

Material

:

Silicon Nitride, Reference Powder

Property

:

(D90 - Dio)/D50

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 3 5.22 6.77 5.81 0.83

11 1 4.74 4.74 4.74 0.00

14 1 4.09 4.09 4.09 0.00

Means 3 4.09 5.81 4.88 0.87

97
0)

E

J3

O

bO

•i-l U

V

G

0)u

0)

o

CO

(M

O

0)taH

0)

iJ

(0(Xc

(d

o

(d

<4 4Jc

s

(I) au

CO

bO

1-1

(UDai^ |D^U8UJIJ8dX3)

98
4.2.3.

4.2.3.2

Centrifugal Sedimentation

Silicon Nitride Test Powder

Table 4.2.3.2.1 Experimental Mean

Material: Silicon Nitride, Test Powder (Figure 32)

Property: EXPTLMEAN

Method: 10

LAB #

// of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 2 0.77 0.78 0.77 0.00

5 4 0.53 0.56 0.53 0.01

14 3 0.55 0.66 0.59 0.06

19 10 0.77 1.10 0.88 0.09

Means 4 0.53 0.88 0.69 0.16

Table 4.2.3.2.2 Size at 90% Finer, Dgo , /xm

Material: Silicon Nitride, Test Powder

Property: Dgo

Method: 10

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 4 1.14 1.89 1.35 0.35

14 3 1.20 1.81 1.41 0.34

Means 2 1.35 1.41 1.38 0.04

99
Table 4.2.3.2.3 Size at 10% Finer, D^q, /xm

Material: Silicon Nitride,

Property: Diq

Method: 10

Test Powder

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 4

14 3

0.24

0.27

0.25

0.34

0.24

0.29

0 . 00

0.04

Means 2 0.24 0.29 0.27 0.03

Table 4,2.3.2.4 Spread Ratio of Size Distribution, (Dgg Dio)/D5o

Material: Silicon Nitride,

Property: (Dgo - Dio)/D5o

Method: 10

Test Powder

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 4

14 . 3

1.68

1.66

2.95

2.23

2.04

1.87

0.60

0.31

Means 2 1.87 2.04 1.95 0.11

100
jQ

E

3

o

CObO

3

(4-1 •H

1-1 4Jc

u

0) •ooa

H

2:M

o

0)N

•H

U)

0)

iJU

COa

c

CO0)a • c ^ o

CO

i-i li C OS

(U 4J a G

)-) B

a> •H

a. •«

(N

CO

bO

(UD8^ |D)Udaiuddx3)

tun 'azis apiviod

101
4.2.3.

4.2.3.3

Centrifugal Sedimentation

Silicon Carbide Powder

Table 4.2.3.3.1 Experimental Mean, D50 , /xm

Material: Silicon Carbide

Property: EXPTLMEAN

Method: 10

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 6 0.58 0.83 0.69 0.08

2 1 0.40 0.40 0.40 0.00

13 10 0.63 0.71 0.66 0.02

Means 3 0.40 0.69 0.58 0.16

e 4.2.3.3.2 Size at 90% Finer > D90. /^m

MaterialSilicon Carbide

Property: D90

Method: 10

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 6 1.50 2.06 1.78 0.18

2 1 0.86 0.86 0.86 0.00

Means 2 0.86 1.78 1.32 0.65

102
Table 4.2.3.3.3 Size at 10% Finer, D^q , m

Material

:

Silicon Carbide

Property:

Method: 10

Dio

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 6 0.29 0.45 0.38 0 . 06

2 1 0.11 0.11 0.11 0.00

Means 2 0.11 0.38 0.24 0.19

e 4.2.3.3.4 Spread Ratio of Size Distribution, (Dgg Dio)/D50

Material

:

Silicon Carbide

Property

Method: 10

(D90 - Dio)/D50

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 6 1.48 2.47 2.05 0.34

2 1 1.87 1.87 1.87 0.00

Means 2 1.87 2.05 1.96 0.13

103
4.2.3. Centrifugal Sedimentation

4.2.3.4 Silicon Powder

Table 4.2.3.4.1 Experimental Mean, D50 , /xm

Material: Silicon (Figure 33)

Property: EXPTLMEAN

Method: 10

Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 4.09 4.29 4.17 0.10

2 1 6.60 6.60 6.60 0.00

5 2 4.90 5.00 4.95 0.07

19 9 4.62 6.05 5.08 0.44

Means 4 4.17 6.60 5.20 1.01

Table 4.2.3.4.2 Size at 90% Finer, Dgo , ^m

Material: Silicon

Property: Dgg

Method: 10

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 3 7.06 7.49 7.30 0.21

2 1 9.80 9.80 9.80 0.00

5 2 11.70 11.80 11.75 0.07

Means 3 7.30 11.75 9.61 2.23

104
Table 4.2.3.4.3 Size at 10% Finer, Djo, /xm

Material: Silicon

Property: D^q

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 1.40 1.95 1.76 0.31

2 1 0.43 0.43 0.43 0.00

5 2 0.56 0.56 0.56 0.00

Means 3 0.43 1.76 0.91 0.73

Table 4.2.3.4.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D50

Material: Silicon

Property: (Dgo - Dio)/D5o

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 1.19 1.47 1.32 0.14

2 1 1.42 1.42 1.42 0.00

5 2 2.25 2.27 2.26 0.01

Means 3 1.32 2.26 1.66 0.51

105
(uD8iAj iD^uaujuadx^)

0)

E

O

Co

!-l

o

1/3

0

OJN

u

cxC

0)S

cfl —I

0)c

•in W CO

CO

1)

5b

.1-1

106
4.2.3.

4.2.3.5

Centrifugal Sedimentation

Yttria-Zirconia Powder

Table 4.2.3.5.1 Experimental Mean, D50 , /xm

Material: Zirconia (Figure 34)

Property: EXPTLMEAN

Method: 10

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 6 1.38 1.62 1.49 0.08

11 1 0.56 0.56 0.56 0.00

14 1 1.73 1.73 1.73 0.00

19 18 1.21 1.69 1.47 0.11

Means 4 0.56 1.73 1.31 0.51

Table 4.2.3.5.2 Size at 90% Finer, D90 , /xm

Material: Zirconia

Property: Dgg

Method: 10

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

11 1 2.90 2.90 2.90 0.00

14 1 7.30 7.30 7.30 0.00

Means 2 2.90 7.30 5.10 3.11

107
Table 4.2.3.5.3 Size at 10% Finer, Djo, m

Material: Zirconia

Property: D^q

Method: 10

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 1 0.18 0.18 0.18 0.00

14 1 0.29 0.29 0.29 0.00

Means 2 0.18 0.29 0.23 0.07

Table 4.2.3.5.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Zirconia

Property: (Dgo - Dio)/D5o

Method: 10

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

11 1 4.86 4.86 4.86 0.00

14 1 4.05 4.05 4.05 0.00

Means 2 4.05 4.86 4.45 0.57

108
L.

£

3

•i-i u

4Jc

<uo

>^

o

a. N

M

>^(M

O

0)N

«H

01

(dP<C

cd

a>^ c ^ o

(d u

C

0) ^ s

c

a

•sr

0)

(uDa^ |D)uaaiu8dx3)

tun 'azis apiviod

109
4.2.4. Light-Scattering Fraunhofer-Mie Type Instruments

4.2.4.1 Silicon Nitride Reference Powder

Table 4.2.4.1.1 Experimental Mean, D50 . A^ni

Material: Silicon Nitride, Reference Powder (Figure 35)

Property: ExPTLMEAN

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 5 1,,33 1.,35 1,,34 0,.00

8 28 0,.98 1.,25 1,.12 0,.06

9 24 1,,14 1.,35 1,.23 0,.05

14 2 0,, 75 0,,77 0.,76 0,.01

20 7 1,,09 1,,52 1,,34 0,.13

21 1 0,,79 0.,79 0,,79 0,.00

22 36 0,,72 0,,90 0,,80 0..06

24 2 0.,40 0,,85 0.,62 0,.31

25 3 0,,73 0.,80 0.,76 0,.03

Means 9 0.,62 1.,34 0,,97 0,.28

Table 4.2.4.1.2 Size at 90% Finer, D90 , m

Material: Silicon Nitride, Reference Powder

Property: Dgo

Method: 13

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

8 28 3..45 7.33 5.19 0..86

9 24 5,.44 7.35 6.46 0,.63

14 1 2..00 2.00 2.00 0,.00

20 7 5,,15 11.52 8.62 2,.10

21 1 3.,20 3.20 3.20 0,.00

22 36 1.,86 2.58 2.26 0,,22

24 2 2,,90 9.60 6.25 4.,73

25 3 2,,61 2.91 2.76 0.,15

Means 8 2.,00 8.62 4.59 2.,39

110
Table 4.2.4.1.3 Size at 10% Finer, Dig, fim

Material

Silicon Nitride, Reference Powder

Property:

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 28 0 . 40 0.43 0.40 0.00

9 24 0.34 0

.

37 0 . 35 0 . 00

14 1 0.31 0.31 0.31 0.00

20 7 0.37 0.40 0.38 0.00

21 1 0.28 0.28 0.28 0.00

22 36 0.31 0.36 0.33 0.01

24 2 0.10 0.24 0.17 0.09

25 3 0.32 0.33 0.32 0.00

Means 8 0.17 0.40 0.32 0.07

Table 4.2.4.1.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material

Property:

Method: 13

Silicon Nitride, Reference Powder

(D90 - Dio)/D5o

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 28 3.10 5.57 4.22 0,.55

9 24 4.36 5.44 4.91 0,.34

14 1 2.25 2.25 2.25 0,.00

20 7 4.39 7.67 6.03 1,.03

21 1 3.70 3.70 3.70 0,.00

22 36 2.12 2.71 2.40 0..18

24 2 7.00 11.01 9.00 2..83

25 3 3.14 3.23 3.18 0..04

Means 8 2.25 9.00 4.46 2.,22

111
(uDa^ |D)U9uiuadx3)

I.

u

o

4JC

CO

o

V4

4-) C

(U 0) N a<

CO u

(U 9) o S •i-i I

>-l (V CO (4^o

0) (0

CO

4-) C

(US

bOC

•i-i u

9) U

p. cd X o U CO

0)

3)

112
4.2.4. Light Scattering Fraunhofer-Mle Type Instruments

4.2.4.2 Silicon Nitride Test Powder

Table 4,2.4.2.1 Experimental Mean, D50 , /xm

Material: Silicon Nitride, Test Powder (Figure 36)

Property: EXPTLMEAN

Method: 13

y/ of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

7 10 0 61 0.63 0.62 0.00

8 35 0 65 0.72 0.67 0.02

9 54 0 60 0.63 0.61 0.00

14 4 0 52 0.57 0.54 0.02

20 3 0 58 0.58 0.58 0.00

22 30 0 56 0.60 0.57 0.01

24 4 0 69 0.77 0.73 0.03

25 3 0 54 0.55 0.54 0.00

Means 8 0 54 0.73 0.61 0.06

Table 4.2.4.2.2 Size at 90% Finer, D90 , fim

Material: Silicon Nitride, Test Powder

Property: Dgg

Method: 13

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

8 35 1.36 1.57 1.45 0.05

9 54 1.18 1.49 1.32 0.06

14 4 1.25 1.60 1.42 0.15

20 3 1.09 1.11 1.10 0.01

22 30 0.99 1.32 1.13 0.09

24 4 1.51 2.01 1.79 0.22

25 3 0.99 1.01 1.00 0.01

Means 7 1.00 1.79 1.31 0.26

113
Table 4.2.4.2.3 Size at 10% Finer, D^q , /xm

Material: Silicon Nitride, Test Powder

Property: D^q

Method: 13

# of

LAB y/ Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

8 35 0 35 0 37 0 36 0 00

9 54 0 28 0 32 0 30 0 00

14 4 0 17 0 23 0 21 0 02

20 3 0 32 0 32 0 32 0 00

22 30 0 30 0 32 0 30 0 00

24 4 0 32 0 41 0 35 0 03

25 3 0 30 0 30 0 30 0 00

Means 7 0 21 0 36 0 30 0 04

Table 4.2.4.2.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon Nitride, Test Powder

Property: (Dgo - Dio)/D5o

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 35 1 54 1 67 1 60 0 03

9 54 1 47 1 92 1 67 0 09

14 4 1 79 2 51 2 23 0 34

20 3 1 33 1 36 1 34 0 01

22 30 1 18 1 67 1 44 0 13

24 4 1 61 2 32 1 96 0 36

25 3 1 25 1 30 1 28 0 02

Means 7 1 28 2 23 1 64 0 34

114
tun 'azis apiviod

u

o

(X 0) H § Z M M -U

Ul o •^^

CO 4-)

0) 0)

.—I ^

1-1 I

cdcx o

to d

0) CO

bO

C

0) u u

CI. <0 X o

CO

fa

115
4.2.4.

4.2.4.3

Light Scattering Fraunhofer-Mie Type Instrument

Silicon Carbide Powder

Table 4.2.4.3.1 Experimental Mean, D50 , /xm

Material: Silicon Carbide (Figure 37)

Property: EXPTLMEAN

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 3 0.39 0.44 0.42 0.02

8 24 0.50 0.52 0.51 0.00

10 4 0.48 0.50 0.48 0.00

20 1 0.72 0.72 0.72 0.00

21 1 0.57 0.57 0.57 0.00

22 47 0.55 0.66 0.59 0.02

25 1 0.53 0.53 0.53 0.00

Means 7 0.42 0.72 0.54 0.09

Table 4.2.4.3.2 Size at 90% Finer, D90 , urn

Material: Silicon Carbide

Property: D90

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 3 0.64 0.67 0.66 0.01

8 24 0.98 1.01 0.98 0.00

10 4 0.99 1.52 1.19 0.24

20 1 1.61 1.61 1.61 0.00

22 47 0.91 1.64 1.22 0.15

25 1 1.17 1.17 1.17 0.00

Means 6 0.66 1.61 1.14 0.31

116
Table 4.2.4.3.3 Size at 10% Finer, Dio> A*"*

Material: Silicon Carbide

Property: D^q

Method: 13

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

7 3 0,,23 0,,29 0,,27 0,.03

8 24 0,,29 0,,30 0,,29 0,.00

10 4 0,,23 0,.23 0,,23 0..00

20 1 0,,35 0,,35 0,,35 0..00

22 47 0,,29 0,,36 0.,32 0,.01

25 1 0,,29 0,,29 0,,29 0,.00

Means 6 0.,23 0.,35 0.,29 0..04

Table 4.2.4.3.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon Carbide

Property: (Dgo - Dio)/D5o

Method: 13

# of

LAB # Values

Minimum

Value

Maximtim

Value

Average

Value

Standard

Deviation

7 3 0.86 1.05 0.92 0.10

8 24 1.33 1.40 1.34 0.01

10 4 1.55 2.58 1.97 0.46

20 1 1.75 1.75 1.75 0.00

22 47 1.02 2.15 1.50 0.23

25 1 1.66 1.66 1.66 0.00

Means 6 0.92 1.97 1.52 0.36

117
q>

E

3

o

(uoa^ ID^uatuuadx^)

tun '9ZIS apiViDci

4->

U

0)

o

4-> c o i

cn .u

(A O -rH

•rlCO 4->

0) 0) —I -H o S •H I 4-) >-t (U n) (4-1 (X o c-S

CO 3

0) CO s t

cd bO

C

p

S

•HU

0)a. cd U CO

to

0)

S-l

118
4.2.4.

4.2.4.4

Li ght -Scattering Fraunhofer-Mie Type Instruments

Silicon Powder

Table 4.2.4.4.1 Experimental Mean , D50 , )um

Material: Silicon (Figure 38)

Property: EXPTLMEAN

Method: 13

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

5 2 6.50 6.50 6.50 0.00

8 24 7.12 7.78 7.37 0.15

9 36 7.34 7.61 7.43 0.06

20 1 7.36 7.36 7.36 0.00

22 24 7.09 8.10 7.57 0.27

Means 5 6.50 7.57 7.25 0.42

Table 4.2.4.4.2 Size at 90% Finer, D90, /im

Material: Silicon

Property: D90

Method: 13

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

5 2 11.70 11.80 11.75 0.07

8 24 12.84 15.01 13.95 0.48

9 36 13.60 14.39 13.98 0.19

20 1 13.89 13.89 13.89 0.00

22 24 12.61 15.14 13.80 0.69

Means 5 11.75 13.98 13.47 0.96

119
Table 4.2.4.4.3 Size at 10% Finer, Diq, A»ni

Material: Silicon

Property: D^q

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 2 1.60 1.60 1.60 0.00

8 24 2.40 2.81 2.58 0.10

9 36 2.73 3.02 2.88 0.06

20 1 2.70 2.70 2.70 0.00

22 24 2.06 2.94 2.35 0.24

Means 5 1.60 2.88 2.42 0.49

Table 4.2.4.4.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Silicon

Property: (Dgo - Dio)/D5o

Method: 13

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 2 1.55 1.57 1.56 0.01

8 24 1.42 1.64 1.54 0.05

9 36 1.45 1.54 1.49 0.02

20 1 1.52 1.52 1.52 0.00

22 24 1.31 1.66 1.51 0.09

Means 5 1.49 1.56 1.52 0.02

120
u

Q> • ^ c

O 0) p. I

u

(4-1 C

O

0) 0) N 04 ^ >^

CO 4J

<U 0) ^ H

O S •H I u u

U 0)

(Tt ^

(X O

^1OJ 3

(V CQ a >^

«0 - 4J bO

C C

0) •H S U

•i-l 0)

S-l 4-) « iJ a cd X o

u u)

00

CO

(uoa^ |D)Udtuudcix3)

tun *8Zis api^Dci

121
4.2.4.

4.2.4.5

Light Scattering Fraunhofer-Mie Type Instruments

Yttrla-Zirconia Powder

Table 4.2.4.5.1 Experimental Mean, D50, nm

Material: Zirconia (Figure 39)

Property: EXPTLMEAN

Method: 13

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

11 1 2.90 2.90 2.90 0.00

14 3 2.20 2.30 2.26 0.05

20 3 4.06 4.19 4.14 0.07

22 7 0.62 0.95 0.76 0.11

24 3 1.40 1.80 1.56 0.20

Means 5 0.76 4.14 2.32 1.28

Table 4.2.4.5.2 Size at 90% Finer, D90, /im

Material: Zirconia

Property: Dgg

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

11 1 9.20 9.20 9.20 0.00

14 3 9.50 9.80 9.60 0.17

20 3 11.33 11.80 11.54 0.23

22 7 2.38 2.96 2.65 0.20

24 3 7.60 8.60 7.96 0.55

Means 5 2.65 11.54 8.19 3.35

122
Table 4.2.4.5.3 Size at 10% Finer, D-^q, /im

Material: Zirconia

Property: Dio

Method: 13

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

11 1 0.37 0.37 0.37 0.00

14 3 0.40 0.40 0.40 0.00

20 3 0.50 0.51 0.50 0.00

22 7 0.15 0.15 0.15 0.00

24 3 0.13 0.14 0.13 0.00

Means 5 0.13 0.50 0.31 0.16

Table 4.2.4.5.4 Spread Ratio of Size Distribution, (Dgo - Dio)/D5o

Material: Zirconia

Property: (Dgo - Dio)/D5o

Method: 13

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

11 1 3.04 3.04 3.04 0.00

14 3 3.96 4.14 4.06 0.09

20 3 2.62 2.71 2.66 0.04

22 7 2.71 4.12 3.31 0.55

24 3 4.70 5.34 5.03 0.32

Means 5 2.66 5.03 3.62 0.93

123
« i

o 9

E

a.

E o>

c

o

o

M

K)

IIc

o

II >

o

CM

CM

loo

CD

in

o

-4-

o

to

q

CM

CO

CM

CM

0)

jQ

E

3

XCM jQ

--00

..CO

+ CM

o

o

o

Uii7 'azis afoiviDd

•a

o

4-> c

N 1

CO M

w

O 1-1

U 4-)

0) 0)

•—Io S 1-1 I U 0)

a. o «l

(U CO e u

4-) bO c c

Q) 1-1 6 )-* iH 0)

>-l 4J

0) 4-) a CO X o u n

ON

CO

u

3

bO

•H

124
4.2.5.

4.2.5.1

Electrical Sensing Zone

Silicon Powder

Table 4.2.5.1.1 Experimental Mean, D50 , nm

Material: Silicon

Property: EXPTLMEAN

Method: 7

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 6 5.20 5.50 5.31 0.11

Means 1 5.31 5.31 5.31 0.00

Table 4.2.5.1.2 Size at 90% Finer, Dgo , yum

Material: Silicon

Property: Dgo

Method: 7

of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

16 5 9.60 10.00 9.82 0.20

Means 1 9.82 9.82 9.82 0.00

Table 4.2.5.1.3 Size at 10% Finer, Dio , m

Material: Silicon

Property: D^q

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 5 1.05 1.15 1.08 0.03

Means 1 1.08 1.08 1.08 0.00

125
.2 « ^ N

(rt % Q)

Q O

^ b

n

•d

o

Within Lab }

| j

Betw.

Labs

0)3

Figure 40. Within lab, between lab, and between methods standard

deviations in the measurement of particle size for the

Si3N^(Ref.) powder as measured by various laboratories

using a variety of methods.

126
Within Lab }

| 1 JQ

Betw. . o

Labs

Within lab, between lab, and between methods standard

deviations in the measurement of particle size for the

SisN^CTest) powder as measured by various laboratories

using a variety of methods.

127
Within Lab } {- Betw -}

Labs

n

ii

Within lab, between lab, and between methods standard

deviations in the measurement of particle size for the SiC

powder as measured by various laboratories using a variety

of methods

128
m)

O

a Q)

o N

cd

V

0)

p—

1

0) a

Q

'd

u

cd

a d cd

cd

w

mthin Lab

Betw.

Labs

n

•d

. o

igure 43. Within lab, between lab, and between methods standard

deviations in the measurement of particle size for the Si

powder as measured by various laboratories using a variety

of methods

.

129
1.0

.2 Q)

irt Q o

S S

CO «

Zr02

0.8-

0.6-. o

0.4-

0.2 -

0.0

d

•a 5

^ I

Is o

I 1

1

13 (d

;3 d

•c a

0) Q)

j_i

u

o

u

d

o

o

04

00

d

0)

«d

o

CO

a o

L

CQ

0.

j Within Lab If

Betw.

Labs

n

Figure 44. Within lab, between lab, and between methods standard

deviations in the measurement of particle size for the Zr02

powder as measured by various laboratories using a variety

of methods

130
Table 4.2.5.1.4 Spread Ratio of Size Distribution, (Dgo - D]^o)/D5o

Material: Silicon

Property: (Dgo - Dio)/D5o

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 5 1.61 1.66 1.64 0.01

Means 1 1.64 1.64 1.64 0.00

4.3. STATISTICAL ANALYSIS . R. Munro , NIST

Several techniques are available to measure particle size distributions in

powders. These techniques may be based on different physical principles and

different instrumentation and may utilize significantly different procedures

for dispersing the particles in a medium before a measurement is performed.

Further, the various methods have different detection limits.

Two of the methods, gravitational sedimentation and centrifugal sedimentation,

utilize the size dependence of the terminal velocity of particles moving

through a viscous medium under the influence of gravity or the rotational

acceleration of the medium. In both methods, an equivalent spherical diameter

is assumed as the measure of the particle size. Two other methods,

Fraunhofer-Mie light scattering and photon correlation spectroscopy, depend on

the size dependence of the distribution or diffraction pattern of the

scattered light. These techniques determine a mean size of the particles in

the diffraction volume.

Results from gravitational sedimentation and centrifugal sedimentation are

shown in Figures 40-44; results for Fraunhofer-Mie light scattering are shown

in Figures 40-43 for all powders except zirconia; and results for photon

correlation spectroscopy are shown in Figure 44 for zirconia. Each method

measures the cumulative particle size distribution and computes the mean

particle size from that distribution. In each case, the standard deviation

was typically less than ten percent of the mean value, and none of the methods

was consistently better than the others. The variances between laboratories

were larger than the differences between methods for silicon nitride and

silicon carbide, but for silicon and zirconia, the discrepancy between methods

was larger.

131
5. PARTICLE MORPHOLOGY

R. Pompe, Swedish Ceramic Institute; A. L. Dragoo , NIST

5.1. MEASUREMENT METHODS

5.1.1. Scanning Electron Microscopy (SEM) /Transmission Electron Microscopy

(TEM)

Use and Significance

Microscopic methods of particle evaluation (SEM, TEM) provide a direct means

of estimating the particle size distribution, degree of agglomeration,

particle or agglomerate shape and aspect ratio. Both techniques are used

extensively to obtain images, usually as micrographs of particles, which

provide a picture of particle features and which offer a qualitative, orderof -magnitude estimate of particle size. By coupling SEM and TEM with

quantitative image analysis, quantitative or semiquantitative evaluation of

particle size and shape characteristics can be obtained. A wide size range

down to approximately 2 nm can be covered with a combination of the two

techniques. Powder sample preparation techniques are crucial in obtaining a

representative image. By virtue of being the only methods of direct particle

observation, they are essential for powder characterization in conjunction

with other physical methods.

Instrument and Experimental Parameters

SEM/TEM micrographs were supplied by the following laboratories:

Lab # Powder Mode

4 All Powders SEM

18 SNT, SiC, Si, YSZ SEM

22 YSZ TEM

23 SNR SEM

Labs 12, 13, 18 and 23 conducted quantitative image analysis of various

powders. The results of the image analysis are summarized in the subsequent

sections

Sample Preparation

For qualitative studies, powder samples were deposited on SEM sample holders

in the as-received state or dispersed and deposited dropwise on a grid. The

following is an example of preparation procedure used by Lab 6:

132
Sic Powder

As -received- A small amount of powder was sprinkled on a

sticky tab which was placed on a carbon grid.

The excess was removed and a thin layer of Au-Pd

metallization was applied to the sample.

Photomicrographs were taken at 200x, 500x, lOOOx

and 2000x.

Dispersed- Approximately 3 mg of powder was placed in a

beaker which contained 80 ml of distilled water

to which had been added 16 drops of concentrated

ammonium hydroxide (pH -10.5). The sample was

dispersed for 30 s in a sonifier. Several drops

of the dispersed sample were placed on a carbon

grid and allowed to dry. A thin layer of Au-Pd

metallization was applied to the samples.

Photomicrographs were taken at 2000x, 5000x and

7500x.

Lab 4 prepared samples by the camphor -naphthalene method. A mixture of 10 mg

powder and 4 mg camphor -naphthalene (6:4) was melted in an oven and was then

ultrasonicated for 4 minutes. After rapid cooling to -20 °C a small amount of

the mixture was suspended on to a preheated SEM aluminum stub and the organic

part was sublimed away.

For quantitative analysis of particle size, Lab 23 reported the dispersion of

a few milligrams of powder in 25 ml of water which contained 0.02 % Darvan.

The suspension was ultrasonicated for 60 s, then filtered through a polycarbonate membrane filter with 0.2 /um diameter pores. The filter and

particles were coated with 5-10 nm of Au-Pd.

Calibration and Standards

In addition to many reference artifacts and resolution grids frequently

supplied by manufacturers, there are several certified references available

from the National Institute of Standards and Technology; namely,

SRM 484e SEM Magnification Standard

SRM 2069a SEM Performance Standard.

In addition, SRM's 1690, 1691, 1960, 1961 and 1965, which consist of

calibrated polystyrene spheres in water can be incorporated into particle

suspensions and applied to SEM grids as a length reference.

Results and Discussion

Qualitative Analysis

Micrographs illustrating various aspects of the powders are presented in

Section 5.2.

133
The main features of all the data received of dispersed powders are summarized

and the relevant SEM/TEM micrographs are collected in Sections 5.2 and 5.3.

Quantitative Analysis

Data for particle size analysis are summarized in Section 5.3.

Lab 23 reported results for all powders. Measurements were made on

approximately 2000 particles for each powder, using backscattered electrons.

The video output of the SEM was processed by a Kevex Delta V image analyzer.

The particle dimension was given in terms of the Wadell diameter (i.e., the

diameter of a circle having the same area as that of the image of a particle)

Five to seven size intervals were used to obtain approximate representations

of the size distributions for each powder. Number-based distributions were

transformed to mass (volume) -based distributions by assuming equivalent

spherical volumes for the particles.

Lab 23 reported determinations of the average particle size for SNR samples;

see Table 5.3.2.1. A 30-40 mg portion of each powder was added to 100 ml of a

surfactant solution and dispersed ultrasonically for 5 minutes. One drop of

the suspension was air dried on a glass slide and then coated with carbon and

Au-Pd conductive coating. Image data were collected from calibrated

micrographs. Results were reported in terms of the arithmetic mean of the

maximum length of the observed grains.

Lab 12 reported one average particle size for each of samples SNR, SNT, and Si

powders, and two results for the YSZ powder. The values reported by Lab 12

appear to be those for mass -based distributions, but this could not be

confirmed.

Lab 18 analyzed as -received and dispersed samples of the YSZ powder. Particle

images on the SEM micrographs were examined with a Zeiss Interactive Digital

System by tracing the images and quantitatively determining agglomerate sizes

and the size distribution. The results of the analysis are summarized in

Table 5.1.1.1 below and, for six samples of the as-received powder, in Table

5.3.6.1. For the quantitative analysis of the as-received powder, between 109

and 305 particles were measured per sample. The mean size and the standard

deviation (not a^) were reported for each powder. They reported the number of

particles versus size, for lEA powder OR012 , using a total of 22 intervals.

Since the spray-dried agglomerates of the as-received powder were

approximately shperical in shape, a mass -based distribution can be calculated

with a fair degree of accuracy from the number-based distribution which they

reported. These two distributions are shown in Figure 45 and illustrate the

marked difference which exists between the two distributions.

134
Table 5.1.1.1 Summary of Agglomerate and Particle Characteristics for

Yttria-Zirconia (YSZ) Powder (Lab 18)

1. Primary Agglomerates (As -received Powder)

Determination:

Average Size:

SEM

30-35 fim (Number)

Shape

:

% Agglomerated:

Aspect Ratio:

> 90%

1

Spherical

2. Secondary Agglomerates (Dispersed Powder)

Determination

:

Average Size:

Shape

:

SEM and Sedigraph

0.1-0.2 ^im

Equiaxed

Aspect Ratio: Not determined

3. Crystallite Size

Determination:

Average Size:

XRD

22-23 nm

Conclusions

Qualitative SEM/TEM evaluation is an important complement to other particle

characterization methods in terms of identifying the fabrication route and of

gaining information on the shape, aspect ratio and agglomeration state of the

particular powder.

Computer-automated techniques for image analysis can be utilized for measuring

average particle size. Detailed quantitative information can be obtained,

such as primary agglomerate size etc., which can be correlated to other,

physical methods of particle size distribution measurements.

135
0) 0)

II^

o

-7-7-

f I / T i /,

-zrr

f f r *

/ / / / / 21

O

o

o

cn

=. o

00

o

o

o

10

o

% 'Xouanbajj

E

N

(/)

o

o

QT3

0)>

•H

(UO

0)

>^

(0

CO

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5.2. PARTICLE MORPHOLOGY - MICROGRAPHS

5.2.1. Scanning Electron Microscopy (SEM) and Transmission

Electron Microscopy (TEM)

Particle morphology of as -received powders and of dispersed powders and

particles was characterized by SEM and TEM studies. Selected micrographs

the five powders are presented in the following pages

.

5.2,1.1 Silicon Nitride Reference Powder

Figure 46. SEM micrograph of powder as -received. Magnification 100

scale bar in lower right of micrograph indicates 100 /xm

length. Sample: SNR 9028. Lab No. 4.

137
Figure 47 . SEM micrograph of powder after dispersal in water and

followed by collection of polycarbonate filter. Scale bar

in lower center of micrograph indicates 1 urn length.

Sample: SNR 0408. Lab No. 23.

138
SEM micrograph of particle collected on polycarbonate

filter. Note dense agglomerated structure of particle.

Scale bar in lower center of micrograph indicates 1 /xm

length. Sample: SNR 0408. Lab No. 23.

139
SEM micrograph of agglomerated SNR particles. Magnification

40,000x; scale bar In lower right of micrograph Indicates 1

urn length. Sample: SNR 9028. Lab No. 4.

140
Silicon Nitride Test Powder

SEM micrograph of powder as -received. Magnification lOOOx

scale bar in lower right of micrograph indicates 10 //m

length. Sample: SNT LSM 2. Lab No. 4.

141
Figure 51. SEM micrograph of powder. Sample: SNT 1385. Lab No,

1A2
Figure 52. SEM micrograph of particle. Magnification 20,000x; scale

bar in lower right of micrograph indicates 1 //m length.

Sample: SNT LSM 2. Lab No. 4.

143
SEM micrograph of particle. Magnification 40,000x; scale

bar In lower right of micrograph Indicates 1 /zm length.

Sample: SNT LSM 2. Lab No . 4

.

144
5.2.1.3. Silicon Carbide Powder

Figure 54. SEM micrograph of powder as -received. Magnification lOOOx;

scale bar in lower right of micrograph indicates 10 /im

length. Sample: SiC 1023. Lab No. 4.

145
15KU 5.0 0KX 2.00M 0588

(

Figure 55. SEM micrograph of powder. Scale bar in lower center of

micrograph indicates 2 fj,m length. Sample: SiC 0588. Lab

No. 21. i

146
SEM micrograph of dispersed powder. Magnification lO.OOOx;

scale bar in lower right of micrograph indicates 1 /im

length. Sample: SiC 1023. Lab No. 4.

147
Figure 57. SEM micrograph of particle. Magnification 20,000x; scale

bar in lower right of micrograph indicates 1 /zm length.

Sample: SiC 1023. Lab No. 4.

148
5.2.1.4. Silicon Powder

Figure 58. SEM micrograph of powder as -received. Magnification lOOOx;

scale bar in lower right of micrograph indicates 10 /xm

length. Sample: Si 1001. Lab No. 4.

149
SEM micrograph of dispersed

scale bar in lower right of

length. Sample: Si 1001.

powder. Magnification lOOOx;

micrograph indicates 10 urn Lab No. 4.

150
SEM micrograph of particle. Magnification lO.OOOx; scale

bar in lower right of micrograph indicates 1 /zm length.

Sample: Si 1001. Lab No. 4.

151
SEM micrograph showing detail of particle. Magnification

20,000x; scale bar in lower right of micrograph indicates

urn length. Sample: Si 1001. Lab No. 4.

152
5.2.1.5. Yttria-Zirconia Powder

SEM micrograph of spray-dried powder as-received.

Magnification lOOx; scale bar in lower right of microgr

indicates 100 /im length. Sample: YSZ AEO 11. Lab No.
SEM micrograph of single spray-dried particle.

Magnification lOOOx; scale bar in lower right of micrograph

indicates 10 /im length. Sample: YSZ AEO 11. Lab No. 4.

154
Figure 64. SEM micrograph of powder after dispersal in water and

partial disruption of agglomerated particles. Magnification

5000x; scale bar in lower right of micrograph indicates 10

fim length. Sample: YSZ ORO 12. Lab No. 18.

155
2 0 0 nm

Figure 65. TEM micrograph of primary particles. Sample: YSZ 0514.

Lab No. 22.

156
157
5.3. PARTICLE MORPHOLOGY - QUANTITATIVE DATA

5.3.1, Scanning Electron Microscope. Wadell Diameter

The Wadell diameter is defined as the diameter of a circle having the same

projected area as the image of the particle.

Image analysis of scanning electron microscope (SEM) micrographs yields a

number based size distribution, from which a mean thickness can be calculated

as

<x>N = SxdN/SdN , (3.3)

where dN is the number of particles with the interval of linear dimension x to

x+dx. A mass- or volume -based distribution can be estimated by assuming that

the out-of-plane dimension is equivalent to the in-plane dimension. The mean

size obtained for the estimated mass distribution is

<x>M = SxMN/SxMN (3.4)

where dN is the number of particles with the specific characteristic linear

dimension between x and x+dx, and where sums over all sizes is implied. The

geometric standard deviation is defined with respect to a lognormal

distribution

5.3.2 Silicon Nitride Reference Powder

Table 5.3.2.1 Experimental Mean, Number Distribution

Lab No

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 0.4

Table 5,,3.2.2 Experimental Mean, Mass Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average Standard

Value Deviation

23 1 1.39

158
Table 5.3.2.3 Standard Deviation (a ) for the Size Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Averag

Value

e Standard

Deviation

23 1 2.2

5 3 3 Silicon Nitride Test Powder

Table 5,,3,.3 . 1 Experimental Mean, Number Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 2 0.4 0.5 0.45 0.05

Table 5.,3..3 . 2 Experimental Mean, Mass Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 2 1.03 1.06 1.05 0.02

Table 5,,3..3 .3 Standard Deviation (ag) for the Size Distributi

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 2 1.8 2.0 1.9 0.1

159
5.3.4.

Table 5.3.4.1

Silicon Carbide Powder

Experimental Mean, Number Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 3 0.32 0.41 0.36 0.05

Table 5 .3 .4 .2 Standard Deviation (o^)

(Number)

for the Size Distribut

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 3 1.64 1.96 1.79 0.16

Table 5,,3 .4 .3 Experimental Mean, Mass Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 3 0.79 0.90 0.84 0.06

Table 5.,3,,4,,4 Standard Deviation (ag)

(Mass)

for the Size Distribut:

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 3 1.61 1.75 1.68 0.070

160
5.3.5.

Table 5.3.5.1

Silicon Powder

Experimental Mean, Number Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 6 1.06 1.23 1.15 0.06

Table 5,.3 . 5 .2 Standard Deviation {o^)

(Number)

for the Size Distribut

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 2.10 2.33 2.24 0.09

Table 5.,3,,5 .3 Experimental Mean, Mass Distribution

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 6 4.89 7.15 6.14 0.83

Table 5. 3. 5,.4 Standard Deviation {o^)

(Mass)

for the Size Distribut:

Lab No.

No. of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

23 6 1.78 2.04 1.94 0.09

161
5.3.6.

Table 5.3.6.1

Yttria-Zlrconia Powder

Experimental Mean, Number Distribution

T „ V XT „ Lab No

No. of

Values

Minimum Maximum

Value Value

Average Standard

Value Deviation

23 1 0.3

Table 5.,3.6.2 Experimental Mean, Mass Distribution

Lab No.

No. of

Values

Minimum Maximum

Value Value

Average Standard

Value Deviation

23 1 2.27

Table 5.3.6.3 Standard Deviation (a„) for the Size Distribution

Lab No.

No. of Minimum Maximum Average Standard

Values Value Value Value Deviation

23 1 -- -- 2.88

5.3.7. SEM, Size Measured as Maximum Particle Dimension

5.3.7.1. Silicon Nitride Reference Powder

Table 5.3,,7.1 Experimental Mean, Number Distribution

Lab No.

No. of Minimum Maximum Average Standard

Values Value Value Value Deviation

13 12 0.6 1.0 0.8 0.1

162
Table 5.3.7.1.1 Experimental Mean, Mass Distribution

Lab No.

No. of Minimum Maximum

Values Value Value

Average Standard

Value Deviation

12 1 ..... 1.5

5.3.7.2 Silicon Nitride Test Powder

Table 5,,3,.7 .3 Experimental Mean, Mass Distribution

Lab No.

No. of Minimum Maximum

Values Value Value

Average Standard

Value Deviation

12 1 1.2

5.3.7.3, Silicon Powder

Table 5,,3,.7 .3 Experimental Mean, Mass Distribution

Lab No.

No. of Minimum Maximum

Values Value Value

Average Standard

Value Deviation

12 1 2.1

5.3.7.4. Yttria-Zirconia Powder

Table 5. 3. 7 .4 Experimental Mean, Number Distribution,

As -Received Powder

Lab No.

No. of Minimum Maximum

Values Value Value

Average Standard

Value Deviation

18 6 27.49 39.36 33.98 4.14

163
5.4. REFERENCES (For Chapters 2-5)

1. McSkimin, H. J.; Bond, W. L. ; Buehler, E.; Teal, G. K. Measurement of

Elastic Constants of Silicon Single Crystals and Their Thermodynamic

Constants. Phys . Rev. 83: 108; 1951.

2. Tibault, N. W. Morphological and Structural Crystallography and Optical

Properties of Silicon Carbide, Part II. Am. Mineral. 29: 327-62; 1944.

3. Ruddlesden, S. N.; Popper, P. On the Crystal Structures of Nitrides of

Silicon and Germanium. Acta Cryst. 11: 465-68; 1958.

4. Turkdogan, E. T.; Bills, P. M. ; Tippett, V. A. Silicon Nitrides : Some

Physicochemical Properties. J. Appl. Chem. 8: 296-302; 1958.

5. Allen, T. Particle Size Measurement, 3rd Ed. London: Chapman and Hall;

1981. Chapter 1, Table 1.1.

6. Allen, T. Particle Size Measurement, Op cit. pp. 215-45, 267-70,

283-87.

7. Stanley-Wood, N. Survey of Some of the Current Instruments and Methods

Available for Particle and Powder Characterization. Part 3. Powder

Metallurgy Internatl . 9 [2]: 138-142; 1977.

8. Dragoo, A. L. ; Robbins, C. R. ; Hsu, S. M. A Critical Assessment of

Requirements for Ceramic Powder Characterization. Advances in Ceramics,

Vol. 21. Columbus, OH: Am. Ceram. Soc; 198. pp. 711-20.

9. Allen, T. Particle Size Measurement. Op cit. Chapter 12.

10. Hausner, H. H. Handbook of Metallurgy . New York: Chemical Publishing;

1973.

11. Irani, R. R. ; Callis, C. F. Particle Size: Measurement Interpretation

and Application . New York: John Wiley; 1963.

164
6. CHEMICAL COMPOSITION OF POWDERS

A. L. Dragoo and S. G. Malghan, NIST

6.1 INTRODUCTION

The importance of measurement and control of the chemical composition of

starting powders for advanced structural ceramics is widely recognized, but

accurate determination of important chemical species remains problematical.

Two examples are:

(1) the presence of oxide in SiC and Si3N4 powders which alter their

sinterability , and

(2) the presence of Ca, and other glass formers, in SisN^^ which reduce

the high- temperature strength of the ceramic.

Chemical analyses which require the dissolution of the material are

complicated by the general chemical refractiveness of the compounds so that

failure to recover all of the component of interest as a reaction product and

contamination by the apparatus, such as pressure bombs, are problems which

require special attention.

The lEA/Annex II Subtask 2 study provides a comparison of methods used for the

determination of major constituents, major impurities (> ICQ ppm) , trace

elements, and volatile adsorbed species, such as water. Results of

determination of volatilized absorbed species are presented in Chapters 11 and

12. The present discussion provides a summary description of the analytical

methods, compares results within a method and between methods for a given

component, and examines the possible sources of variance in the analytical

procedures used to determine nonvolatile components of the powders.

Analytical Procedures

Analytical procedures generally consist of five discrete steps:

1. Sampling

2. Sample preparation

3 . Measurement

4. Data processing

5. Analytical process correction, involves testing, controlling

and eventually correcting one or more of the above processing

steps

.

Sampling and Sample Preparation

A description of the preparation of the lEA samples (vials) is given in

Section 1.3. of this report. The extraction of analytical samples from the

lEA samples was carried out at the discretion and according to the method of

the analyst. Use of the entire lEA sample was recommended whenever possible,

otherwise random sampling from the lEA sample was recommended.

165
Sampling errors, such as contamination and fractionation, may arise at three

steps in sampling process: (1) during the manufacture and handling of the

powder, (2) during the taking or the division of samples for testing, and (3)

during the taking of analytical samples by the analyst. Errors associated

with "(1)" are expected to appear in overall large variability in the results

for the population of all laboratories reporting results; whereas "(2)" and

"(3)" are expected to appear as a large excursion of the result for a single

group of samples or of a single sample, respectively, from the mean value for

all samples. Since a record of the powder division history was maintained

during the preparation of lEA samples, the validity of "(2)" may be inferred

if two or more samples from the same division pathway were analyzed in the

round-robin. A type "(3)" error may be expected if types "(1)" and "(2)" can

be ruled out, or if the laboratory in question has run replicate samples from

the same TEA sample and has obtained widely different results. A type "(3)"

error is likely to result if the analyst did not carefully sample randomly

throughout the lEA sample but instead extracted a grab sample. However, a type "(3)" error can be easily confused with an error arising in Step 2,

Sample Preparation.

Measurement, Data Processing and Testing

The variance associated with Step 3, Measurement, can be estimated from

replicate runs on the same sample. Such errors can be reduced in laboratory

practice by frequent running of a control sample and the use of control charts

to verify instrument and operator performance. Similarly, with regard to Step

4, Data processing, replicate readings of a chart, meter or digital display of

an instrument output provide an estimate of the variance of the reading of the

instrument response to the phenomenon measured.

An error occurring in Step 5, Analytical Process Correction, most likely

appears as a bias which is evident in the deviation of all results of a

particular laboratory. However, since analytical standards are not presently

available for the materials used in this study, assessment of this bias is not

generally possible. Further, standard analytical practices have not been

established in many cases, nor are common; nor the best practices widely known

or used. Consequently, we were too frequently informed that analysts used the

same practice for all materials, with little regard to chemical and analytical

problems introduced. It is hoped that the present study, and the comparison

of practices which it has made possible, will result in an improvement in

analytical practices for SisN^, SiC, Si and ZrOg.

Methods for Chemical Characterization

The methods presented for each type of analysis are arranged in the general

order: whole sample methods, such as neutron activation analysis and x-ray

fluorescence; spectrochemical methods requiring dissolution of the sample,

with absorption followed by various emission types; electrochemical methods;

ion chromatography; gravimetry; and volumetric analysis.

The various spectrochemical methods can be classified on the basis of (1)

whether the mode of analysis uses the characteristic emissions or absorptions

by the sample, (2) type of excitation, (3) form of the sample preparation, and

166
(4) the analytical range of the analysis, including the number of elements and

the concentration range. The methods included in this study are compared in

Table 6.1.1 with respect to the four categories. The section in which the

method is discussed in this report is given in the left hand most column along

with the acronym. The acronyms TCP (inductively coupled plasma) and DCP (dc

plasma jet) when used alone are assumed to refer here to their use in the

emission mode; when used in the absorption mode, these acronyms are usually

prefixed to AAS (atomic absorption spectroscopy) . Flame-AAS is used to

designate flame absorption spectroscopy.

Table 6.1.1 Comparison of Spectrochemical Methods for Elemental Analysis

METHOD TYPE EXCITATION SAMPLE PREP'N RANGE

XRF E

(4.2.1.1.)

X-rays Homogeneous powder

compacts

,

Major components

Major impurities

Z > 22 (Ti) air,

13 (Al) in He,

9 (F) in vac.

OES E

(4.1.1.3.)

AAS A

(4.2.1.2. )

ICP E or A

(4.2.1.3.

)

DCP E or A

(4.2.1.4.)

Electric Powder sample

arc

Flame

DCP jet

Solution

Inductively

coupled

plasma

DC plasma

Solution

Solution

General, use; most

elements; sensitivity varies

General use; most

elements; sensitivity varies

General use; most

elements; sensitivity varies

General use; most

elements; sensitivity varies

E - emission, A - Arc, Z - atomic number

Some methods described here have a sufficiently large dynamic range to enable

them to be used for more than one range of concentrations. These instruments

are discussed once for one component range and mentioned with supplemental

descriptions as needed for other ranges for which they are relevant. For each

component range, the instruments used in the study are described and then the

measurement results are presented and compared.

167
7. MAJOR CHEMICAL COMPONENTS

A. L. Dragoo, S. G. Malghan, R. G. Munro , S. M. Hsu; NIST

7.1. METHODS FOR SILICON IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

The principal methods investigated were inductively coupled plasma-emission

spectroscopy, dc plasma-emission spectroscopy and gravimetric analysis.

Results also were reported for measurements by x-ray fluorescence

spectrometry, optical emission spectroscopy, atomic absorption spectrometry

and coulometric titration.

7.1.1. X-Ray Fluorescence Spectrometry (XRF) ^• ^

Use and Significance

X-ray fluorescence spectroscopy is primarily used for semiquantitative and

quantitative determination of major elemental constituents and major

impurities with atomic number greater than 9 (vacuum operation) . XRF is

capable of performing rapid, high-quality multielement determinations on a

single sample preparation. Reference standards are required for the

conversion of x-ray intensities to concentrations.

Instrvunent and Experimental Parameters

The XRF method uses xray to excite the characteristic x-ray fluorescence of

elements in a sample. Two methods are used to analyze the fluorescent

radiation:

(1) In energy-dispersive or fluorescence analysis, the spectrum of

fluorescent radiation emitted by the sample is separated on the

basis of energy using a Si (Li) detector and a multichannel

analyzer (MCA), This method is widely used in industry.

(2) In wavelength- dispersive analysis, the fluorescent radiation from

the sample is collimated and directed on to an analyzing crystal.

Radiation diffracted by the crystal is detected by a counter which

is moved along the spectrometer circle.

The excitation radiation must be of slightly higher frequency (shorter

wavelength) than that of the characteristic fluorescence of interest. In

practice, the excitation radiation is produced using an x-ray tube with a tungsten or other heavy metal target for heavy elements or with a chromium

target for light elements. Energy-dispersive spectrometers may use the

monochromatic fluorescent radiation from a secondary fluoresces rather than

the direct radiation from an x-ray tube.

The dynamic range of XRF is 0.2 A (62 keV) to 20 A (0.6 keV) . Resolution of

an energy-dispersive spectrometer improves with shorter wavelength or greater

energy. For wavelength- dispersive spectrometers the reverse is true.

168
Preparative methods reported are summarized in Table 7.1.1.1. Although XRF

can be carried out nondestructively , the most accurate results are obtained by

dissolving the sample in a glass matrix. Typically the sample is mixed with a

material such as lithium tetraborate, with the possible addition of a heavy

absorber such as barium carbonate, fused and cast into a glass bead. Pressed

powder samples may also be used, but the uniformity of the mixing in this case

may be somewhat less precise. The principle in sample preparation is to

obtain samples which will totally absorb all of the incident x-rays and which

will contain a uniform dispersion of the fluorescing elements.

Table 7.1.1.1 Preparative Methods Used for Total Silicon Analysis by X-ray

Fluorescence Spectrometry

LAB METHOD

5 First melt with Li2C03 + B2O3 ; second melt after

addition of more B2O3 and of Lil.

25 Oxidation with CaO; Li2B^07 bead.

Calibration and Standards

To accurately derive elemental concentrations from the measured fluorescent x- ray intensities, it is necessary to correct the intensities for matrix

absorption and enhanced excitation. The first effect arises from secondary

absorption of the fluorescent radiation by the sample. The second effect

results from the stimulated emission of secondary fluorescent radiation by the

primary fluorescent emission of the sample. Corrections can be made for these

effects by use of an empirical calibration curve or by fundamental calculation

of parameters

.

A variety of rocks , minerals and ores are available from the National

Institute of Standards and Technology as compositional references for both

multi- component and impurity concentrations. In addition, SRM 477 is a glass

fluorescence source which is used for determining detector window absorption

in semiconductor x-ray spectrometers.

7.1.2 Atomic Absorption Spectrometry (AAS)

Use and Significance

Flame atomization and electrically heated furnace atomization AAS have become

among the most widely used analytical procedures for the determination of

metallic elements (at least 67 elements) . Inductively coupled plasma and dc

plasma jets, see Sections 7.1.3. and 7.1.4. below, respectively, can also be

used as atomization sources for this method. Flame atomic emission

spectroscopy also exists, but since it was not used in this study, it will not

be considered further here.

169
Instrumental and Experimental Parameters-"^'^

Chopped monochromatic light is passed through the flame to a detector. The

source radiation consists of a line spectrum of the element of interest. The

sources commonly used for AAS are (1) hollow- cathode discharge tubes, (2)

metal-vapor arc lamps, and (3) electrodeless discharge tubes. A linear flame

with multiple beam passes or more than one linear flame may be used to

increase the pathlength through the flame. Most flame AAS studies have been

performed with air- acetylene flames, although oxyhydrogen, oxyacetylene

nitrous oxide - acetylene and other flames have been used. Continuum sources

also can be used where high sensitivity is not required and if the

monochromator has a narrow spectral bandwidth. In analytical work, the

fraction of radiation absorbed at the line center is measured rather than the

integrated intensity. Thus, a narrow line source is desirable. Single beam

optics have been used on most commercial systems. This requires a wellregulated source of power supply and a longer warm up time for the source

lamp. Data output is usually to a meter, recorder, digital readout, or

computer

Parameters which may influence performance include the following: aspirating

gas flow rate; fuel- to -oxidant flow ratio; solution flow rate into the flame;

orifice size; temperature of chamber, if a constant temperature chamber is

used; height of measurement in the flame; entrance optics, only if optics can

be varied; monochromator slit width; light power source; and pathlength

through flame

The material to be analyzed is dissolved and nebulized into a gas stream which

carries the aerosol into the flame. Since ceramic powders are often not

easily decomposed, drastic decomposition conditions such as fluxes or strong

acids must be employed. In geochemical practice, it is customary to decompose

the material with a borate melt, followed by dissolving in a solution buffered

with citric or tartaric acid. These solutions have been reported to be

unstable.'^ One laboratory (14) which reported the use of AAS decomposed

silicon nitride samples in NaOH-Na202 melts. Lab (13) reported that strong

NaOH solutions have been presumed to yield unstable AAS measurements and to

attack the burner.

Running a blank solution to establish a correction for background absorption

is recommended if a solution has a high ionic strength. A background

correction can also be made by measuring the intensity of a second nonabsorbed

line, such as a signal from a deuterium lamp.

Results and Discussion

The average result for AAS is compared with other spectrochemical methods in

Table 7.1.2.1. One laboratory reported results for two samples of the SNR

SigN^ and one sample of SNT SigN^ in this study. Good agreement between

results was found with respect to the samples for the SNR powder and with

respect to results reported for other methods. Although the high precision

for the analysis of N in the SNR powder by AAS and the close agreement with

the XRF determination lend encouragement toward the further use of AAS , the

limited number of determinations reduces the overall confidence in the present

result

170
Conclusions

Determinations of Si content of SigN^ by AAS are comparable to those obtained

with XRF, ICP and DCP . However, the number of results was insufficient for an

adequate evaluation of this method.

TABLE 7.1.2.1 Determination of Si in Silicon Nitride and Silicon Carbide

by Spectrochemical Methods . Concentrations are in percent

by weight.

NUMBER OF

MATERIAL METHOD LABS SAMPLES MEAN STANDARD DEVIATION

SigN^ (SNR) XRF 2 2 59 .7

AAS/Flux 1 2 59 .5 0,.0^

ICP/Flux 2 5 59 .2 0,,8

ICP/Acid 1 1 59 .4

ICP/NS^ 1 2 58. 7 1,.0

DCP /Fl 11V 0 « 1

J.

.

7

SigN^ (SNT) XRF 2 3 59,.5 0.,3

AAS/Flux 1 1 60,.0

ICP/Flux 2 5 59,.8 0,.5

ICP/Acid 1 1 60,.2

DCP/Flux 2 2 61..0 1.,9

SiC XRF 1 6 69,,1 0. 2

ICP/Flux 2 4 69,,2 0. 2

ICP/Acid 1 1 70,,1

^ Could not be estimated

^ NS- not specified

171
7.1.3. Inductively Coupled Plasma (ICP)

Use and Significance

Inductively coupled plasma-atomic emission spectroscopy (ICP) uses the

excitations of atoms in a plasma to obtain their characteristic emissions. It

has found wide industrial application for the quantitative elemental analysis

of materials since it provides a determination of major, minor and various

trace elements. The material to be analyzed is dissolved, and the solution is

then injected as an aerosol into the axial channel of a toroidal argon plasma.

Dissolution of the sample and preparation of solutions are critical steps in

the accurate use of this method.

Instrumental and Experimental Parameters*'^

The operating parameters are rf power, gas flow rates to the nebulizer and the

plasma. Ambient conditions in the axial channel may be characterized by gas

temperatures of 4000-6000 K, ionization temperatures of approximately 8000 K,

and electron number densities on the order of lO-"^^ cm"'^ . Under these

conditions a high yield of singly charged, monatomic ions is obtained for most

elements . Quantitative determination of an element requires the use of

spectral line intensities which are selected by optimizing the criteria of low

detection limit, low background equivalent concentration, and absence of

interfering lines of major elements.

Sample preparation is perhaps the most important experimental consideration

since accurate determinations require the quantitative recovery of the

elements of interest from the solid samples. Analysis of ceramic materials

which are chemically very stable may pose special analytical problems and most

of the analytical error may be assignable to the preparation of analytical

samples. Due to the drastic conditions required to achieve dissolution, the

determination of blank values is important.

Two approaches for dissolution of ceramic samples were used in this study:

1. fusion of the sample in a borate or carbonate, followed by the

dissolution of the fluxed material in an acid solution;

2. dissolution of the sample in an acid mixture, such as HF plus HNO3

Fluxes used for the analysis of Si -based materials included sodium carbonate

with boric acid and lithium metaborate (LiB02) .

Acid dissolution was carried out in a pressure bomb; both teflon or glassy

carbon were investigated as liners for the bombs. The various methods are

summarized in Table 7.1.3.1.

Results and Discussion

For the each material analyzed in this study, three or more labs reported

determinations, two of which used flux dissolution of the materials. Good

172

I

I'
agreement between results was found in all cases, as evidenced by the results

given in Table 7.1.2.1.

Table 7.1.3.1 Preparative Methods for Analysis of Total Silicon in Silicon

Nitride, Silicon Carbide and Silicon by Inductively Coupled

Plasma Emission Spectroscopy

LAB $ METHOD

1 Not specified.

6 Lithivun metaborate (LiBOz) fusion at 1000 °C for 2h;

quenched into a solution of H2O2 + HNO3 + tartaric acid.

15 HF + HNO3, 150 °C, pressure decomposition.

21 Decomposition with Na2C03 + H3BO3

.

Conclusions

Determinations of silicon content of SisN^ and SiC by ICP are comparable to

those obtained with XRF, AAS and DCP. Flux and acid decomposition methods

also appeared to yield comparable Si concentrations in the cases of the two

SisN/, analyses and of the one SiC. However, the number of results reported

was insufficient for an accurate comparison of methods.

7.1.4. Direct-Current Plasma (DCP) - Emission Spectroscopy

Use and Significance

Direct-Current Plasma Jet-Emission Spectroscopy (DCP) is very similar to the

flame emission spectroscopy with the exception that the excitation source is a

dc plasma jet. An analyte solution is nebulized, similar to the manner of

ICP, or a finely ground powder is dispersed in a gas stream and carried into

the plasma jet. Chambers yielding very stable arcs and good gas mixing have

been built in recent years. As with ICP, dissolution of the sample and

preparation of solutions for analysis are critical steps in this method.

Instrximent and Experimental Parameters^

The plasma jet is formed between a graphite ring anode and a graphite ring

cathode with the jet passing through the orifice of the cathode. Nitrogen,

air or inert gases may be used for the plasma. The sample is injected along

the axis of the jet. Stabilizing gases are introduced into the water-cooled

chamber which encloses the space between the anode and cathode. Special

burner designs have been developed to achieve a stable plasma, to evaporate an

aerosol completely, and to achieve sufficient penetration of the aerosol into

the plasma by turbulent mixing of the aerosol into the gas stream.

173
The emission spectra are analyzed with a prism or grating monochromator

Photodetection is usually carried out with a vacuum single-stage or, more

commonly, multistage phototube. The output current is amplified and then fed

to a readout device

Instrumental parameters include flow-rates for the nebulizing gas, carrier

gas, plasma gas and stabilizing gas; voltage and current to the plasma jet; as

well as parameters of photodetector and readout device.

Experimental considerations are similar to those for TCP. In this study, only

flux decomposition was used to prepare samples for DCP analysis. Experimental

conditions for dissolution and analysis of SisN^, were discussed by Davis and

Merkle^ and by Czupryna and Natansohn^.

Results and Discussion

DCP was used for analysis of total Si in Si3N^ in this study. Examination of

the results given in Table 7.1.2.1 indicates that measurements by DCP are in

agreement with those obtained by XRF and ICP; however, the precision of the

result by DCP is perhaps worse than that for the ICP results: DCP gave a

relative standard deviation of 3%, whereas, that by ICP was about 1%.

Conclusions

Determinations of silicon content of Si3N^ by DCP are comparable to those

obtained with XRF and ICP. The between laboratory precision obtained with

this method appears to be somewhat poorer than that for XRF and ICP. However,

the data are inadequate in all cases for an accurate comparison of precision

to be "made

7.1.5. Gravimetry

Use and Significance

Gravimetry refers to the determination of a component by isolation of it in a

solid form which can be weighed, thus providing an independent determination

of that component. Estimation of the amount of a component by subtraction of

the amounts of all other components from the total weight of the sample does

not constitute an independent measurement, albeit such an estimate may be

useful for the purpose of comparison.

Components, such as Si, which can be readily converted to a stable oxide that

can be recovered and weighed, may be determined by gravimetry. Much depends

upon the procedure required to separate the component and to precipitate or

collect in such a manner as to exclude other chemical species.

Instrument and Experimental Parameters

No special instrumental considerations are required.

Decomposition of the nitrides and carbide was carried out in borate or

174
carbonate fluxes, followed by dissolution in nitric or hydrochloric acids and

precipitation of Si02 or fumed in perchloric acid to form Si02.

Results and Discussion

Results are generally consistent with those from spectrochemical methods. The

large standard deviation for Si in SiC suggests that all of the Si may not

have been effectively recovered with the chemical methods used. Refer to

Table 7.1.5.1.

Conclusions

Data were insufficient for statistical analysis of variances in the cases of

SNT SisN/, and SiC. For the two silicon nitride powders gravimetry yielded

results which were consistent with those from the spectrochemical methods.

The gravimetric result for SiC was about 2% low with respect to those results

and has much lower precision. The reliability of this method for SiC needs to

be established.

TABLE 7.1.5.1 Determination of Si in Silicon Nitride and Silicon Carbide by

Gravimetric Determination as SIO2. Concentrations are in

percent by weight.

MATERIAL LABS

NUMBER

SAMPLES

OF

MEAN STANDARD DEVIATION

SigN^ (SNR) 3 15 59.42 0.50

(SNT) 2 3 59.32 0.19

SiC 2 3 67.66 1.56

7.2 METHODS FOR NITROGEN IN SILICON NITRIDE

Nitrogen in silicon nitride was determined primarily by combustion analysis.

Some determinations were made using electrochemical means of detection and by

Kjeldahl analysis, but these also required decomposition of the powder and,

hence, were very similar to the combustion method in regard to decomposition

chemistry.

7.2.1. Combustion Method

Use and Sigiiificance

Combustion, or fusion, is used when the chemical component can be liberated in

a gaseous form from the sample by a decomposition reaction. Usually, a

reactive flux is used. The quantity of gaseous product obtained is determined

from a property of the gas. This method is widely used in industrial

175
laboratories for the analysis of C, 0, N and S in SisN^, SiC and Si.

Instrximent and Experimental Parameters

Measurement of quantity of gas liberated was not clearly specified in most

cases but is presumed to have been by the usual method of measuring the

thermal conductivity of the product gas. Manufacturers of instrumentation for

this method supply N-containing pellets for calibration of their instruments.

Method of decomposition was not identified by most labs. Two labs reported

use of graphite crucibles, with one of those labs reporting the encapsulation

of the sample in Sn/Ni and comparison against an Si3N4 laboratory standard.

Results and Discussion

The average results for determinations of N in SNR SigN^, SNT SigN^, SiC and Si

by combustion analysis are compared in Table 7.2.1.1 with results obtained by

other methods.

For the case of SNR, 4 labs reported a total of 21 determinations which were

in very close agreement (s.d. of 0.24). Two other labs reported results which

were not included here. One of the laboratories reported a single low value

of 32.10, which is suspected to be due to a very large measurement error from

loss or failure to recover all of the N present. The other laboratory

reported results for 11 samples, a single determination for each sample, with

a mean of 40.80 and s.d. of 0.48. From the standpoint of stoichiometry , a

value greater than 39.94 is not expected. Further, the difference between the

two mean was significantly different. Thus, the high results are not included

in Table 7.2.1.1.

TABLE 7.2.1.1 Determination of N in Silicon Nitride, Silicon Carbide,

Silicon and Yttria-Zirconia by Combustion. Concentrations are

in percent by weight.

NUMBER OF

MATERIAL DETECTION LABS SAMPLES MEAN STANDARD DEVIATION

SNR TO 9 15 38.23 0.29

SNT TC 8 19 38.95 0.78

SiC TC 4 6 0.076 0.007

Si TC 4 7 0.04 0.03

YSZ TC 1 2 0.027 0.004

176
Conclusions

Determination of the N content of silicon nitride materials by decomposition

followed by detection and measurement by thermal conductivity measurements is

capable of high precision. However, care must be taken to recover all of the

N and to determine that the instrument is correctly calibrated. Development

of a reference material for verification of measurements is desirable.

7.2.2. Kieldahl Analysis

Use and Significance

Kjeldahl analysis is a neutralization titration method which is the standard

means for the determination of N in a variety of materials . The

neutralization technique is carried out using a standard solution of strong

acid or strong base.

Instrument and Experimental Parameters

Nitrogen in the material is liberated as ammonia, which is recovered and the

amount determined. Recovery and determination are accomplished either by:

(1) collecting the ammonia in a known quantity of standard acid and

back- titrating with a standard base; or

(2) collecting the ammonia in an unmeasured excess of boric acid and

the borate ion formed is titrated back to boric acid with a

standard solution of hydrochloric acid.

Decomposition of the nitrogenous material in hot sulphuric acid is used in

many cases. However, in this study, one laboratory reported the use of a LiOH

flux and two other laboratories reported the use of hydrofluoric acid or

hydrofluoric acid with nitric acid in a pressure bomb.

Results and Discussion

For the SNR, a total of two determinations were reported by two laboratories,

with a mean value of 38.66. However, for the SNT, 11 determinations were

reported by three laboratories which used four samples . The mean value and

standard deviation were 38.91 and 0.12, respectively.

These results are comparable to those obtained with the other methods of

detection which are preceded by sample decomposition since similar

decomposition chemistries were used. The precision of this method appears to

be slightly better than that obtained by decomposition followed by measurement

of the N2 with thermal conductivity.

Conclusions

Nitrogen concentrations were determined with good precision in silicon

nitride. The somewhat more extensive chemical operation required by Kjeldahl

analysis as compared to the decomposition- gas detection methods may be more

177
than offset by the better precision obtained. This method may be preferred

for high-quality analyses or when reference measurements are required.

Further, testing of the method is recommended to establish a fully evaluated

procedure and to obtain good estimates of the sources of variance.

7.2.3. Electrochemical Methods

Under the general category of Electrochemical Methods are included coulometry,

specific ion potentiometry , and potentiometric and argentometric titrations.

Use and Significance

Electrochemical methods do not find as wide application as the spectrochemical

methods described above, since after desolution of the material, further

chemical steps may be required to remove interfering chemical species.

However, where an electrochemical method has been established in a laboratory,

its use may yield very reliable results. Furthermore, the determination may

be directly related to the concentration of the analyte present, without the

introduction of a calibration.

Instrument and Experimental Parameters

Coulometry

Coulometry or coulometric titrations measure the quantity of electricity (in

Coulombs) passed to an electrode by a chemical reaction involving the ion of

interest. Two techniques are in use, 1. controlled potential coulometry,

2. constant current coulometry.

If the reaction is 100% current efficient, then the passage of one Faraday of

electricity will cause the reaction of one equivalent of material. The

concentration of an ion is usually determined by one of the following methods:

a. measurement of the current integrated over the elapsed time,

b. measurement of the change in weight of an electrode due to plating

out of an element,

c. measurement of the charge transfer in the opposite direction in a subsequent circuit after the coulometric reaction of interest has

been carried out.

The method is particularly suited and accurate in the range from milligram to

microgram quantities of material, hence it is suitable for trace element

analysis. It is highly useful for the determination of volatile reactants

(CI, Br and I) and unstable reactants (Ti^"^, Cr^"^, Cu"*" and Ag^"^) .

Standards are not generally required since the determination is referable to

fundamental quantities (current and time)

Ion Selective Potentiometry

Ion selective potentiometry measures the activity of a specific ion - i.e.,

the thermodynamically effective free -ion concentration and not the total

178
concentration - study, specific

silicon nitride

by direct measurement

ion potentiometry was

of an electrode potential,

used for the determination

In this

of F" in

Electrodes for specific ionic activity determinations can be grouped as:

a. glass electrodes,

b. solid-state and precipitate electrodes,

c. liquid- liquid and membrane electrodes,

d. enzyme and gas sensing electrodes.

All of these yield potentials that can be adequately described by the

classical Nernst equation or its modifications.

Selective ion electrodes are subject to interferences due to method and

electrodes . Method interferences occur when the sample prevents the probe

from sensing the ion of interest. For example, in acid solutions, F" forms

complexes with H^O'*' which are not measured by the electrode. Electrode

inferences arise when the electrode responds to ions in the solution other

than the ion of interest.

Specific ion activity is obtained by use of a calibration chart to convert

measurements of pH or mV or by direct reading from a calibrated meter. For

concentrations less than 10"'' M, calibration procedures must use solutions of

known activity or concentration, depending on which parameter is required.

Potentiometric Titration

Changes in electromotive force (emf) of a cell with the addition of a titrant

can be used to locate the equivalence point of a reaction. Potentiometric

titrations are particularly useful when detection of the endpoint of the

titration is obscured by turbidity, fluorescence, opaqueness, highly colored

solutions or when a visual indicator is not available. Automatic titrators

are available which permit precise control and continuous recording of the

process to be carried out.

The solution containing the unknown is titrated against a standard solution

until the equivalence point, as determined by a rapid change in electrode

potential, is reached. The concentration of the unknown is calculated from

the volume of standard solution added. The determination is expedited, if the

approximate concentration of the unknown is known, by adding standard solution

rapidly until in the neighborhood of the equivalence point and then carefully

titrating through the equivalence point. Automated systems can be programmed

to carry out such a procedure

.

Argentometric Titration

Argentometric titrations are a specific category of potentiometric titration

in which silver-related equilibria are employed. Two specific equilibria, are

associated with the solubility of AgCl and with the formation of the Ag(CN)2"

complex. In the case of AgCl equilibrium the emf associated with the CI.

concentration is measured with an electrode "of the second kind", i.e., an

179
electrode in which a cation is in equilibrium with its sparingly soluble salt.

At the equivalence point of the titration:

[Ag+] = [ci-i = yK3p

Ion selective electrodes can be used in conjunction with the titration process

to determine the cation (Ag"*") or anion concentrations.

Experimental considerations are similar to those for potentiometric titration.

Results and Discussion

One laboratory reported the use of potentiometric titration to determine the

concentration of nitrogen in both types of silicon nitride. The samples were

reacted with a LiOH flux and the nitrogen recovered as anmionia. In case of

SNR, three samples were analyzed; two samples were found to have Nconcentrations comparable with values found by other methods, mean of 37.9,

but one sample was significantly low. For SNT, two specimens of the one lEA

sample were analyzed with a mean of 38.15.

Conclusions

The number of results are insufficient to permit valid comparisons and

inferences to be made. Further evaluation of this method is needed.

7.3. METHODS FOR TOTAL CARBON IN SILICON CARBIDE

Total carbon in silicon carbide was carried out primarily by combustion

analysis. Coulometric titration also was used. One gravimetric measurement

was reported.

7.3.1. Combustion (See 7.2.1.)

Instrument and Experimental Parameters

Carbon in the sample which is liberated as CO2 is determined by measuring the

infrared absorption of a precise IR wavelength. A reaction is used which

liberates C as CO or CO2 . The CO is further oxidized to CO2 before reaching

the IR detector.

Results and Discussion

The average result for determination of total carbon in SiC is presented in

Table 7.3.1.1, along with determination of carbon impurities in silicon

nitride, silicon and yttria- zirconia . The limited amount of data does not

permit an accurate estimate of the sources of variance - within laboratory

(sample, determination) and between laboratories. Two laboratories reported

multi - determi itions on a single lEA sample, with a standard deviation of

about 0.05. le l-boratory reported single measurements on two samples with a

standard d vie ;ion of about 0.4. Apprc ima'cely, half of the observed variance

180
may be assigned to between- laboratory variance. The approximately equally

large sample- to -sample and between- laboratory variances suggest that either

significant sample- to -sample inhomogeneity was present or that

TABLE 7.3.1.1 Determination of C in Silicon Nitride, Silicon Carbide,

Silicon and Yttria-Zirconia by Combustion. Concentrations are

in percent by weight.

NUMBER OF

MATERIAL DETECTION LABS SAMPLES MEAN STANDARD DEVIATION

SNR IR 13 24 0.15 0.02

SNT IR 12 23 0.13 0.03

SiC IR 5 6 29.62 1.00

Si IR 6 9 0.08 0.02

YSZ IR 3 4 0.036 0.003

the significant differences existed in the effectiveness and uniformity of the

chemical procedures used.

The results obtained by combustion are slightly below the C values obtained by

ICP and DCP. Also, the values obtained by these two spectrochemical methods

show greater sample- to -sample , between laboratory and between method

consistency

.

Conclusions

The present determination of total carbon in SiC by combustion is suspected of

yielding results which are about 2% below the true value and shows poorer

reproducibility than for its other applications in this study. Development of

a chemical method yielding 100% recovery of the carbon in SiC as CO2,

standardization of the procedure and development of a certified material are

recommended.

7.3.2. Electrochemical Methods - Coulometry (See 7.2.3.)

Results and Discussion

Three laboratories reported a total of 10 determinations for three samples.

The carbon concentration is 30.04% by weight, with a standard deviation of

0.05. Estimate of the standard deviation for a single sample is 0.04.

181
ConeIlls ions

The results obtained indicate that this method can yield highly reproducible

results. Carbon values determined by coulometry for the lEA SiC samples are

30.04±0.15 (ninety-five percent confidence limits).

7.4. METHODS FOR ZIRCONIUM IN YTTRIA-ZIRCONIA

Three laboratories reported results of measurements by ICP, while one reported

six determinations by XRF and one reported three determinations by AAS

Data are summarized in Section 7.6.4.

7.4.1. X-ray Fluorescence Spectrometry (See 7.1.1.)

Instrument and Experimental Parameters

Samples were prepared by fusion in lithium tetraborate.

Conclusion

Data were insufficient to establish between- laboratory variance. Further

testing of this method is needed.

7.4.2. Atomic Absorption Spectrometry (See 7.2.1.)

Results and Discussion

One laboratory reported single results for three samples: mean 67.1, and

standard deviation 0.1.

The values obtained by AAS are significantly less than those obtained by XRF.

Possible incomplete recovery of Zr in dissolution of yttria-zirconia during

preparation of analyte solutions may be a possible source of this bias.

TABLE 7.4.1.1 Determination of Major Elements in Yttria-Zirconia (YSZ) by Xray Fluorescence. Concentrations are in percent by weight.

NUMBER OF

ELEMENT LAB SAMPLES MEAN STANDARD DEVIATION

Zr 1 6 68.50 0.04

Y 2 9 4.29 0.17

182
Conclusions

Data were insufficient for an adequate analysis of this method. However,

results appear to be slightly low with respect to XRF.

7.4.3. Inductively Coupled Plasma (See 7.1.3.)

Results and Discussion

One laboratory reported single results for three samples: mean 66.5, and

standard deviation 2.0. The other laboratory reported single results for two

samples: mean 71.4, and standard deviation could not be determined.

Conclusions

In view of the large imprecision in the results, Zr concentrations determined

by ICP may be expected to have large uncertainties, and its application for Zr

in yttria-zirconia appears questionable. However, the amount of data was

insufficient for an adequate analysis.

7.5. METHODS FOR YTTRIUM IN YTTRIA-ZIRCONIA

The largest number of laboratories reported results from ICP measurements.

Two laboratories reported a total of nine determinations by XRF. AAS , neutron

activation analysis and DCP also were used, but the amount of data was

insufficient for statistical evaluation.

Data are summarized in Section 7.6.5,

7.5.1. Neutron Activation Analysis (NAA)

Use and Significance

The utility of neutron activation analysis is limited by the availability of a

fission reactor facility and the turn-around time for analysis. Consequently,

NAA is usually applied selectively when the value of the material is

important, when the material cannot be analyzed accurately by other methods,

and when high accuracy or low trace level limits are important. The method

(thermal neutrons) is not recommended for light elements C, N, 0, F, Si, P,

Al, Mg and S, as well as Fe, due to their low cross -sections for thermal

neutrons. Fast neutron activation is required for light elements.

Results and Disctisslon

One determination of Y concentration by NAA was reported with a value of 4.30

percent by weight.

183
Conclusions

Data were insufficient to establish between- laboratory and sample- to -sample

variances. Due to the expense of this method, detailed testing is recommended

only for those cases where other methods prove inadequate.

7.5.2. X-ray Fluorescence (See 7.1.1.)

Instrument and Experimental Parameters

One laboratory dissolved their samples by fusion in lithium tetraborate. A

second laboratory reported dispersion of the powder in a special wax matrix.

Results and Discussion

The combined results for the two laboratories are summarized in Table 7.4.1.1.

The values obtained using the lithium tetraborate flux were slightly less than

the value obtained by NAA; while those obtained using the wax matrix were

slightly above. However, due to the small amount of data, a high degree of

confidence cannot be assigned to these apparent biases.

Conclusions

Results are consistent with NAA. Additional data for interlaboratory

comparison of this method are desirable toward its possible establishment as a

reference method for yttria-zirconia.

7.5.3. Atomic Absorption Spectrometry (See 7.1.2.)

Results and Discussion

One laboratory reported single results for three samples: mean 4.46, and

standard deviation 0.11. The precision appears comparable to that obtained

with XRF, but a between- laboratory component was not included in the present

result

.

Conclusions

Data were insufficient for a complete analysis of variance.

7.5.4. Inductively Coupled Plasma (See 7.1.3.)

Results and Discussion

Single determinations for seven samples were reported by 5 laboratories: mean

4.16, standard deviation 0.43.

Conclusions

In view of the large uncertainty associated with this method, the accuracy of

the method or the reliable procedures may be suspected for analysis of yttrium

184
7.5.5. Direct-Current Plasma (See 7.1.4.)

Results and Discussion

Two results reported by two laboratories had a mean 4.3 ± 0.1.

Conclusions

Data were insufficient for an analysis of variance. However, based on very

limited results, the observed bias and imprecision obtained with this method

suggest that this method should not be used for accurate or precise work.

7.6. MAJOR CHEMICAL COMPONENTS - STATISTICAL DATA

7.6.1. Silicon in Silicon Nitride. Silicon Carbide and Silicon

7.6.1.1 X-ray Fluorescence Spectrometry

Table 7.6.1.1.1 Silicon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Si

Method: 12

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

5 1 59.90 59.90 59.90 0.00

25 1 59.40 59.40 59.40 0.00

Means 2 59.40 59.90 59.65 0.35

Table 7.6.1.1.2 Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Si

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 6 59.60 59.90 59.75 0.10

25 6 59.18 59.43 59.31 0.10

Means 2 59.31 59.75 59.53 0.30

185
Table 7.6.1.1.3 Silicon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Si

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 6 69.11 69.78 69.47 0.23

Means 1 69.47 69.47 69.47 0.00

7.6.1.2. Atomic Absorption Spectroscopy

Table 7.6.1.2.1 Silicon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Si

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 59.50 59.50 59.50 0.00

Means 1 59.50 59.50 59.50 0.00

Table 7.6.1.2.2 Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Si

Method: 1

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

14 1 60.00 60.00 60.00 0.00

Means 1 60.00 60.00 60.00

186

0.00
Table 7.6.1.2.3 Silicon Concentration (wt. %) in Si Powder

Material: Silicon

Property: Si

Method: 1

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 99.40 99.40 99.40 0.00

Means 1 99.40 99.40 99.40 0.00

7.6.1.3. Inductively Coupled Plasma - Emission Spectroscopy

Table 7.6.1.3.1 Silicon Concentration (wt. %) in SNR Powder

Material

:

Silicon Nitride, Reference Powder

Property

:

Si

Method: 2

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 56.30 58.50 57.40 1.55

6 1 58.07 58.07 58.07 0.00

15 1 59.38 59.38 59.38 0.00

21 4 58.68 59.92 59.42 0.53

Means 4 57.40 59.42 58.56 0.99

187
Table 7.6.1.3.2 Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 67)

Property: Si

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 59.10 59.10 59.10 0.00

15 1 60.15 60.15 60.15 0.00

21 4 59.60 60.40 59.97 0.33

Means 3 59.10 60.15 59.74 0.56

Table 7.6.1.3.3 Silicon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Si

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 63,.73 63..73 63,.73 0..00

15 1 70,.11 70,,11 70,,11 0..00

21 3 69,.00 69,.30 69,,16 0..15

Means 3 63,,73 70,.11 67,,66 3..44

Table 7.6.1.3.4 Silicon Concentration (wt. %) in Si Powder

Material: Silicon

Property: Si

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 94.06 94.06 94.06 0.00

15 1 98.59 98.59 98.59 0.00

Means 2 94.06 98.59 96.32 3.20

188
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189
7.6.1.4. DC Plasma - Emission Spectroscopy

Table 7.6.1.4.1 Silicon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Si

Method: 17

// of Minimvim Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 6 57 40 61 40 59.10 1 54

3 1 59 10 59 10 59.10 0 00

18 1 59 41 59 41 59.41 0 00

Means 3 59 10 59 41 59.20 0 17

Table 7.6.1.4.2 Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Si

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 61.60 62.60 62.10 0.70

18 1 58.89 58.89 58.89 0.00

Means 2 58.89 62.10 60.49 2.26

190
7.6.1.5. Gravimetry

Table 7.6.1.5.1 Silicon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Si

Method: 20

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

13 11 59.05 59.76 59.47 0.19

18 1 58.74 58.74 58.74 0.00

24 3 58.10 60.20 59.43 1.15

Means 3 58.74 59.47 59.21 0.41

Table 7.6.1.5.2 Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Si

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

18 1 59.46 59.46 59.46 0.00

24 2 59.10 59.40 59.25 0.21

Means 2 59.25 59.46 59.35 0.14

191
Table 7.6.1.5.3 Silicon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Si

Method: 20

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 2 65.86 68.63 67.24 1.95

18 1 68.49 68.49 68.49 0.00

Means 2 67.24 68.49 67.86 0.88

Table 7.6.1.5.4 Silicon Concentration (wt. %) in Si Powder

Material: Silicon

Property: Si

Method: 20

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

5 6 98.60 98.90 98.80 0.10

8 2 94.77 98.19 96.48 2.41

18 1 99.00 99.00 99.00 0.00

Means 3 96.48 99.00 98.09 1.40

192
7.6.2

7.6.2.1

Nitrogen in Silicon Nitride

Combustion

Table 7.6.2.1.1 Nitrogen Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 68)

Property: N

Method: 8

# of

LAB y/ Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 6 38 33 38 67 38 50 0 13

3 8 38 20 38 30 38 22 0 04

5 1 38 50 38 50 38 50 0 00

6 4 37 70 38 50 38 10 0 40

13 11 40 03 41 52 40 79 0 48

14 1 38 00 38 00 38 00 0 00

18 2 32 10 37 58 34 84 3 87

19 1 37 72 37 72 37 72 0 00

21 3 38 10 38 30 38 20 0 10

24 3 38 30 40 50 39 36 1 10

Means 10 34 84 40 79 38 22 1 48

Table 7.6.2.1.2 Nitrogen Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 69)

Property: N

Method: 8

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 4 37 40 38 40 38 00 0 45

5 4 38 40 39 30 38 90 0 39

6 2 38 50 39 00 38 75 0 35

14 1 38 50 38 50 38 50 0 00

15 1 38 10 38 10 38 10 0 00

18 1 32 30 32 30 32 30 0 00

19 7 37 88 39 20 38 43 0 43

21 6 38 70 38 90 38 83 0 08

24 14 38 50 41 00 39 65 0 73

Means 32.30 39.65 37.94 2.17

193
I

0.2

E

.2 § o p o

en Li- ^ ^ in

00

11o

4>

li >O

-4-'

CD

csf O

CO

_

o

CO

CD

-- C>l o 0 0• 0 q 0 q 0• 0 00 CO • 0 m

o

JQE3 k

T)

0) PU0

(X

0)U

01 10

&.

NRM

n

•H

(Q>^

<d < c0 c

T-l 0

•H

iJ

}-l CQ c0 0 c u 0u bOG c •H « W

bO 3 0

0) 4J

1-1 -§

00vO

%N

194
too

h-I —

p

o

h

r< II

11 co >Q

cn

CD

CM

CM

_

O

00

CD

CM

00

CD

-- CMO

uuo

p.

0)u

CO

(d HZ

on^ (0 dP -HU • >^ ego c

•H

O

4J -H

CO 4J U CQ

4-) 3

<= -s

0)

Q

O

O

C

O

o

c

C -H « CO bO :3 oU CO JJ ^ •H (0 Z -1

q

o« q

q

o

q

o 00 CD 9 CM % N

195
I.e. 1.1. Kieldahl Analysis

Table 7.6.2.2.1 Nitrogen Concentration (wt. %) in SNR Powde

Material: Silicon Nitride, Reference Powder

Property: N

Method: 15

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 38.91 38.91 38.91 0.00

25 1 38.40 38.40 38.40 0.00

Means 2 38.40 38.91 38.65 0.36

Table 7.6.2.2.2 Nitrogen Concentration (wt. %) in SNT Powde

Material: Silicon Nitride, Test Powder

Property: N

Method: 15

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 4 38.70 39.10 38 87 0 17

15 1 39.04 39.04 39 04 0 00

25 6 38.79 39.00 38 91 0 08

Means 3 38.87 39.04 38 94 0 08

196
7.6.2.3 Potentiometric Titration

Table 7.6.2.3.1 Nitrogen Concentration (wt. %) in SNR Powder by

Potentiometric Titration

Material: Silicon Nitride, Reference Powder

Property: N

Method: 13

# of Minimum Maximxim Average Standard

LAB // Values Value Value Value Deviation

24 3 32.07 40.50 36.72 4.28

Means 1 36.72 36.72 36.72 0.00

Table 7.6.2.3.2 Nitrogen Concentration (wt . %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: N

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 2 37.90 38.40 38.15 0.35

Means 1 38.15 38.15 38.15 0.00

197
7.6.3 Total Carbon in Silicon Carbide

7.6.3.1 Combustion

Table 7.6.3.1.1 Total Carbon Concentration (wt . %) in SiC Powder

Material: Silicon Carbide (Figure 70)

Property: C Total

Method: 8

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 4 28,,89 29,.01 28,.95 0,,05

6 2 31,,45 31,.46 31,.45 0,,00

7 2 30,,10 30,.10 30,.10 0,.00

8 2 28,,96 29,.45 29,.20 0,.34

15 1 29,,34 29,.34 29,.34 0,.00

18 1 29,,70 29,.70 29..70 0,,00

Means 6 28.95 31.45 29.79 0.90

7.6.3.2. Electrochemical Methods - Potentiometric Titration

Table 7.6.3.2.1 Total Carbon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: C Total

Method: 16

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

10 1 29.97 29.97 29.97 0.00

21 3 30.04 30.10 30.08 0.03

25 6 29.97 30.07 30.03 0.04

Means 3 29.97 30.08 30.02 0.05

I

198
ED

0) •p

}-i o

>-l

CO

ca

(Uo

•H

dp CQ •H • W

t!> -t w CO o

4J

O

CO •H U 4J

4J 0) C 3

(U ^ c o o o o

to

c

c

O •H Xi tn U CO ^ nj O >^ H 43 O

a>

199
7.6.3.3. Gravimetry

Table 7.6.3.3.1 Total Carbon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: C Total

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

18 1 29.70 29.70 29.70 0.00

Means 1 29.70 29.70 29.70 0.00

7.6.4. Zirconium in Yttria-Zirconia

7.6.4.1 X-ray Fluorescence Spectrometry

Table 7.6.4.1.1 Zirconium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Zr

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 6 68.44 68.54 68.50 0.03

Means 1 68.50 68.50 68.50 0.00

200
Atomic Absorption Spectroscopy

Table 7.6.4.2.1 Zirconium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Zr

Method: 1

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

18 3 67.00 67.20 67.10 0.10

Means 1 67.10 67.10 67.10 0.00

7.6.4.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 7.6.4.3.1 Zirconium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Zr

Method: 2

// of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

1 2 65.00 65.60 65.30 0.42

6 1 68.78 68.78 68.78 0.00

22 2 71.40 71.40 71.40 0.00

Means 3 65.30 71.40 68.49 3.06

201
7.6.5. Yttrium in Yttria-Zirconia

7.6.5.1 Neutron Activation Analysis

Table 7.6.5.1.1 Yttrium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Y

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 4.30 4.30 4.30 0.00

Means 1 4.30 4.30 4.30 0.00

7.6.5.2 X-ray Fluorescence Spectrometry

Table 7.6.5.2.1 Yttrium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Y

Method: 12

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

22 6 4.15 4.23 4.18 0.02

24 3 4.52 4.52 4.52 0.00

Means 2 4.18 4.52 4.35 0.23

202
7.6.5.3 Atomic Absorption Spectroscopy

Table 7.6.5.3.1 Yttrium Concentration (wt. %) in YSZ Powder

Material: Zirconia (Figure 71)

Property: Y

Method: 1

y/ of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

18 3 4.33 4.54 4.45 0.11

Means 1 4.45 4.45 4.45 0.00

7.6.5.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 7.6.5.4.1 Yttrium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Y

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 3,,88 3,.92 3.90 0,.02

6

' 1 3,.48 3,.48 3.48 0..00

15 1 4.,11 4,.11 4.11 0,.00

17 1 4,,52 4,.52 4.52 0..00

22 2 4.,60 4,,60 4.60 0,,00

Means 5 3,,48 4,,60 4.12 0,,46

203
(U 4J

S-l O

O.

(U

!-i

CO

0)o

IX

a.oowo

4JU

<1> • o- U OTo o m

t-l

M

<d

S

U I C CM

<u

u

O

M

cO bO o c

•H

$-1

u

•M 43

(0 -I

0)

bO

%A

204
7.6.5.5 DC Plasma - Emission Spectroscopy

Table 7.6.5.5.1 Yttrium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Y

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 4.20 4.20 4.20 0.00

17 1 4.41 4.41 4.41 0.00

Means 2 4.20 4.41 4.30 0.14

7.7. STATISTICAL ANALYSIS . R. Munro , NIST

Quantitative analysis of the major elemental components of the powders

generally involved some form of decomposition of the material. Results from

two methods, the combustion and Kjeldahl techniques which used chemical

reactions to decompose silicon nitride, are shown in Figures 72-73 for the

determination of nitrogen. The combustion method involves the detection and

measurement of the quantity of gaseous nitrogen released from a measured mass

of silicon nitride. The Kjeldahl method is a neutralization titration

technique that determines the amount of nitrogen based on the amount of

ammonia produced by a controlled chemical reaction.

The level of precision of the Kjeldahl method was only somewhat better than

the precision attained by the combustion technique. The between- laboratory

variances, however, were significantly different. Much better agreement

between laboratories was achieved by the Kjeldahl method.

205
o 2

Q O

(0

d

d

o

>4

3.00

2.50 -

-

2.00 -

-

1.50 -

1.00 -

^ ^ 0.50 +

0.00

Si3N4 (Ref.)

C.

1

! 1

Idahl

}—Combustion— } g»

K. .11 1 1 1

\ Within Lab ]

| 1

Betw.

Labs

n

•d

. o

Figure 72. Within lab, between lab, and between methods standard

deviations in the measurement of nitrogen content for the

SigN^CRef.) powder as measured by various laboratories using a

variety of methods.

206
o 3

.2 d

II O

CO d

a) O

3.00

2.50

2.00

1.50

1.00

0.50

0.00

Si3N^ (Test)

(

• J— Combustion —|

1 1 1 . 1 Tr f 1

J Within Lab 1 I 1

Betw.

Labs

•3

Figure 73. Within lab, between lab, and between methods standard

deviations in the measurement of nitrogen content for the

Si3Nz,(Test) powder as measured by various laboratories using a

variety of methods

.

207
7.8 References

1. Vickers , T. J.; Winefordner , J. D. Flame Spectrometry, Analytical

Emission Spectroscopy . Part II. E. by Grove, E. L. New York: Marcel

Dekker; 1972. Chapter 7.

2. Vickers, T. J. Atomic Fluorescence and Atomic Absorption Spectroscopy,

Physical Methods in Modern Chemical Analysis . Vol. 1. New York:

Academic Press; 1972. pp. 189-254.

3. Willard, H. H. ; Merritt, L. L. and Dean, J. A. "Instrument Methods of

Analysis," Chapter 10, 1974, pp. 258.

4. Boumans , P. W. J. M. Excitation of Spectra, Analytical Emission

Spectroscopy . op cit. pp. 192-204.

5. Rozsa, J. T. Quantitative Analysis, Analytical Emission Spectroscopy , op cit. Chapter 9.

6. Boumans, P. W. J. M. Excitation of Spectra, Analytical Emission

Spectroscopy . op cit. pp. 204-13.

7. Davis, W. F. ; Merkle, E. J. Dissolution of Bulk Samples of Silicon

Nitride. Anal. Chem. 53: 1139; 1981.

8. Czupryna, G.; Natansohn, S. Analysis of Silicon Nitride, Advances in

Materials Characterization . Materials Science Research, Vol. 15. Ed. by

Rossington, D. R. ; Condrate , R. A.; Snyder, R. L. New York: Plenum

Press; 1983.

208
8. MAJOR NONMETALLIC IMPXJRITIES (Concentration > 100 ppm by weight)

A. L. Dragoo, S. G. Malghan, R. G. Munro and S. M. Hsu; NIST

8.1. METHODS FOR TOTAL CARBON IN SILICON NITRIDE AND SILICON

Combustion analysis was the principal method used for determination of carbon

impurity in silicon nitride and silicon. Other decomposition methods employed

electrochemical measurements and gravimetric analysis; however, the amount of

data reported was insufficient for evaluation of these other methods.

Data are summarized in Section 8.10.2.

8.1.1. Combustion (See 7.2.1.)

Results and Discussion

The results are summarized in Table 7.3.1.1 for SNR SigN^,, SNT SigN^ and Si.

The method of detection was presumed to be IR absorption in all cases. The

standard deviations for the total set of measurements for each material are

comparable to the within laboratory standard deviation for that material.

The results for determination of total carbon impurity by combustion analysis

are compared in Table 8.1.2.1 with those obtained by electrochemical methods

and gravimetry.

Conclusions

Good agreement was evident among laboratories using combustion methods.

Presently, lower limit of reliable detectability for carbon impurity in SigN^

and Si by combustion analysis appears to be about 0.05%.

8.1.2. Electrochemical Methods (See 7.2.)

Instrument and Experimental Parameters

Po tent iome try

The experimental method (Lab 24) was comparable to the combustion method;

however, the evolved CO2 was collected in Ba(0H)2 solution and the solution

was potentiometrically titrated to determine the amount of CO2 recovered.

Coulometry

Two methods were reported.

The first method was used by Lab 3. A powder sample was decomposed in a Pb0/B203 flux and the carbon reacted with a stream of O2 . The CO2 was

recovered by precipitation of BaCOg . The amount of BaCOg formed was

determined by coulometric titration to a constant pH (pH = 10)

.

209
The second method was used by Lab 21. The sample was oxidized with O2, the

CO2 recovered (procedure not specified) and the amount determined by

coulometric titration.

Results and Discussion

As shown by the results in Table 8.1.2.1, coulometric titration appears to

have yielded results in agreement with those obtained by combustion followed

by IR detection; whereas, the results obtained by potentiometric titration

appear to be low. Since both electrochemical methods employ combustion of the

sample to obtain the analyte , it is expected that recovery of CO2 may have

been incomplete in the case of the potentiometric titration method.

The precision of the two electrochemical methods appears to be comparable.

Conclusions

Results obtained with potentiometric titration may have been low due to

insufficient recovery of the evolved CO2 from the decomposition process.

However, data were insufficient for a complete evaluation of the method.

Table 8.1.2.1 Comparison of Methods of Determination of Total Carbon

Impurity in Silicon Nitride and Silicon Powder Samples

Number of

Material Method Labs Samples Mean Standard

Deviation

SNR Combustion 13 22 0,.15 0,.02

SNR Potentiometric 1 3 0,.04 0,.01

SNR Coulometric 2 5 0.,29 0..03

SNT Combustion 12 23 0,.13 0,.03

SNT Potentiometric 1 2 0.,053 0,.009

SNT Coulometric 1 1 0,.11 0,.01

SNT Gravimetry 1 1 0,.12

Si Combustion 8 12 0,.08 0..03

Si Coulometric 1 4 0..061 0.,002

210
8.2. METHODS FOR FREE CARBON IN SILICON CARBIDE

A very limited number of determinations of free-carbon in silicon carbide were

reported by combustion analysis, coulometric titration and gravimetric

analysis. Significant differences appear to exist in the data, and the data

were insufficient for statistical evaluation.

Data are summarized in Section 8.10.3.

8.2.1. Combustion (See 7.2.1.)

Instrument and Experimental Parameters

A standard method for determination of free carbon in SiC by combustion

analysis is described in DIN 51075, Part 2. Kerber et al . ^ discussed the

problems encountered in applying this method to fine SiC powders.

The sample was treated in an oxidizing atmosphere to convert the free carbon

to CO2. The amount of CO2 generated was measured by IR absorption.

Only combustion analysis was used to measure carbon in the yttria-zirconia

powder

.

Data are summarized in Section 8.10.3.

Instrximent and Experimental Parameters

A tin-coated Cu as an accelerator for combustion was used in the decomposition

reaction. Measurements were calibrated with standards supplied by the vendor

of the instrvunent.

Results and Discussion

The average result for the method is compared in Table 7.3.1.1 with results

for combustion analysis of the other powders. Good agreement was evident

between the three laboratories reporting. The improved sensitivity of this

method for C in yttria-zirconia is to be noted as compared to similar

determinations of C in SigN^ and Si.

Conclusions

Combustion appears to offer a method for reproducible determination of C in

yttria-zirconia.

8.3. METHODS FOR TOTAL CARBON IN YTTRIA-ZIRCONIA

8.3.1. Combustion (See 7.2.1.)

211
8.4. METHODS FOR NITROGEN IN SiC. SILICON AND YTTRIA-ZIRCONIA

Nitrogen impurity concentrations were determined by combustion analysis.

Data are summarized in Section 8.10.5.

8.4.1. Combustion (See 7.2.1.)

Instrument and Experimental Parameters

Sic, Si: One laboratory reported that the samples were reacted with tin powder

in a nickel basket. The same laboratory reported that standards supplied by

the vendor of the instrument were used.

Results and Discussion

The results are summarized in Table 7.1.2.1. Good agreement is evident for

results obtained for N in SiC. In the case of Si, the poorer precision makes

the reproducibility of the measurements suspect. The lack of sufficient data

does not permit the method to be adequately evaluated for this material.

Conclusions

Combustion analysis appears to offer good reproducibility and sensitivity for

the determination of N in SiC. In the case of Si, the utility of this method

is questionable in view of the low N concentration in the material and the

apparent limiting precision of the method. Further evaluation of the method

is required for yttria-zirconia.

8.5. METHODS FOR OXYGEN IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

Oxygen impurity concentrations in these materials was carried out by a large

number of laboratories using combustion analysis. In addition, the following

four methods were used for oxygen analysis in silicon nitride, silicon carbide

and silicon: fast neutron activation analysis, thermal neutron activation

analysis, ICP and Coulometric titration.

Data are summarized in Section 8.10.6.

8.5.1. Fast Neutron Activation Analysis (FNAA)

Use and Significance

Fast neutron activation analysis is used for light elements where NAA with

thermalized ("slow") neutrons is not indicated due to the low absorption

cross - sections of light elements for thermal neutrons. Fast neutrons are used

to produce (n,2n), (n,p) and (n,Q:) reactions. Results are given here for the

analysis of oxygen in the four nonoxide powders. See also remarks in Section

7.5.1. on N/L..

212
Instrument and Experimental Parameters

Fast neutrons of different energies may be produced in several ways, but the

most favorable energy for the analysis of light elements is 14 MeV.

Monoenergetic neutrons of this energy can be produced by bombardment of a

tritium target with deuterium ions to produce neutrons from a helium fusion

reaction, ^H(d,n)''H. Oxygen determination is carried out using the reaction

^^0(n,p)^^N with a threshold of 10 MeV. Fast neutron fluxes of about 2x10^

neutrons/cm^/s are delivered to the sample, giving a detection limit of about

15 ppm for a 20 g sample. Time -dependent flux changes are monitored via a

plastic scintillator placed behind the sample and coupled to a photomultiplier

detector. The photomultiplier output is fed to a discriminator adjusted so

that only pulses originating from a proton recoil of at least 7 MeV are

recorded. The measurement is calibrated by analyzing oxygen standards along

with unknowns. The use of benzoic acid, hydroxytriphenylsilane and N-1-

naphthylacetamide as standards was reported in this study.

Samples were placed in small polyethylene vials with tight fitting caps and

submitted along with standards for analysis. Results were uncorrected for

fluorine which is a direct interference to the determination of oxygen. The

correction for fluorine is

:

%0corrected %0expected 0.4( %F )

Results and Discussion

Results are summarized in Table 8.5.1.1. Although FNAA results are reported

by only one of the participating laboratories, the results were obtained by

submitting samples to laboratories specializing in FNAA. Since no difference

was discernable in the results from both the FNAA laboratories , the results

have been aggregated here.

One other laboratory reported results obtained with slow neutron activation.

These are included for comparison in Table 8.5.1.1. The results obtained with

FNAA for silicon nitride and SiC powders are in agreement with selected

results obtained by combustion analysis: compare the results in Table 8.5.1.1

with those in Table 8.5.1.2.

The results obtained for 0 in Si are about 20% larger than those obtained by

combustion analysis. The sources of this bias are not evident.

Conclusions

FNAA appears capable of providing accurate and precise data regarding the 0-

content of silicon nitride, SiC and Si. The utility of this method is limited

by the requirement of a specialized facility. However, it is recommended that

the services of one or more of such facilities should be employed in

establishing an oxygen reference standard for nonoxide ceramics.

213

1
Table 8.5.1.1 Determination of 0 in Silicon Nitride, Silicon Carbide and

Silicon by Neutron Activation Analysis. Concentrations are

in percent by weight. "SLOW" refers to thermal neutrons.

NUMBER OF

MATERIAL TYPE LABS SAMPLES MEAN STANDARD

DEVIATION

SNR FAST* 1 12 2.16 0.14

SNT FAST 1 8 1.16 0.06

Sic FAST 1 8 0.75 0.02

SLOW 1 2 1.48 0.15

Si FAST 1 8 0.64 0.04

SLOW 1 2 1.70 0.18

^Corrected for F.

8.5.2. Combustion (See 7.2.1.)

Instrxunent and Experimental Parameters

Oxygen was determined by measuring the thermal conductivity (TC) of the

evolved gas, as with the case of N2 above, or by recovering the oxygen in CO2

and measuring the intensity of IR- absorption.

Samples were encapsulated in a metal, such as tin, with powdered nickel added

as a flux. Reduction was carried out in a graphite crucible with helium or

argon used as a carrier gas . Temperature and heating rate for the reaction

may have significant effect on the extent of the reduction or on possible loss

of oxygen as SiO. Purity of carrier gas is also important.

Results and Discussion

For SNR SisN/i, a total of 17 laboratories reported determinations of oxygen

concentrations for 59 samples and 87 determinations. Six of the laboratories

reporting results by TC detection and six reporting results by IR detection

showed very good agreement, with means close to 2.22. One each of the labs

reporting results by these two methods of detection reported significantly

larger values: above 2.50. These higher values may be due to bias in

experimental conditions or instrument calibrations since similar deviations

were evident for SNT samples reported by the same laboratories.

Generally good agreement was found between the two methods of detection for

SNT, Sic and Si samples.

214
Conclusions

Determination of oxygen- concentrations in silicon nitride, silicon carbide and

silicon generally showed good agreement, although some cases of experimental

bias were evident in the case of silicon nitride. Better definition of

analytical conditions and development of a generally available reference

material are recommended.

Table 8.5.2.1

MATERIAL

Determination of 0 in Silicon Nitride, Silicon Carbide and

Silicon by Combustion. Concentrations are in percent by

weight.

DETECTION

NUMBER OF

LABS . SAMPLES MEAN

STANDARD

DEVIATION

SNR TC

TC

IR

IR

NS*

1

6

1

3

20

2

19

3

5

2.22

2.53

2.21

2.60

2.14

0.08

0.05

0.19

0.09

0.07

SNT TC

IR

IR

NS

4

5

1

2

12

6

1

3

1.26

1.18

1.34

1.15

0.05

0.05

0.03

0.11

SiC TC

IR

NS

1

4

1

2

5

1

0.64

0.72

0.74

0.07

0.01

Si TC

IR

NS

3

4

1

4

8

1

0.51

0.53

0.50

0.01

0.02

0.04

^NS , method of detection not specified.

215
8.6. METHODS FOR FLUORINE IN SILICON NITRIDE AND SILICON CARBIDE

Fluorine impurity concentrations in silicon nitride and silicon carbide were

measured by mass spectrometry, ion chromatography, potentiometric titration

and specific ion electrode. The amount of data reported for each method was

insufficient for an adequate evaluation of the method.

8.6.1. Ion Chromatography (IC)

Use and Significance

Ion chromatography is a highly efficient method for the determination of

anions including F"- CI"- and SO^"^; especially at low concentrations of these

ions. A prerequisite for the use of this method is the dissolution of the

powder in an appropriate solvent.

Instrument and Experimental Parameters

The three major components of an ion chromatography system are the separator

columns, suppressor columns and conductivity detectors. Some of the most

common separator columns are AS-1 and AS-2^^\ which have

polystyrene/divinylbenzene base resin core particles with a diameter of 25 /zm.

A common eluent is bicarbonate/carbonate for common anion chromatography. The

suppressor column in AS-1 converts bicarbonate/carbonate eluent to carbonic

acid. Since the carbonic acid has a high conductivity, it increases the

detection limit. However, in AS- 3 the suppressor column consists of potassium

phosphate

.

No information was given in this study with regard to the types of columns and

eluents used.

Depending on the powder composition and laboratory practice, different

procedures are used for powder dissolution or for powder leaching. One

laboratory reported that F" was extracted by leaching with water (water

temperature unreported) . Details were not given for the ion chromatography

measurement.

Measurements may be affected by filtration and preconcentration of dilute

samples or by dilution of highly concentrated samples.

Results and Discussion

Results are comparable to those obtained by electrochemical methods

ion electrode and potentiometric titration) . Measurements were not

for the SiC powder.

(R) - Registered name by Dionics Corporation

8.6.2 Electrochemical Methods (See 7.2.3.)

216
Experimental Parameters

Specific Ion Electrode (SIE)

Experimental details were not reported.

Potentiometric Titration

In the case of the silicon nitride powders, one laboratory reported that

analytical samples were dissolved in a NaOH-Na02 flux, followed by dissolution

of the material in sulphuric acid. Experimental details were not given by the

other two laboratories.

Results and Discussion

Average results of these two methods are consistent with each other and with

IC in the cases of the two silicon nitride powders. However, data are

insufficient for a reliable evaluation of the uncertainties of these methods.

8.7. METHODS FOR CHLORINE IN SILICON CARBIDE AND SILICON

Chlorine concentrations were determined in silicon carbide and silicon by ion

chromatography - one determination on one sample for each material. Although

the reported values were in excess of 100 ppm, the results are included in

Section 10.5 for comparison with those for the two silicon nitride powders.

8.8. METHODS FOR SULFUR IN YTTRIA- ZIRCONIA

Results of a few measurements of sulfur concentrations were reported for ICP,

mass spectrometry and combustion analysis. Data were insufficient for a

reliable evaluation and comparison of methods.

Data are summarized in Section 8.10.8.

8.8.1 Ion Chromatography (See 7.3.1.)

Instrument and Experimental Parameters

One laboratory reported the extraction of leachable anions with boiling water.

Results and Discussion

Results are low relative to those obtained by combustion. The source of this

discrepancy cannot be established from the data reported. However, it is to

be noted that the combustion method would recover S from both the surface and

interior of the particles; whereas, a leaching method may have extracted only

S at or near the surface of the particles.

217
Conclusions

Results are low as noted above . This method may be more appropriate for

surface, rather than bulk, analysis of powders.

8.9. METHODS FOR CHLORINE IN YTTRIA-ZIRCONIA

A few measurements of chlorine concentrations in yttria-zirconia were made by

ion chromatography, neutron activation analysis and argentometric titration.

The data were insufficient for an evaluation and comparison of these methods.

Data are summarized in Section 8.10.9.

8.10. STATISTICAL DATA ON MAJOR NONMETALLIC IMPURITIES (concentration >

100 ppm by weight)

Impurities present at concentrations greater than 100 ppm are termed "major

impurities." This lower boundary for the major impurity category is

arbitrary, and in a few instances it was desireable to include cases in which

the impurity concentration was less than 100 ppm for a particular material

because it permitted a convenient comparison with another material in which

the impurity concentration was greater than 100 ppm. For example, see Tables

8.10.7.2 and 3 for the impurity concentration of F in the SNR and SNT powders,

respectively.

8.10.1. Free Silicon in Silicon Nitride

8.10.1.1 Electrochemical Methods - Potentiometric Titration

Table 8.10.1.1 Free Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: FREESI

Method: 4

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 5 0.021 0.029 0.02 0.004

Means 1 0.025 0.025 0.02 0.00

218
8.10.1.2 Volumetric Determination

Table 8.10.1.2 Free Silicon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: FREEST

Method: 9

# of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

21 2 0.07 0.09 0.08 0.014

Means 1 0.08 0.08 0.08 0.00

8.10.1.3 Standardized Method (DIN 51075)

Table 8.10.1.3 Free Silicon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: FREEST

Method: 18

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 4 0.1000 0.1400 0.1250 0.0173

Means 1 0.1250 0.1250 0.1250 0.0000

219
8.10.2 Total Carbon in Silicon Nitride and Silicon

8.10.2.1 Combustion Analysis

Table 8.10.2.1.1 Carbon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: C Total

Method: 8

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1

5

6

7

14

15

16

17

18

19

22

24

25

6

1

5

17

2

1

4

2

3

1

10

1

1

0.15

0.12

0.14

0.11

0.16

0.15

0.15

0.15

0.13

0.19

0.15

0.17

0.18

0.17

0.12

0.16

0.17

0.16

0.15

0.17

0.19

0.16

0.19

0.18

0.17

0.18

0.16

0.12

0.15

0.14

0.16

0.15

0.15

0.17

0.14

0.19

0.16

0.17

0.18

0.00

0.00

0.00

0.01

0.00

0.00

0.00

0.02

0.01

0.00

0.01

0.00

0.00

Means 13 0.12 0.19 0.15 0.01

220
Table 8.10.2.2.2 Carbon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: C Total

Method: 8

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 4 0,.10 0,.16 0.13 0,.03

5 4 0,,09 0..10 0.09 0..00

6 3 0.,09 0,.09 0.09 0..00

7 5 0,,19 0..22 0.20 0,.01

14 1 0,,10 0,.10 0.10 0,.00

15 1 0.,10 0,.10 0.10 0..00

16 12 0,,11 0..16 0.13 0,.01

18 2 0,,12 0,.16 0.14 0,.02

19 7 0,,11 0,.16 0.12 0..01

22 6 0,,11 0,.14 0.12 0..01

24 8 0,,10 0,.14 0.11 0,.01

25 6 0,,12 0,.14 0.13 0..00

Means 12 0..09 0..20 0.12 0,.02

Table 8.10.2.2.3 Carbon Concentration (wt. %) in Si Powder

Material: Silicon

Property: C Total

Method: 8

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 2 0,.08 0,,08 0,.08 0,.00

5 4 0,,05 0,,05 0,.05 0,.00

6 3 0,,08 0,,08 0,.08 0,,00

7 2 0.,07 0,,07 0,.07 0,.00

8 2 0,,01 0,,02 0,.02 0,.00

15 1 0,,05 0,,05 0,.05 0..00

16 9 0,,08 0,,12 0..09 0..01

18 1 0,,21 0,,21 0,.21 0..00

22 6 0,,06 0.,07 0,.07 0..00

Means 9 0,,02 0,,21 0,.08 0..05

221
8.10,2.2 Electrochemical Methods - Potentionmetrlc Titration

Table 8.10.2.2.1 Carbon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: C Total

Method: 13

# of Minimum Maximvim Average Standard

LAB // Values Value Value Value Deviation

24 0.0270 0.0520 0.0352 0.0114

Means 0.0352 0.0352 0.0352 0.0000

Table 8.10.2.2.2 Carbon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: C Total

Method: 13

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 0.0450 0.0630 0.0532 0.0091

Means 0.0532 0.0532 0.0532 0.0000

222
8.10.2.3 Electrochemical Methods - Coulometric Titration

Table 8.10.2.3.1 Carbon Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: C Total

Method: 16

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 4 0.2500 0.2800 0.2650 0.0129

21 3 0.3000 0.3300 0.3133 0.0153

Means 2 0.2650 0.3133 0.2892 0.0342

Table 8.10.2.3.2 Carbon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: C Total

Method: 16

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

21 4 0.1000 0.1200 0.1075 0.0096

Means 1 0.1075 0.1075 0.1075 0.0000

Table 8.10.2.3.3 Carbon Concentration (wt. %) in Si Powder

Material: Silicon

Property: C Total

Method: 16

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 4 0.0580 0.0630 0.0608 0.0022

Means 1 0.0608 0.0608 0.0608 0.0000

223
8.10.2.4 Gravimetrv

Table 8.10.2.4 Carbon Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: C Total

Method: 20

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

18 1 0.1200 0.1200 0.1200 0.0000

Means 1 0.1200 0.1200 0.1200 0.0000

8.10.3. Free Carbon in Silicon Carbide

8.10.3.1 Combustion Analysis

Table 8.10.3.1 Free Carbon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: CFREE

Method: 8

# of Minimiam Maximum Average Standard

LAB # Values Value Value Value Deviation

10 3 0.6900 0.7090 0.6987 0.0096

Means 1 0.6987 0.6987 0.6987 0.0000

224
8.10.3.2 Electrochemical Methods - Coulometric Titration

Table 8.10.3.2 Free Carbon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: CFREE

Method: 16

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

10 1 0.2700 0.2700 0.2700 0.0000

21 4 0.5700 0.6000 0.5825 0.0126

Means 2 0.2700 0.5825 0.4263 0.2210

8.10.3.3 Gravimetry

Table 8.10.3.3 Free Carbon Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: CFREE

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 2 0.6300 0.6600 0.6450 0.0212

Means 1 0.6450 0.6450 0.6450 0.0000

225
8.10.4 Carbon in Yttria-Zirconia

8.10.4.1 Combustion Analysis

Table 8.10.4.1 Carbon Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: C

Method: 8

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0370 0.0370 0.0370 0.0000

17 1 0.0350 0.0350 0.0350 0.0000

22 5 0.0310 0.0390 0.0354 0.0034

Means 3 0.0350 0.0370 0.0358 0.0011

8.10.5. Nitrogen in Silicon Carbide. Silicon and Yttria-Zirconia

8.10.5.1 Combustion Analysis

Table 8.10.5.1.1 Nitrogen Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: N

Method: 8

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

6 3 0,.0780 0,.0860 0,,0817 0,.0040

10 1 0,.1450 0..1450 0,,1450 0,,0000

15 1 0,.0800 0,.0800 0,,0800 0,,0000

18 1 0,,0650 0,.0650 0.,0650 0,,0000

21 3 0.,0690 0,.0710 0,,0703 0.,0012

22 2 0,,0750 0,.0800 0,,0775 0.,0035

Means 6 0.0650 0.1450 0.0866 0.0293

226
Table 8.10.5.1.2 Nitrogen Concentration (wt. %) in Si Powder

Material: Silicon

Property: N

Method: 8

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

3 4 0,.0600 0,,0700 0,.0650 0,.0058

6 4 0,.0100 0,.0200 0..0125 0,.0050

15 1 0,.0600 0,.0600 0,.0600 0..0000

18 1 0,.0100 0,.0100 0..0100 0,,0000

Means 4 0,.0100 0,.0650 0..0369 0.,0297

Table 8.10.5.1.3 Nitrogen Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: N

Method: 8

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

22 8 0.0220 0.0320 0.0265 0.0036

Means 1 0.0265 0.0265 0.0265 0.0000

227
8.10.6.

8.10.6.1

Oxygen in Silicon Nitride. Silicon Carbide and Silicon

Neutron Activation Analysis

Table 8.10.6.1,1 Oxygen Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: 0

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

23 12 2.0500 2.4100 2.2158 0.1252

Means 1 2.2158 2.2158 2.2158 0.0000

Table 8.10.6.1.2 Oxygen Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: 0

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

23 8 1.1000 1.2400 1.1613 0.0589

Means 1 1.1613 1.1613 1.1613 0.0000

Table 8.10.6.1.3 Oxygen Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: 0

Method: 6

# of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

8 2 1.3700 1.5800 1.4750 0.1485

23 8 0.7300 0.7800 0.7500 0.0169

Means 2 0.7500 1.4750 1.1125 0.5127

228
Table 8.10.6.1.4 Oxygen Concentration (wt. %) in Si Powder

Material: Silicon

Property: 0

Method: 6

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

8 2 1.5700 1.8200 1.6950 0.1768

23 8 0.5600 0.6900 0.6375 0.0388

Means 2 0.6375 1.6950 1.1663 0.7478

8.10.6.2 Combustion Analysis

Table 8.10.6.2.1 Oxygen Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 74)

Property: 0

Method: 8

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 6 2 4490 2 5680 2 5300 0 0488

3 8 2 3100 2 3300 2 3175 0 0089

5 1 1 9000 1 9000 1 9000 0 0000

6 4 2 0400 2 2000 2 1325 0 0727

7 6 2 1900 2 3200 2 2650 0 0472

13 11 2 1100 2 2800 2 1745 0 0573

14 1 2 0000 2 0000 2 0000 0 0000

15 1 2 4000 2 4000 2 4000 0 0000

16 4 1 7500 2 0400 1 9000 0 1463

17 2 2 2100 2 2300 2 2200 0 0141

18 2 2 0500 2 1300 2 0900 0 0566

19 1 2 0900 2 0900 2 0900 0 0000

21 6 2 1800 2 3700 2 2533 0 0647

22 12 2 1300 2 4200 2 2525 0 0984

24 2 2 0800 2 1000 2 0900 0 0141

25 3 2 5100 2 6900 2 6000 0 0900

ans 16 1 9000 2 6000 2 2010 0 1991

229
Table 8.10.6.2.2 Oxygen Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 75)

Property: 0

Method: 8

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 4 1 5500 2 5900 2 0675 0 5976

5 4 1 0800 1 1900 1 1300 0 0455

6 2 1 3300 1 4800 1 4050 0 1061

7 3 1 3400 1 3600 1 3533 0 0115

14 1 1 1000 1 1000 1 1000 0 0000

15 1 1 2400 1 2400 1 2400 0 0000

16 12 1 1070 1 2530 1 2068 0 0434

18 2 1 2000 1 2500 1 2250 0 0354

19 7 1 1900 1 2600 1 2271 0 0206

21 6 1 1600 1 2100 1 1783 0 0172

22 4 1 2500 1 2800 1 2625 0 0150

24 14 1 0400 1 1800 1 1150 0 0372

25 5 1 3030 1 3780 1 3410 0 0275

Means 13 1.1000 2.0675 1.2963 0.2495

Table 8.10.6.2.3 Oxygen Concentration (wt. %) in SiC Powder

Material: Silicon Carbide (Figure 76)

Property: 0

Method: 8

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

2 2 0. 6750 0 6750 0 6750 0 0000

6 3 0. 7330 0 7490 0 7397 0 0083

7 2 0. 7300 0 7400 0 7350 0 0071

10 1 0. 8250 0 8250 0 8250 0 0000

15 1 0. 4500 0 4500 0 4500 0 0000

21 3 0. 6900 0 7100 0 7000 0 0100

22 2 0. 6400 0 6450 0 6425 0 0035

25 13 0. 7160 0 7650 0 7387 0 0145

Means 8 0.4500 0.8250 0.6882 0.1104

230
ED

>1

•o

(U

4-> UOuw

(0

V4 1oa

NRc

•H

u

•Hu

dP

c<co

o •H

•H 4J P U3

-i

C

o

0)

o

uco

•HW

c

bO

u

CO

o

•H

(N CM % 0

231
x>

•d

0)

4-> uo

o.

<u%4n

(d 1oH

C/3

•H

W

•H

«*

•-( • «d

4->

c *—

c § O

•H +J

iJ cn

CO 3

>-i ^ U S c o

(V

u

uG bO O C O •H

0)

c

d

<ubO CO X (0 O

in

CM

% 0

232
E

3

\j

0) U

^

Li

rnwJ

H

r >

w]

,^ 1 PA dP m 1 \

:»

c 0

o •H

•H 4-> 4J (0

(0 3

UU •i c OU

uG bO

o c o

W

c:

0)

Ul o

(U o o

C3 —1

—1

—1

ho bO

•H o o o O

in

• o• o

• o

• o

% 0

233
Table 8.10.6.2.4 Oxygen Concentration (wt. %) in Si Powder

Material: Silicon (Figure 77)

Property: 0

Method: 8

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

2 2 0,.5100 0,,5100 0,,5100 0,,0000

3 4 0,,5400 0.,5560 0.,5478 0,,0075

5 4 0,,4900 0.,5500 0,,5075 0,.0287

6 4 0,.4700 0,,5500 0.,4975 0,.0359

15 1 0..5400 0.,5400 0,,5400 0,.0000

16 5 0,.5160 0,,5490 0,,5352 0,.0138

18 1 0..4900 0.,4900 0.,4900 0,,0000

22 4 0,.5100 0,,5200 0,,5175 0 .0050

Means 8 0,.4900 0,,5478 0,,5182 0,.0209

8.10.6.3 Electrochemical Methods - Coulometric Titration

Table 8.10.6.3 Oxygen Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: 0

Method: 16

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1.7800 1.9800 1.8967 0.1041

Means 1.8967 1.8967 1.8967 0.0000

234
CD

in in

o

—1—1

—hCM o

tn in

• • o• o o

CD

O

•o

u

o

0)

>-l

CO

cdu

0)

o

(X •H

c

(0

dP

CO iJ <

c

c o

O

•H 4J 4J n

(0 3

J-i U •i

c ou

c

o c u •r-l a 3 «

CO

><! CO O

1^

3>

X 0

235
8.10.7. Fluorine in Silicon Nitride and Silicon Carbide

8.10.7.1 Mass Spectrometry

Table 8.10.7.1 Fluorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: F

Method: 5

# of Minimum Maximvim Average Standard

LAB // Values Value Value Value Deviation

8 3 0.0000 0.0000 0.0000 0.0000

Means 1 0.0000 0.0000 0.0000 0.0000

8 . 10 . 7 . 2 Ion Chromatography

Table 8.10.7.2.1 Fluorine Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: F

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 3 0.1100 0.1500 0.1293 0.0200

25 1 0.1700 0.1700 0.1700 0.0000

Means 2 0.1293 0.1700 0.1497 0.0288

236
Table 8.10.7.2.2 Fluorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: F

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 4 0.0020 0.0020 0.0020 0.0000

25 6 0.0070 0.0080 0.0075 0.0005

Means 2 0.0020 0.0075 0.0047 0.0039

8 . 10 . 7 . 3 Electrochemical Methods - Potentiometric Titration

Table 8.10.7.3.1 Fluorine Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: F

Method: 13

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

5 1 0.1200 0.1200 0.1200 0.0000

14 2 0.1200 0.1200 0.1200 0.0000

21 2 0.0760 0.0800 0.0780 0.0028

Means 3 0.0780 0.1200 0.1060 0.0242

237
Table 8.10.7.3.2 Fluorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: F

Method: 13

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

5 4 0.0040 0.0040 0.0040 0.0000

14 2 0.0060 0.0060 0.0060 0.0000

21 2 0.0050 0.0050 0.0050 0.0000

Means 3 0.0040 0.0060 0.0050 0.0010

Table 8.10.7.3.3 Fluorine Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: F

Method: 13

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

21 3 0.0400 0.0420 0.0407 0.0012

Means 1 0.0407 0.0407 0.0407 0.0000

8.10.7.4 Electrochemical Methods - Specific Ion Electrode

Table 8.10.7.4.1 Fluorine Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: F

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 2 0.1500 0.1640 0.1570 0.0099

Means 1 0.1570 0.1570 0.1570 0.0000

238
Table 8.10.7.4.2 Fluorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: F

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0110 0.0110 0.0110 0.0000

Means 1 0.0110 0.0110 0.0110 0.0000

Table 8.10.7.4.3 Fluorine Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: F

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0730 0.0730 0.0730 0.0000

Means 1 0.0730 0.0730 0.0730 0.0000

8.10.8 Sulfur in Yttria-Zirconia

8.10.8.1 Mass Spectrometry

Table 8.10.8.1 Sulfur Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: S

Method: 5

if of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.2000 0.2000 0.2000 0.0000

Means 1 0.2000 0.2000 0.2000 0.0000

239
8.10.8.2 Combustion Analysis

Table 8.10.8.2 Sulfur Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: S

Method: 8

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0900 0.0900 0.0900 0.0000

15 1 0.0910 0.0910 0.0910 0.0000

17 1 0.1000 0.1000 0.1000 0.0000

Means 3 0.0900 0.1000 0.0937 0.0055

8.10.8.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 8.10.8.3 Sulfur Concentration (wt, %) in YSZ Powder

Material: Zirconia

Property: S

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.1160 0.1160 0.1160 0.0000

Means 1 0.1160 0.1160 0.1160 0.0000

240
8.10.8.4 Ion Chromatography

Table 8.10.8.4 Sulfur Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: S

Method: 3

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

6 1 0.0310 0.0310 0.0310 0.0000

24 3 0.0160 0.0210 0.0180 0.0026

Means 2 0.0180 0.0310 0.0245 0.0092

8,10.9 Chlorine in Yttria-Zirconia

8,10.9.1 Neutron Activation Analysis

Table 8.10.9.1 Chlorine Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: CI

Method: 6

# of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

2 1 0.0340 0.0340 0.0340 0.0000

Means 1 0.0340 0.0340 0.0340 0.0000

241
o t<

C5

0) Q

-«->

0)

d

d

0)

CO O

0.30

d

0.20+0^

0.10 -

0.00

SigN^ (Ref.)

Combustion

O O 1 1

d

o

C.

T.

Within Lab \ \ }

09

•d

Betw.

Labs -g-g

Figure 78. Within lab, between lab, and between methods standard

deviations in the measurement of oxygen content for the

Si3Ni,(Ref.) powder as measured by various laboratories using a

variety of methods

.

242
0.30

a d

g o

o d

S tf

tn o

0.00

SigN^ (Test)

0.20 •

-

d

0.104- d 1:3

C.

Combustion

} j

1

1

I 1 1

Within Lab Betw.

Labs

89

. o

Figure 79. Within lab, between lab, and between methods standard

deviations in the measurement of oxygen content for the

SisN^CTest) powder as measured by various laboratories using a

variety of methods

243
0.30

St

0) Q

d

-»->

d

0)

d

d

0)

W O

0.20 •

•

0.10

0.00

I- Within Lab -J Beiw.

Labs

t9

. o

Figure 80. Within lab, between lab, and between methods standard

deviations in the measurement of oxygen content for the SiC

powder as measured by various laboratories using a variety of

methods

244
0.30

O ^

^

-s ^

0)

Q d

n-l O

^ d

w o

0.20 -

0.10-

0.00

I Within Lab ]

Betw.

Labs

•d

. o

Figure 81. Within lab, between lab, and between methods standard

deviations in the measurement of oxygen content for the Si

powder as measured by various laboratories using a variety of

methods

,

245
8.10.9.2 Ion Chromatography

Table 8.10.9.2 Chlorine Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: CI

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 2 0.0180 0.8600 0.4390 0.5954

24 3 0.0250 0.0280 0.0260 0.0017

Means 2 0.0260 0.4390 0.2325 0.2920

8.10.9.3 Electrochemical Methods - Argentometric Titration

Table 8.10.9.3 Chlorine Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: CI

Method: 14

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

14 1 0.0220 0.0220 0.0220 0.0000

Means 1 0.0220 0.0220 0.0220 0.0000

8.11. STATISTICAL ANALYSIS . R. Munro , NIST

The major nonmetallic impurities in the powders were carbon, nitrogen, and

oxygen, whenever they were not major constituents, along with chlorine,

fluorine, and sulfur. Two of the methods used for detecting these elements,

combustion and coulometric titration, involved the decomposition of the

powders in chemical reactions. A third method, fast neutron activation

analysis, provided on alternative technique that did not require a

decomposition reaction. Use of the latter method, however, was very limited

because of the need for a nuclear reactor facility, and there were

insufficient results to obtain a valid measure of its reproducibility.

Results for oxygen as an impurity, Figures 78-81, indicated that all the

methods were able to achieve approximately the same level of precision.

246
9. MAJOR METALLIC IMPURITIES

A. L. Dragoo, S. G. Malghan, R. G. Munro and S. M. Hsu; NIST

9.1. METHODS FOR FREE SILICON IN SILICON NITRIDE

Three determinations of free silicon in silicon nitride - 2 samples of SNT

powder and 1 of SNR powder - were reported. Each determination was carried

out by a different method. Although the data were insufficient for analysis,

a brief summary of the methods is of interest. Data are summarized in Section

8.10.1.

9.1.1. Electrochemical Methods - Potentiometric Titration (See 7.2.3.)

This method was reported by Lab 16. The silicon nitride sample was leached

with an AgF/HF solution. Free Si dissolves according to the reaction

4AgF(aq) + 2HF(aq) + Si(s) = HzSiFgCaq) + Ag(s)

The free silver was dissolved in nitric acid, and the amount of AgNOg

determined by potentiometric titration with a standardized KCl solution,

9.1.2. Volumetric Analysis

Lab 21 reported the use of this method, A silicon nitride powder sample was

reacted with a solution of NaOH. H2 formed by the reaction of NaOH with free

Si was collected and the volume of gas evolved was measured.

9.1.3. Standardized Method

A method described in DIN 51075, Part 2, for the determination of free Si in

SiC was used by Lab 3 for the analysis of free Si in the SNR powder.

Conclusions

Data were insufficient for adequate comparison of the methods.

9.2. METHODS FOR ALUMINUM. CALCIUM AND IRON

Aluminum and iron were determined as major impurities in SNR, SiC, Si and YSZ

powders and possibly as a major impurity in the SNT powder. Ca was determined

as a minor impurity in the Si powder,

ICP was the primary measurement method used, but AAS and DCP also were used

significantly for the analysis of the SNR powder. One or two measurements

were reported by XRF, optical emission spectroscopy and mass spectrometry.

However, the data obtained by these latter methods were insufficient for

statistical evaluation.

Data are summarized in Section 9,4,1. for Al , in Section 9.4.2. for Ca, and in

Section 9.4.3. for Fe

247
9.2.1. Atomic Absorption Spectroscopy (See 7.1.2.)

Instrument and Experimental Parameters

The predominant method of sample preparation for SisN^;, was acid digestion in a

pressure bomb. HF-HNO3 was the usual acid mixture; one laboratory reported

the addition of HCIO^ as a third component. The sample was reacted at 160 to

180 °C for 8 to 16 h. The solution which was obtained was usually treated

with HCIO^ and fumed to dryness to remove Si as SiF^. The residue was

dissolved, for example, in 5% hydrogen iodide and diluted to a standard

volume

Flux decomposition was used by a smaller number of laboratories for the

dissolution of Si3N^. Na02-Na2C03, KOH and Na2B^07 were used as fluxes. The

glass bead was dissolved in H2S0^ and the solution treated with HCIO^. The

solution was fumed to precipitate Si02, which was filtered off. The volume

and pH of the solution were adjusted.

SiC also was decomposed primarily with acids. A pressure bomb apparently was

not used by all laboratories. One laboratory reported using a HF-HNO3-H2SO4

(1:3:5) mixture and conducting the reaction at 210 °C for 12 h. Flux

decomposition using Li2C03 was reported by one laboratory.

One analyst noted that often the procedures for SiC and SisN^ are the same;

however, many times the SiC did not dissolve in the pressure bomb. When this

happened, Na02-Na2C03 was used. Even this was not a completely satisfactory

method.

In preparing Si samples for AAS , ICP or DCP analysis, most laboratories

decomposed the Si samples by dissolution in an acid solution which usually

consisted of a mixture of HF and HNO3 or HF and HCl. A pressure bomb was used

in some cases. After dissolution, H2SO4 or HCIO4 was added, and the solution

was fumed to remove Si.

With regard to preparation of Si samples by the flux method, one laboratory

reported decomposing samples in a Na02-Na2C03 flux; another laboratory

reported the use of a Na2Pi,07 flux.

Results and Discussion

A comparison of the sample dissolution and detection methods for the

determination of Al , Ca and Fe is presented in Table 9.2.1 for the SNR powder,

in Table 9.2.2 for the SNT powder and in Table 9.2.3 for the SiC powder.

Results for the determination of Al and Fe in Si powder are presented in Table

9.2.4.

In general AAS, ICP and DCP yielded very consistent results for Si3N^, when

acid digestion in a pressure bomb was used for the preparation of silicon

nitride and silicon carbide samples.

AAS and ICP gave consistent results when acid decomposition was used for the

preparation of Si samples.

248
Conclusions

See Section 7.1.2.

9.2.2. Inductively Coupled Plasma (See 7.1.3.)

Instrument and Experimental Parameters

Laboratory $8 reported the following operating conditions:

Coolant gas

Plasma gas

Nebulizer gas

Sample uptake

Power

Frequency

12 L/min

0.8 L/min

0.8 L/min

1 . 1 mL/rain

1200 W

17.2 MHz

This laboratory also reported the addition of 10 /ig/g Sc as an internal

standard and the use of synthetic standard solutions for calibration.

Results and Discussion

A comparison of the sample dissolution and detection methods for the two

silicon nitride powders, silicon carbide and silicon is presented in Tables

9.2.2.1, 9.2.2.2, 9.2.2.3 and 9.2.2.4, respectively.

In general AAS , ICP and DCP yielded very consistent results for SisN^ when

acid digestion in a pressure bomb was used.

Conclusions

Acid decomposition as described in Section 7.1.3 gave the most consistent

results. Results obtained with flux decomposition were frequently high with

respect to the results from acid decomposition.

AAS, ICP and DCP gave comparable results. The best precision is achieved when

an internal standard is incorporated into the solution and when synthetic

standard solutions are used for calibration.

9.2.3. Optical Emission Spectroscopy (PES)

Use and Significance

Since classical spectrochemical analysis was usually conducted with an arc

emission spectrograph, analysis by this method is often termed

"spectrochemical analysis." However, today spectrochemical analysis may be

carried out by other methods, such as AAS, ICP and DCP. To avoid confusion,

"spectrochemical analysis" or "spectrochemical methods" will only be used in

the generic sense in this report.

249
il

I

1

For qualitative analysis, the emission spectrograph is capable of detecting

0.001% or less of most metallic elements and certain nonmetallic ones,

| including P, Si, As, C and B, in a few milligrams of material. Quantitative

analysis can be conducted with automatic recording spectrographs. The typical

concentration range is normally 0.0001% to 75%; however, quantitative I precision is badly degraded by concentrations above the 30% level-'^^.

Instrximent and Experimental Parameters

The steps in emission spectroscopy are sample excitation, radiation

dispersion, radiation detection, data recording, data processing and

information reporting. The arc is powered and controlled by a high-voltage

arc generator. The control parameters are the self - inductance , L, of the

discharge circuit; and the resistance, R, of the discharge circuit; the

capacitance, C, of the charging capacitor; the voltage, Vj, , at the capacitor;

and the voltage, Vq, at the gap. By adjusting combinations of V^, , Vq, C, L

and R, the energy consumed by the spark and the duration of the discharge,

reproducible spectrochemical characteristics can be generated.

Since emission spectrographic methods are relative rather than absolute,

calibration with high-quality standards is required. Alteration of conditions

which affect the consistency of results necessitates the recalibration of the

instrument. For a high level of accuracy for a method, all samples should

exhibit similar rates of volatilization and spectral emission lines.

Standards and samples must be matched in physical and chemical composition.

Differences occurring during excitation must be minimized by the use of an

internal standard.

For optimum results, analysis of refractories, sinters and ores requires a

short time duration for the spark.

Details were not reported for preparative methods used in this study.

Results and Discussion

The single determination of Al in SNR SisN^ is high with respect to results

given by other methods. The result reported for Fe in SNR SisN^ also may be

slightly high with respect to the other methods, but the limited amount of

data does not permit a valid comparison to be made. The result reported for

SNT SigN^ appears to be in agreement with results obtained by NAA and DCP, but

again the limited amount of data does not permit valid comparisons to be made.

The result reported for Al in SiC appears to be low with respect to other

spectroscopic methods; whereas, the value for Ca is difficult to compare due

to the large amount of uncertainty in the results by all methods. Again, the

limited data make any comparison subject to question.

Conclusions

Data were insufficient for an analysis of variance and for valid comparisons

to be made with other data.

250
Table 9.2.2.1 Effects of Sample Dissolution Method and Spectrochemical

Analysis Method Measured Concentrations of Al , Ca and Fe in

SNR SisNz,. Concentrations are in percent by weight.

Uncertainties in parentheses are given as Student's t (95%

confidence level) to adjust for the different numbers of

determinations reported.

METHOD ACID FLUX

Al in SNR SigN^

AAS

ICP

DCP

0.040 (0.013)

0.040 (0.016)

0.042 (0.013)

0.030 ( -- )

0.037 (0.026)

0.040 ( -- )

Ca in SNR SigN^,

AAS

ICP

DCP

0.011 (0.014)

0.010 (0.014)

0.009 (0.011)

0.06 (0.10)

0.010 ( -- )

0.030 ( -- )

Fe in SNR SigN^

AAS

ICP

DCP

0.020 (0.010)

0.019 (0.014)

0.023 (0.013)

0.026 (0.035)

0.02 (0.09)

0.040 ( -- )

251
Table 9.2.2.2 Effects of Sample Dissolution Method and Spectrochemical

Analysis Method Measured Concentrations of Al , Ca and Fe in

SNT SisN^,. Concentrations are in percent by weight.

Uncertainties in parentheses are given as Student's t (95%

confidence level) to adjust for the different numbers of

determinations reported.

METHOD ACID FLUX

Al in SNT SigN^

AAS . 0.0011 (0.0013) NA

ICP 0.0003 (0.0013) NA

DCP 0.0016 (0.0013) NA

Ca in SNT SigN^

AAS 0.0032 ( -- ) 0.04 (0.14)

ICP 0.0006 (0.0011) NA

DCP 0.0029 (0.0013) NA

Fe in SNT SiaN^

AAS 0.0049 (0.0043) 0.033 (0.013)

ICP 0.0040 (0.0013) NA

DCP 0.0040 (0.0014) NA

NA, not available

252
Table 9.2.2.3 Effects of Sample Dissolution Method and Spectrochemical

Analysis Method Measured Concentrations of Al , Ca and Fe in

SiC. Concentrations are in percent by weight. Uncertainties

in parentheses are given as Student's t (95% confidence

level) to adjust for the different numbers of determinations

reported

.

METHOD ACID FLUX

Al in SiC

AAS

ICP

DCP

0.025 (0.013)

0.048 (0.040)

0.044 (0.005)

NA

0.06 (0.7)

NA

Ca in SiC

AAS

ICP

DCP

0.009 (0.02)

0.011 (0.020)

0.008 (0.002)

NA

0.13 (0.19)

NA

Fe in SiC

AAS

ICP

DCP

0.0015 (0.0014)

0.007 (0.010)

0.0027 (0.0016)

NA

0.1 (1.2)

NA

NA, not available

253
Table 9.2.2.4 Effects of Sample Dissolution Method and Spectrochemical

Analysis Method on Measured Concentrations of Al and Fe in

Si. Concentrations are in percent by weight. Uncertainties

in parentheses are estimated as Student's t (95 % confidence

level) to adjust for the different number of determinations

reported.

METHOD ACID FLUX

Al in Si

AAS 0.024 (0.005) 0.030 ( -- )

ICP 0.026 (0.021) NA

DCP NA 0.043 (0.003)

Fe in Si

AAS 0.042 (0.006) 0.050 ( -- )

ICP 0.040 (0.013) 0.1 (1.2)

DCP NA 0.050 (0.029)

NA, not available

9.2.4. DC Plasma (See 7.1.4.)

Instrument and Experimental Parameters

With regard to sample preparation, see Section 9.2.1.

Czupryna and Natansohn-"^^ discussed experimental conditions for the analysis of

major metallic impurities in SisN^. They employed an alkali fusion technique

to decompose their samples: namely, Na2C03 + Na2S0^ . The fused material was

dissolved in 1 M nitric acid. They observed that the DCP measurement is

affected by the following factors:

a. Total dissolved solids content which affects the amount of

background signal and broadening of emission lines;

b. Spectral line overlap;

c. Physico-chemical (matrix) effects which affect the ionization of the

system and either enhance or suppress the analyte signal.

254
In particular they investigated the suppression of Ca and Mg signals by Si.

They determined the detectability limits shown in Table 9.2.4.1.

Results and Discussion

See Tables 9 . 2 . 2 . 1 to 4

.

Flux decomposition was the only sample preparation method used to prepare Si

samples for DCP analysis. Results were high for both Ca and Fe determinations

as compared to results obtained with either AAS or ICP and acid decomposition.

This bias is suspected to be due to the flux decomposition method.

Conclusion

See Section 9.2.2.

Table 9.2.4.1 Detectability for Impurity Measurements in SigN^,.

Measurements made in 24 g/L of alkaline flux; Si3N4 at 1 mg/mL

(from Czupryna and Natansohn, Ref . 1)

Element Wavelength Measured in Determinable in

(nm) Solution (/ig/mL) Solid (/xg/g)

Al 396.15 0.01 10

B 249.77 0.10 100

Ca 393.37 0.010 10

Cr 425.43 0.001 1

Fe 371.99 0.10 100

Mg 279.55 0.01 10

Mo 379.82 0.010 10

W 400.87 0.10 100

9.3. METHODS FOR OTHER MAJOR METALLIC IMPURITIES IN YTTRIAZIRCONIA (Si, Ti, Hf, Sn, Nd, Ho)

The results obtained by the various methods are summarized in Table 9.3.1. Si

and Hf were the only impurities measured by at least 3 laboratories. In both

cases, ICP was the method used. For most of the results only one

determination per lab was reported. These determinations are not evaluated

here due to insufficient.

255
Table 9.3.1 Major Impurities in Yttria- Zirconia, % Weight

Method Si Ti Hf Sn Nd Ho

NAA NA U . UZo NT A NA NA NA

MS NA NAViirx 0 60 NA NA NA

XRF NA 0.025 1.83 NA NA NA

AAS 0.016 0.046 1.86 0.04 0.0281 0.025

ICP 0.007 0.024 1.32 NA NA NA

DCP 0.01 0.025 1.76 NA NA NA

NA, not available

9.4. STATISTICAL DATA ON MAJOR METALLIC IMPURITIES

9.4.1 Aluminum in All Powders

9.4.1.1 Mass Spectrometry

Table 9.4.1.1.1 Aluminum Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Al

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 2 0.0040 0.0050 0.0045 0.0007

Means 1 0.0045 0.0045 0.0045 0.0000

256
Table 9.4.1.1.2 Aluminum Concentration (wt. %) in Si Powder

Material: Silicon

Property: Al

Method: 5

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

8 2 0.015 0.015 0.015 0.000

Means 1 0.015 0.015 0.015 0.000

Table 9.4.1.1.3 Aluminum Concentration (wt. %) in Zr02 Powder

Material: Zirconia

Property: Al

Method: 5

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.003 0.050 0.023 0.024

Means 1 0.023 0.023 0.023 0.000

9.4.1 Aluminum in All Powder

9.4.1.2 Neutron Activation Analysis

Table 9.4.1.2 Aluminum Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Al

Method: 6

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.046 0.046 0.046 0.000

Means 1 0.046 0.046 0.046 0.000

257
9.4.1.3 X-ray Fluorescence Spectrometry

Table 9.4.1.3.1 Aluminum Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Al

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 1 0.038 0.038 0.038 0.000

Means 1 0.038 0.038 0.038 0.000

Table 9.4.1.3.2 Aluminum Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Al

Method: 12

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

10 1 0.026 0.026 0.026 0.000

Means 1 0.026 0.026 0.026 0.000

Table 9.4.1.3.3 Aluminum Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Al

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 3 0.042 0.042 0.042 0.000

Means 1 0.042 0.042 0.042 0.000

258
9.4.1.

9.4.1.4

Aluminum in All Powder

Atomic Absorption Spectroscopy

Table 9.4.1.4.1 Aluminum Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 82)

Property: Al

Method: 1

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 1 0.030 0,.030 0..030 0,,000

14 2 0.044 0,.045 0,.044 0,.000

16 6 0.035 0..042 0,.038 0,.002

18 1 0.460 0..460 0,.460 0,,000

Means 4 0.030 0,.460 0,.143 0,.211

Table 9.4.1.4.2 Aluminum Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 83)

Property: Al

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0010 0.0012 0.0011 0.0001

Means 1 0.0011 0.0011 0.0011 0.0000

259
•

•

1

z

r II o

•1 ^

S5

Silicon AA/AE

1

—1 1—1 ^

CD

CM

CM

CM

CM

O

CM

00

CD

jQ

E

3

CM jQ

00

CD

-d

u

o

P<u

m

u

(U Tlw

o

onC

•1-1

/—

dP

O

•1-1

4-) COU

C

CO

nc AA o

u bO

C

•r-i i

(0

—I

•

00

0)

bO

•1-1 o

in

o o o

CM

o o

• o

o

• o

• o

• o

• o

• o

X IV

260
E

.0)

4-> 5-1 o

0)U

Ui

0)o

(X

•l-l

dPo

•H

4-) (du

i-> c • 0) CO o c B •H 3 w C 3

•HS CO 3 XI

CO

00

(U

261
Table 9.4.1.4.3 Aluminum Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Al

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 2 0.025 0.026 0.025 0.0007

Means 1 0.025 0.025 0.025 0.0000

Table 9.4.1.4.4 Aluminum Concentration (wt. %) in Si Powder

Material: Silicon

Property: Al

Method: 1

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 1 0.006 0.006 0,,006 0.000

16 2 0.025 0.025 0,.025 0.000

18 1 0.030 0.030 0,,030 0.000

19 9 0.021 0.028 0,,024 0.002

Means 4 0.006 0.030 0,,021 0.010

Table 9.4.1.4.5 Aluminum Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Al

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.035 0.036 0.035 0.0007

19 8 0.070 0.080 0.071 0.0035

Means 2 0.035 0.071 0.053 0.0253

262
9.4.1. Aluminum in All Powders

9.4.1.5 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.1.5.1 Aluminum Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 84)

Property: Al

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 0 030 0 040 0 037 0 006

5 1 0 038 0 038 0 038 0 000

6 2 0 036 0 048 0 042 0 008

7 6 0 043 0 046 0 045 0 001

13 11 0 020 0 040 0 035 0 008

15 1 0 041 0 041 0 041 0 000

19 1 0 043 0 043 0 043 0 000

20 1 0 001 0 001 0 001 0 000

21 4 0 043 0 045 0 044 0 001

22 8 0 028 0 053 0 041 0 010

Means 10 0 0015 0 0450 0 0369 0 0128

Table 9.4.1.5.2 Aluminum Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 85)

Property: Al

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 4 0 000 0 000 0 000 0 000

17 1 0 504 0 504 0 504 0 000

18 1 0 200 0 200 0 200 0 000

19 7 0 000 0 000 0 000 0 000

20 1 0 000 0 000 0 000 0 000

22 8 0 016 0 022 0 020 0 002

Means 6 0.0001 0.504 0.120 0.203

263
264
265
Table 9.4.1.5.3 Aluminum Concentration (wt. %) in SiC Powder

Material: Silicon Carbide (Figure 86)

Property: Al

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

6 1 0,,026 0.,026 0.,026 0,,000

15 1 0.,033 0,,033 0,,033 0,,000

17 1 0,,013 0,,013 0,,013 0,,000

20 2 0,,019 0,,100 0,,059 0,.057

21 3 0,,044 0..047 0,.046 0..001

22 8 0,,024 0,.086 0..050 0,.022

Means 6 0.,013 0,.059 0,.038 0,.017

Table 9.4.1.5.4

Material: Silicon

Property: Al

Method: 2

Aluminum Concentration (wt. %) in Si Powder

(Figure 87)

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 4 0,,016 0,.017 0.,017 0,,000

6 1 0,,035 0,.035 0,,035 0,,000

7 2 0,,032 0,.033 0,,032 0,,001

15 1 0.,040 0,.040 0,,040 0,.000

17 1 0.,024 0,.024 0,,024 0,.000

20 2 0,.028 0,.031 0,,029 0,.002

22 8 0,.013 0,,032 0,,027 0,.006

Means 7 0..017 0,.040 0,,029 0,.007

266
% IV

267
x>

-o

<u uuoa

0)

S-i n

(1) O

a.

•H

on

4-> o

•H

4-) (0C •

0) Pli O U C M OU bOC C 3 g m

oou

00

X IV

268
Table 9.4.1.5.5 Aluminum Concentration (wt. %) in YSZ Powde

Material: Zirconia (Figure 88)

Property: Al

Method: 2

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 2 0 040 0 050 0.045 0 007

6 2 0 066 0 314 0.190 0 175

15 1 0 052 0 052 0.052 0 000

17 1 0 260 0 260 0.260 0 000

ans 4 0 045 0 260 0.137 0 106

9.4.1. Aluminum in All Powder

9.4.1.6 Arc Emission Spectroscopy

Table 9.4.1.6.1 Aluminum Concentration (wt. %) in SNR Powde

Material: Silicon Nitride, Reference Powder

Property: Al

Method: 7

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

7 1 0.060 0.060 0.060 0.000

23 1 0.010 0.010 0.010 0.000

Means 2 0.010 0.060 0.035 0.035

269
E

3

•d

<u u

u

o

IXu

n

cd

0)

o

a. N

CO

4J

o

to U

c • o o

C M

o c

3 (0 C 3

1-1§m

.—I cfl

o lO o in o in o in o

• fO to o o• o• o• o

• o

• o• o• o

• o o

00CO

0)u

•l-t b

% IV

270
Table 9.4,1.6.2 Aluminum Concentration (wt. %) in SiC Powde

Material: Silicon Carbide

Property: Al

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.010 0.010 0.010 0.000

Means 1 0.010 0.010 0.010 0.000

Table 9.4.1.6.3 Aluminum Concentration (wt. %) in Si Powder

Material: Silicon

Property: Al

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

i 1 0.020 0.020 0.020 0.000

Means 1 0.020 0.020 0.020 0.000

9.4.1. Aluminum in All Powder

9.4.1.7 DC Plasma - Emission Spectroscopy

Table 9.4.1.7.1 Aluminum Concentration (wt. %) in SNR Powde

Material: Silicon Nitride, Reference Powder (Figure 89)

Property: Al

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 1 0.040 0.040 0.040 0.000

14 1 0.043 0.043 0.043 0.000

17 2 0.040 0.040 0.040 0.000

25 1 0.042 0.041 0.042 0.000

Means 4 0.040 0.043 0.041 0.001

271
u

o

o

CO

dp

G

o

(du

u

c

(U CM

C

•HW

u

00

u

a.

% IV

272
Table 9.4.1.7.2 Aluminum Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Al

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0015 0.0017 0.0016 0.0001

Means 1 0.0016 0.0016 0.0016 0.0000

Table 9.4.1.7.3 Aluminum Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Al

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 6 0.0415 0.0464 0.0436 0.0019

Means 1 0.0436 0.0436 0.0436 0.0000

Table 9.4.1.7.4 Aluminum Concentration (wt . %) in Si Powder

Material: Silicon

Property: Al

Method: 17

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

3 4 0.0420 0.0440 0.0428 0.0010

Means 1 0.0428 0.0428 0.0428 0.0000

273
Table 9.4.1.7.5 Aluminum Concentration (wt. %) in YSZ Powde

Material: Zirconia

Property: Al

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.048 0.048 0.048 0.000

17 1 0.250 0.250 0.250 0.000

Means 2 0.048 0.250 0.149 0.143

9.4.1. Aluminum in All Powder

9.4.1.8 Method not specified

Table 9.4.1.8 Aluminum Concentration (wt. %) in SiC Powde

Material: Silicon Carbide

Property: Al

Method: 21

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

18 1 0.260 0.260 0.260 0.000

Means 1 0.260 0.260 0.260 0.000

274
9,4.2. Calcium in Silicon Nitride. Silicon Carbide and YttriaZirconia

9.4.2.1 Mass Spectrometry

Table 9.4.2.1.1 Calcium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ca

Method: 5

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

8 3 0.0005 0.0016 0.0009 0.0006

Means 1 0.0009 0.0009 0.0009 0.0000

Table 9,4.2.1.2 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ca

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 2 0.004 0.006 0.005 0.001

Means 1 0.005 0.005 0.005 0.000

Table 9.4.2.1.3 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 5

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.002 0.007 0.0037 0.0029

Means 1 0.0037 0.0037 0.0037 0.000

275
9.4.2.2 Neutron Activation Analysis

Table 9.4.2.2 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 6

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

2 1 0.027 0.027 0.027 0.000

Means 1 0.027 0.027 0.027 0.000

9.4.2.3 X-ray Fluorescence Spectrometry

Table 9.4.2.3.1 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ca

Method: 12

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

10 1 0.002 0.002 0.002 0.000

Means 1 0.002 0.002 0.002 0.000

Table 9.4.2.3.2 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 12

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 3 0.022 0.023 0.023 0.0006

Means 1 0.023 0.023 0.023 0.0000

276
9.4.2.4 Atomic Absorption Spectroscopy

Table 9.4.2.4.1 Calcium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 90)

Property: Ca

Method: 1

of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 1 0 020 0.020 0 020 0 000

14 2 0 020 0.020 0 020 0 000

16 6 0 006 0.011 0 008 0 002

18 1 0 020 0.020 0 020 0 000

24 3 0 050 0.098 0 072 0 024

Means 5 0 008 0.072 0 028 0 025

Table 9.4.2.4.2 Calcium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ca

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.003 0.003 0.003 0.000

24 2 0.029 0.045 0.037 0.011

Means 2 0.003 0.037 0.020 0.023

277
oo

H

—1

—

00 (D o• O• o• o o oCMO

O

0)£3O

T3

di •uuo

(Uuu

COuoaC

4Jco

•H

•U

1%O bO y C

•iH

S CO 3 3

•HU CQ ^ XI o

0)

X DO

278
Table 9.4.2.4.3 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ca

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

10 1 0.014 0.014 0.014 0.000

16 2 0.006 0.006 0.006 0.000

Means 2 0.006 0.014 0.010 0.005

Table 9.4.2.4.4 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 1

# of Minimum Maximtun Average Standard

LAB # Values Value Value Value Deviation

14 2 0.014 0.040 0.027 0.018

18 3 0.012 0.014 0.013 0.001

19 8 0.010 0.010 0.010 0.000

Means 3 0.010 0.027 0.017 0.009

279
9.4.2.5 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.2.5.1 Calcium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 91)

Property: Ca

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 3 0 010 0 010 0 010 0 000

5 1 0 008 0 008 0 008 0 000

6 2 0 010 0 014 0 012 0 003

7 6 0 009 0 010 0 010 0 000

13 11 0 010 0 040 0 015 0 009

15 1 0 009 0 009 0 009 0 000

19 1 0 009 0 009 0 009 0 000

20 1 0 001 0 001 0 001 0 000

21 4 0 Oil 0 012 0 Oil 0 000

22 11 0 001 0 012 0 005 0 004

Means 10 0.0015 0.015 0.009 0.004

Table 9.4.2.5.2 Calcium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 92)

Property: Ca

Method: 2

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

5 4 0 000 0.000 0 000 0 000

6 1 0 007 0.007 0 007 0 000

15 1 0 000 0.000 0 000 0 000

17 1 0 012 0.012 0 012 0 000

18 1 0 010 0.010 0 010 0 000

19 7 0 000 0.000 0 000 0 000

20 1 0 000 0.000 0 000 0 000

21 4 0 001 0.001 0 001 0 000

22 2 0 001 0.002 0 001 0 001

Means 9 0.000 0.012 0.004 0.004

280
CD

CM

\ 1 1 1 ho

in o ID o in o

CM CM o o

o• O• O o o• o• o o

• o• o o o

% DO

281
0) 4J

VIo

Cu

a>u

w

C0

VI

4) 1

O

H

CO

G

o

f-l

<d

vi *j • C Ou O M

c ^ U C

•H §0)

•HU (0

CM

0)

04 o 00 CO CM o

o o o o o

O o o o o o• o• d

• o

• o

• o

• o o o

% DO

282
Table 9.4.2.5.3 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide (Figure 93)

Property: Ca

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0 010 0. 010 0. 010 0.000

15 1 0 008 0. 008 0. 008 0.000

17 1 0 007 0. 007 0. 007 0.000

20 2 0 120 0. 150 0. 135 0.021

21 3 0 006 0. 006 0. 006 0.000

22 8 0 001 0. 027 0. 013 0.010

Means 6 0 006 0. 135 0. 030 0.051

Table 9.4.2.5.4 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 2

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.034 0.034 0.034 0.000

15 1 0.011 0.011 0.011 0.000

17 1 0.020 0.020 0.020 0.000

Means 3 0.011 0.034 0.021 0.011

283
Xi

•O

0) 4JU

O

(X«

»4

o

a. o1-1 CO

4J

o

•H

•P • C Pu

<U U

O M

c

O bO

O C

•H §(0

OS

o o o o o o o o o

CO CM o 00 CO CM o

• • • o o o o o• o o o

• o• o

• o• o

• o o

X 00

284
9.4.2.6 Arc Emission Spectroscopy

Table 9.4.2.6 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ca

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.010 0.010 0.010 0.000

Means 1 0.010 0.010 0.010 0.000

9.4.2.7 DC Plasma - Emission Spectroscopy

Table 9.4.2.7.1 Calcium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 94)

Property: Ca

Method: 17

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 1 0,.030 0,.030 0.030 0,.000

14 1 0,.008 0,.008 0.008 0,.000

17 2 0,.007 0,.010 0.008 0,.002

25 1 0,.009 0,.009 0.009 0,.000

Means 4 0,,008 0,.030 0.014 0,.010

285
puo«

0)

cdo

a.

4Jo

•HU

Cdu

a> cj u a cO bO o C

•H

E

w 3 3 u n ^ Xi

cd cd

ONu

X DO

286
Table 9.4.2.7.2 Calcium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ca

Method: 17

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

14 2 0.003 0.003 0.003 0.000

Means 1 0.003 0.003 0.003 0.000

Table 9.4.2.7.3 Calcium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ca

Method: 17

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 6 0.007 0.009 0.008 0.001

Means 1 0.008 0.008 0.008 0.000

Table 9.4.2.7.4 Calcium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ca

Method: 17

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

17 1 0.020 0.020 0.020 0.000

Means 1 0.020 0.020 0.020 0.000

287
9.4.3 Iron in All Powders

9.4.3.1 Mass Spectrometry

Table 9.4.3.1.1 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Fe

Method: 5

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

8 3 0.002 0.008 0.006 0.003

Means 1 0.006 0.006 0.006 0.000

Table 9.4.3.1.2 Iron Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Fe

Method: 5

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.060 0.100 0.087 0.023

Means 1 0.087 0.087 0.087 0.000

288
9.4.3.2 Neutron Activation Analysis

Table 9.4.3.2 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Fe

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.0037 0.0037 0.0037 0.000

Means 1 0.0037 0.0037 0.0037 0.000

9.4.3.3 X-ray Fluorescence Spectrometry

Table 9.4.3.3.1 Iron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Fe

Method: 12

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

10 1 0.014 0.014 0.014 0.000

Means 1 0.014 0.014 0.014 0.000

289
Table 9.4.3.3.2 Iron Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Fe

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 3 0.014 0.015 0.014 0.000

Means 1 0.014 0.014 0.014 0.000

9.4.3.4 Atomic Absorption Spectroscopy

Table 9.4.3.4.1 Iron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 95)

Property: Fe

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.010 0.010 0.010 0.000

14 2 0.015 0.015 0.015 0.000

16 6 0.019 0.026 0.021 0.002

18 1 0.270 0.270 0.270 0.000

24 3 0.030 0.035 0.031 0.003

Means 5 0.010 0.270 0.069 0.112

290
Table 9.4.3.4.2 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Fe

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.005 0.005 0.005 0.000

16 1 0.004 0.004 0.004 0.000

24 2 0.030 0.035 0.032 0.003

Means 3 0.004 0.033 0.014 0.016

Table 9.4.3.4.3 Iron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Fe

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

10 1 0.001 0.001 0.001 0.000

16 2 0.001 0.002 0.002 0.000

Means 2 0.001 0.001 0.001 0.000

Table 9.4.3.4.4 Iron Concentration (wt. %) in Si Powder

Material: Silicon (Figure 96)

Property: Fe

Method: 1

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 1 0 045 0 045 0 045 0 000

16 2 0 038 0 038 0 038 0 000

18 1 0 050 0 050 0 050 0 000

19 9 0 042 0 047 0 043 0 001

Means 4 0 038 0 050 0 044 0 005

291
292
E3 m

<u uuo

a.

0)uoa

«H

4Jco

•H

4J

CdU

+Jcocoocou CO3

Oiu3

bO

•H

1^

% 3J

293
Table 9.4.3.4.5 Iron Concentration (wt . %) in YSZ Powder

Material: Zirconia

Property: Fe

Method: 1

# of Minimum Maximum Average Standard

LA.B # Values Value Value Value Deviation

18 3 0.120 0.150 0.133 0.015

19 8 0.010 0.010 0.010 0.000

Means 2 0.010 0.133 0.071 0.087

9.4.3.5 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.3.5.1 Iron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 97)

Property: Fe

Method: 2

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0 010 0 010 0 010 0 000

5 1 0 018 0 018 0 018 0 000

6 2 0 019 0 049 0 034 0 021

7 6 0 021 0 023 0 022 0 001

13 7 0 010 0 010 0 010 0 000

15 1 0 021 0 021 0 021 0 000

19 1 0 020 0 020 0 020 0 000

20 1 0 006 0 006 0 006 0 000

21 4 0 023 0 024 0 024 0 000

22 11 0 Oil 0 029 0 021 0 008

leans 10 0 006 0 034 0 019 0 008

294
CO

CN

CO

o•

in

o o

roO

CMO o• o

o• o

• o

• o

• o

• o o o

295
Table 9.4.3.5.2 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder (Figure 98)

Property: Fe

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

5 4 0 003 0 003 0 003 0 000

6 1 0 005 0 005 0 005 0 000

7 3 0 002 0 003 0 003 0 000

15 1 0 004 0 004 0 004 0 000

17 1 0 019 0 019 0 019 0 000

18 1 0 200 0 200 0 200 0 000

19 7 0 004 0 004 0 004 0 000

20 1 0 000 0 001 0 001 0 000

21 4 0 004 0 005 0 005 0 000

22 8 0 010 0 Oil 0 010 0 000

Means 10 0 001 0 200 0 025 0 061

Table 9.4.3.5.3 Iron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide (Figure 99)

Property: Fe

Method: 2

# of Minimum Maximum Average

LAB # Values Value Value Value

Standard

Deviation

6 1 0 004 0 004 0 004 0 000

15 1 0 005 0 005 0 005 0 000

20 2 0 060 0 190 0 125 0 092

21 3 0 001 0 001 0 001 0 000

22 8 0 004 0 013 0 009 0 004

Means 5 0 001 0 125 0 029 0 054

296
297
Table 9.4.3.5.4 Iron Concentration (wt. %) in Si Powder

Material: Silicon (Figure 100)

Property: Fe

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

5 4 0,,034 0.,036 0,.035 0,.001

6 1 0,,046 0,.046 0..046 0,,000

7 2 0,,047 0,.049 0,.048 0,,001

15 1 0,,040 0,.040 0,.040 0,,000

17 1 0,,040 0,.040 0,.040 0.,000

20 2 0.,040 0,.042 0..041 0.,001

22 8 0,,050 0,.054 0,.052 0,,002

Means 7 0,,035 0,.052 0,.043 0,,006

Table 9.4.3.5.5 Iron Concentration (wt. %) in YSZ Powder

Material: Zirconia (Figure 101)

Property: Fe

Method: 2

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0,,003 0,.004 0,,003 0,.001

6 1 0,,002 0,.002 0,,002 0,,000

15 1 0.,005 0,.005 0.,005 0..000

17 1 0.,020 0,.020 0,,020 0.,000

Means 4 0,,002 0..020 0,,008 0,,008

298
E

O

,Q

•O

(U

1-1 O

<U

1-1 n

cdu

0)

o

a.

CO

o

•H

4-> COV4 4J

(Uo

C

ou

c

o

5-i

o

bfi c

•H3

ONOn

0)

bO

in o in o m o

CM

• <N o• o• o

• o

• o

• o o o

% 9J

299
01

cd

x>

•o

di uuo

0)u

(0uo

1-1

4J5co

•H

Cd

>-l 4JC

0) • U CM c u O M oc c O -r-l u cn oo

0)

CkO

300
9.4.3.6 Arc Emission Spectroscopy

Table 9.4.3.6.1 Iron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Fe

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 1 0.030 0.030 0.030 0.000

23 1 0.020 0.020 0.020 0.000

Means 2 0.020 0.030 0.025 0.007

Table 9.4.3.6.2 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Fe

Method: 7

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 1 0.004 0.004 0.004 0.000

Means 1 0.004 0.004 0.004 0.000

Table 9.4.3.6.3 Iron Concentration (wt. %) in Si Powder

Material: Silicon

Property: Fe

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.030 0.030 0.030 0.000

Means 1 0.030 0.030 0.030 0.000

301
E3

01

Xt

•O

0)

4-)

>-l O

a.

CO

(du

0)oNW

>^

4Jco

f-i 4J

COU

4-> cuCooou

bO

(0

u

bO

% 9J

302
9.4.3.7 DC Plasma - Emission Spectroscopy

Table 9.4.3.7.1 Iron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder (Figure 102)

Property: Fe

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 1 0,.040 0.040 0,,040 0,,000

14 1 0,,022 0.022 0,,022 0.,000

17 2 0,,020 0.020 0.,020 0.,000

25 1 0,,023 0.023 0,,023 0,,000

ans 4 0,,020 0.040 0,,026 0.,009

Table 9.4.3.7.2 Iron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Fe

Method: 17

# of Minimum Maximum Average Standard

LAB if Values Value Value Value Deviation

14 1 0.003 0.003 0.003 0.000

25 4 0.004 0.004 0.004 0.000

Means 2 0.003 0.004 0.004 0.001

303
JQE3O

0) uo

a)u

a>o

p.G

4Jo

•Huycooco

PLI uQu

o

a>

bO

304
Table 9.4.3.7.3 Iron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Fe

Method: 17

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

25 6 0.002 0.003 0.003 0.001

Means 1 0.003 0.003 0.003 0.000

Table 9.4.3.7.4 Iron Concentration (wt. %) in Si Powder

Material: Silicon

Property: Fe

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 4 0.043 0.063 0.050 0.009

Means 1 0.050 0.050 0.050 0.000

Table 9.4.3.7.5 Iron Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Fe

Method: 17

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.003 0.003 0.003 0.000

17 1 0.030 0.030 0.030 0.000

Means 2 0.003 0.030 0.016 0.019

305
9.4.3.8 Method not specified

Table 9.4.3.8 Iron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Fe

Method: 21

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

18 0.190 0.190 0.190 0.000

Means 0.190 0.190 0.190 0.000

9.4.4 Silicon in Yttria-Zirconia

9.4.4.1 Atomic Absorption Spectroscopy

Table 9.4.4.1 Silicon Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Si

Method: 1

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

18

19

3

8

0.026

0.010

0.033

0.010

0.030

0.010

0.004

0.001

Means 0.010 0.030 0.020 0.014

306
9.4.4.2 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.4.2 Silicon Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Si

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0.006 0.007 0.006 0.001

6 1 0.004 0.004 0.004 0.000

17 1 0.010 0.010 0.010 0.000

Means 3 0.004 0.010 0.007 0.003

9.4.4.3 DC Plasma - Emission Spectroscopy

Table 9.4.4.3 Silicon Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Si

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 0.010 0.010 0.010 0.000

Means 1 0.010 0.010 0.010 0.000

307
9.4.5 Titanium in Yttria-Zlrconla

9.4.5.1 Neutron Activation Analysis

Table 9.4.5.1 Titanium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ti

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.026 0.026 0.026 0.000

Means 1 0.026 0.026 0.026 0.000

9.4.5.2 X-ray Fluorescence Spectrometry

Table 9.4.5.2 Titanium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ti

Method: 12

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

24 3 0.025 0.026 0.025 0.001

Means 1 0.025 0.025 0.025 0.000

308
9.4.5.3 Atomic Absorption Spectroscopy

Table 9.4.5.3 Titanium Concentration (wt. %) In YSZ Powder

Material: Zlrconla

Property: Tl

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.024 0.025 0.024 0.001

19 8 0.040 0.060 0.051 0.008

Means 2 0.024 0.051 0.038 0.019

9.4.5.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.5.4 Titanium Concentration (wt. %) in YSZ Powder

Material: Zlrconla

Property: Tl

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 0.026 0.028 0.027 0.001

6 1 0.018 0.018 0.018 0.000

15 1 0.024 0.024 0.024 0.000

Means 3 0.018 0.027 0.023 0.004

309
9.4.5.5 DC Plasma - Emission Spectroscopy

Table 9.4.5,5 Titanium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ti

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 i 0.025 0.025 0.025 0.000

Means 1 0.025 0.025 0.025 0.000

9.4.6 Hafnium in Yttria- Zirconia

9.4.6.1 Mass Spectrometry

Table 9.4.6.1 Hafnium Concentration (wt. %) in YSZ Powder

Material : Zirconia

Property: Hf

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.60 0.60 0.60 0.00

Means 1 0.60 0.60 0.60 0.00

310
9.4.6.2 X-ray Fluorescence Spectrometry

Table 9.4.6.2 Hafnium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Hf

Method: 12

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 6 1.820 1.840 1.828 0.007

Means 1 1.828 1.828 1.828 0.000

9.4.6.3 Atomic Absorption Spectroscopy

Table 9.4.6.3 Hafnium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Hf

Method: 1

# of Minimtun Maximum Average Standard

LAB if Values Value Value Value Deviation

18 3 1.790 1.950 1.860 0.082

Means 1 1.860 1.860 1.860 0.000

311
9.4.6.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.6.4 Hafnium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Hf

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 2 1.720 1.720 1.720 0.000

6 1 0.080 0.080 0.080 0.000

17 1 1.770 1.770 1.770 0.000

Means 3 0.080 1.770 1.190 0.961

9.4.6.5 DC Plasma - Emission Spectroscopy

Table 9.4.6.5 Hafnium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Hf

Method: 17

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 1.760 1.760 1.760 0.000

Means 1 1.760 1.760 1.760 0.000

312
9.4.7 Tin in Yttrla-Zirconia

9.4.7.1 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.7.1 Tin Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Sn

Method: 2

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 2 0.014 0.059 0.036 0.032

Means 1 0.036 0.036 0.036 0.000

9.4.8 Neodymium in Yttria- Zirconia

9.4.8.1 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.8.1 Neodymium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Nd

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 i 0.028 0.028 0.028 0.00

Means 1 0.028 0.028 0.028 0.00

313

I
9.4.9 Holmium In Yttria-Zirconia

9.4.9.1 Inductively Coupled Plasma - Emission Spectroscopy

Table 9.4.9.1 Holmium Concentration (wt. X) in YSZ Powder

Material: Zirconia

Property: Ho

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.025 0.025 0.025 0.000

Means 1 0.025 0.025 0.025 0.000

314
10. MINOR NONMETALLIC AND METALLIC IMPURITIES (Concentration < 100 ppm

by weight) A. L. Dragoo, S. G. Malghan, S. M. Hsu and R. G. Munro,

NIST

10.1. METHODS FOR MINOR NONMETALLIC AND METALLIC IMPURITIES

Methods used for determination of minor impurities have been described in

Chapters 7 , 8 and 9 . Nearly all of the instrumental methods were used to

measure one or more of the minor impurities . Impurities with relative

concentrations in the range of 1 ppm to 100 ppm are termed "Minor Impurities .

Minor impurities are reported below for which determinations were included in

this study. In most cases, the data were insufficient for an evaluation of

the method. The impurities and the methods used are given without further

comment unless four or more determinations were reported.

10.2. NONMETALLIC IMPURITIES (S. F. CI) IN SILICON NITRIDE. SILICON

CARBIDE AND SILICON

10.2.1. Sulfur

Table 10.2.1 Sulfur in SisN^,, SiC and Si. Concentrations are in ppm by

weight

Method SNR SNT SiC Si

MS 3 —

Combustion 110 —

ICP 182 44 5

not available

10.2.2. Fluorine

Fluorine was reported at 40 ppm in silicon by one laboratory which used the

specific ion electrode method and at 20 ppm by one laboratory which used

potentiometric titration.

10.2.3. Chlorine

The results for chlorine determinations are summarized in Table 10.2.3. With

the exception of the following three determinations, most results for a method

and material were reported by only one laboratory and with less than four

replications

.

315
Lab 25 reported six determinations of the chlorine concentration in the SNT

powder using ion chromatography: mean 87 ppm, s.d. 6 ppm.

Two laboratories reported the determination of chlorine concentration in SNT

powder, total of six samples, using potentiometric titration: mean 87 ppm,

s.d, 20 ppm.

Lab 5 reported four determinations of chlorine in Si by potentiometric

titration: mean 40 ppm, s.d. 6 ppm.

Table 10.2.3 Chlorine in SisN/,, SiC and Si. Concentrations are in ppm by

weight

Method SNR SNT SiC Si

Ion Chromat- 35 87 241 210

ography

NAA — 80 — —

SCA 55 68 — —

Potentiometric — 87 51 40

Titration

Gravimetry 100 — — —

— not available

10.3. METALLIC IMPURITIES IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

(Na, Mg, K, Ti, Cr, Mn, Ni, W, B)

10.3.1. Sodium. Magnesium and Potassium

Results for Na and K impurities were, in most cases, for a single laboratory

and a single determination. The average ICP result for Na in SiC was strongly

skewed by a very large result obtained by one of the three laboratories

reporting. If the outlying result is discarded, the average is about 18 ppm.

With the exception of the determination by mass spectrometry, Mg

concentrations were replicated and were performed by more than one laboratory.

The largest number of determinations by laboratories was that for Mg in the

SNR powder by ICP. The means and standard deviations given in the Table

10.3.1 were averaged with respect to the laboratories. The ICP result for Mg

in SNR powder is the average of the results of eight laboratories;

replications by individual laboratories range from 1 to 11 determinations.

316
Table 10.3.1 Summary of Data for the Metallic Impurities Na, Mg and K in

Silicon Nitride and Silicon Carbide for All Methods

Reported. Concentration in ppm.

Material Method Na Mg K

SigN^, SNR SCA

AAS

ICP

DCP

Grav.

8

27

19

31

100

90(14)

140(110)

60(32)

73(3)

100

SigN^ SNT

SiC

Si

MS

AAS

ICP

DCP

MS

AAS

ICP

DCP

AAS

ICP

DCP

3

8

6

8

1510

11

11

50

1

60(70)

33(44)

4

10

9

72

3

25(5)

44(7)

2

21

37

( ) replicate values; not available

317
10.3.2. Titanium. Chromium and Manganese

The results for Ti , Cr and Mn impurities are summarized in Table 10.3.2. With

the exception of determinations of Ti concentrations by TCP, the data were

insufficient for any statistical evaluation. The large standard deviations

which were obtained for the ICP determinations of Ti in the SNR and SNT

powders suggest that sample preparation errors may have been a significant

source of experimental error for the analyses of those powders.

Table 10.3.2 Summary of Data for the Metallic Impurities Ti, Cr and Mn in

Silicon Nitride and Silicon Carbide for All Methods

Reported. Concentration in ppm.

Material Method Ti Cr Mn

SigN^ SNR OES 30 20

AAS 15 6

ICP 186(272) 3 7

DCP 30

SigN^ SNT NAA 6 >1

MS 1 3

AAS 3

ICP 225 5 >1

SiC XRF 60

ICP 33(20) 23 >1

DCP 38

Si AAS 7 2 8(2)

ICP 8(2) 4 8

( ) replicate values; not available

I

318

I
10.3.3. Nickel. Tungsten and Boron

The results for Ni, W and B impurities are summarized in Table 10.3.3. The

data were insufficient for statistical evaluation.

Table 10.3.3 Summary of Data for the Metallic Impurities Ni , W and B in

Silicon Nitride and Silicon Carbide for All Methods

Reported. Concentration in ppm.

Material Me thod Ni W B

SigN^ SNR OES

AAS

ICP

DCP 50

10

20

SigN^ SNT MS

OES

ICP

2

5

5(1)

SiC ICP 30

Si AAS 10

Si ICP 6(3)

not available

319
10.4. METALLIC IMPURITIES IN YTTRIA-ZIRCONIA (Na, Mg, K, Ga, Ba)

The results are summarized In Table 10.4.1.

Table 10.4.1 Summary of Data for the Metallic Impurities Na, Mg, K, Ga

and Ba in Yttria-Zirconia for All Methods Reported.

Concentration in ppm.

Method Na Mg K Ga Ba

NAA

MS

AAS

ICP

DCP

77

230

70(31)

22

70

53(45) 50

48(36)

20

58 330

not available

10.5 SULFUR IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

Sulfur is classed here as a minor impurity although it was detected as a less

abundant major impurity, in the range of a few hundred ppm in some

measurements . However , in other measurements and for the SNT powder

especially, it was detected as a minor impurity.

10.5.1 Mass Spectroscopy

Table 10.5.1 Sulfur Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: S

Method: 5

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

0.0001 0.0005 0.0003 0.0003

Means 1 0.0003 0.0003 0.0003 0.0000

320
10.5.2 Combustion Analysis

Table 10.5.2 Sulfur Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: S

Method: 8

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 0.011 0.011 0.011 0.000

Means 1 0.011 0.011 0.011 0.000

10.5.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.5.3.1 Sulfur Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: S

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 2 0.0040 0.0323 0.0182 0.0200

Means 1 0.0182 0.0182 0.0182 0.0000

Table 10.5.3.2 Sulfur Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: S

Method: 2

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0044 0.0044 0.0044 0.0000

Means 1 0.0044 0.0044 0.0044 0.0000

3p
Table 10.5.3.3 Sulfur Concentration (wt. %) in Si Powder

Material: Silicon

Property: S

Method: 2

# of

LA.B # Values

Minimum Maximum Average Standard

Value Value Value Deviation

0.0005 0.0005 0.0005 0.0000

Means 0.0005 0.0005 0.0005 0.0000

10.6 FLUORINE IN SILICON

10.6.1 Electrochemical Methods - Potentiometrlc Titration

Table 10.6.1 Fluorine Concentration (wt. %) in Si Powder

Material: Silicon

Property: F

Method: 13

// of

LAB # Values

Minimum Maximum Average Standard

Value Value Value Deviation

0.002 0.002 0.002 0.000

Means 0.002 0.002 0.002 0.000

322
10.6.2 Electrochemical Methods - Specific Ion Electrode

Table 10.6.2 Fluorine Concentration (wt. %) in Si Powder

Material: Silicon

Property: F

Method: 4

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 i 0.004 0.004 0.004 0.000

Means 1 0.004 0.004 0.004 0.000

10.7. CHLORINE IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.7.1 Neutron Activation Analysis

Table 10.7.1 Chlorine Concentration (wt . %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Cl

Method: 6

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 i 0.008 0.008 0.008 0.000

Means 1 0.008 0.008 0.008 0.000

323
10.7.2 Arc Emission Spectroscopy

Table 10.7.2.1 Chlorine Concentration (wt, %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: CI

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 2 0.0046 0.0063 0.0055 0.0012

Means 1 0.0055 0.0055 0.0055 0.0000

Table 10.7.2.2 Chlorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: CI

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

22 3 0.0056 0.0075 0.0068 0.0011

Means 1 0.0068 0.0068 0.0068 0.0000

10.7.3 Ion Chromatography

Table 10.7.3.1 Chlorine Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: CI

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 2 0.0004 0.0065 0.0034 0.0043

Means 1 0.0034 0.0034 0.0034 0.0000

324
Table 10.7.3.2 Chlorine Concentration (wt . %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Cl

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 6 0.0082 0.0094 0.0087 0.0006

Means 1 0.0087 0.0087 0.0087 0.0000

Table 10.7.3.3 Chlorine Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Cl

Method: 3

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0241 0.0241 0.0241 0.0000

Means 1 0.0241 0.0241 0.0241 0.0000

Table 10.7.3.4 Chlorine Concentration (wt. %) in Si Powder

Material: Silicon

Property: Cl

Method: 3

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

6 1 0.021 0.021 0.021 0.000

Means 1 0.021 0.021 0.021 0.000

325
10.7.4 Electrochemical Methods - Potentiometrlc Titration

Table 10.7.4.1 Chlorine Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: CI

Method: 13

# of Minimum Maximum Average Standard

lAB # Values Value Value Value Deviation

5 4 0.0069 0.0076 0.0072 0.0003

21 2 0.0100 0.0102 0.0101 0.0001

Means 2 0.0072 0.0101 0.0087 0.0020

Table 10.7.4.2 Chlorine Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Cl

Method: 13

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

21 3 0.0049 0.0055 0.0051 0.0003

Means 1 0.0051 0.0051 0.0051 0.0000

Table 10.7.4.3 Chlorine Concentration (wt. %) in Si Powder

Material: Silicon

Property: Cl

Method: 13

# of Minimum Maximxim Average Standard

LAB # Values Value Value Value Deviation

5 4 0.0033 0.0046 0.0040 0.0006

Means 1 0.0040 0.0040 0.0040 0.0000

326
10.7.5 Gravimetry

Table 10.7.5 Chlorine Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: CI

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 i 0.010 0.010 0.010 0.000

Means 1 0.010 0.010 0.010 0.000

10.8. SODIUM IN ALL POWDERS

10 . 8 . 1 Mass Spectrometry

Table 10.8.1.1 Sodium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Na

Method: 5

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

8 1 0.0003 0.0003 0.0003 0.0000

Means 1 0.0003 0.0003 0.0003 0.0000

327
Table 10.8.1.2 Sodium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Na

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.0100 0.0500 0.0233 0.0231

Means 1 0.0233 0.0233 0.0233 0.0000

10 . 8 . 2 Neutron Activation Analysis

Table 10.8.2 Sodium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Na

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.0077 0.0077 0.0077 0.0000

Means 1 0.0077 0.0077 0.0077 0.0000

10.8.3 Atomic Absorption Spectroscopy

Table 10.8.3.1 Sodium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Na

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0021 0.0024 0.0022 0.0002

16 6 0.0010 0.0070 0.0028 0.0023

Means 2 0.0022 0.0028 0.0025 0.0004

328
Table 10.8.3.2 Sodium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Na

Method: 1

# of Minimum Maximum Average Standard

LA.B y/ Values Value Value Value Deviation

14 2 0.008 0.008 0.008 0.000

Means 1 0.008 0.008 0.008 0.000

Table 10.8.3.3 Sodium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Na

Method: 1

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

16 1 0.0008 0.0008 0.0008 0.0000

Means 1 0.0008 0.0008 0.0008 0.0000

Table 10.8.3.4 Sodium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Na

Method: 1

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 1 0.0010 0.0010 0.0010 0.0000

16 1 0.0012 0.0012 0.0012 0.0000

Means 2 0.0010 0.0012 0.0011 0.0001

329
Table 10.8.3.5 Sodium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Na

Method: 1

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

14

19

24

2

8

3

0.0036

0.0100

0.0070

0.0039

0.0100

0.0080

0.0037

0.0100

0.0073

0.0002

0.0000

0.0006

Means 0.0038 0.0100 0.0070 0.0031

10.8.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.8.4.1 Sodium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Na

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

6

13

15

20

1

2

1

1

0.0047

0.0300

0.0012

0.0002

0.0047

0.0600

0.0012

0.0002

0.0047

0.0450

0.0012

0.0002

0.0000

0.0212

0.0000

0.0000

Means 4 0.0002 0.0450 0.0128 0.0216

330
Table 10.8.4.2 Sodium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Na

Method: 2

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6

20

1

1

0.0119

0.0002

0.0119

0.0002

0.0119

0.0002

0.0000

0.0000

Means 0.0002 0.0119 0.0061 0.0083

Table 10.8.4.3 Sodium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Na

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0011 0.0011 0.0011 0.0000

15 1 0.0024 0.0024 0.0024 0.0000

20 2 0.3000 0.6000 0.4500 0.2121

Means 3 0.0011 0.4500 0.1512 0.2588

Table 10.8.4.4 Sodium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Na

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0012 0.0012 0.0012 0.0000

20 2 0.0008 0.0013 0.0010 0.0004

Means 2 0.0011 0.0012 0.0011 0.0001

331
Table 10.8.4.5 Sodium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Na

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0022 0.0022 0.0022 0.0000

Means 1 0.0022 0.0022 0.0022 0.0000

10.8.5 Arc Emission Spectroscopy

Table 10.8.5.1 Sodium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Na

Method: 7

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

7 1 0.0008 0.0008 0.0008 0.0000

Means 1 0.0008 0.0008 0.0008 0.0000

10.8.6 DC Plasma - Emission Spectroscopy

Table 10.8.6.1 Sodium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Na

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.0031 0.0031 0.0031 0.0000

Means 1 0.0031 0.0031 0.0031 0.0000

332
Table 10.8.6.2 Sodium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Na

Method: 17

# of Minimiam Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.0070 0.0070 0.0070 0.0000

Means 1 0.0070 0.0070 0.0070 0.0000

10.8.7 Gravimetrv

Table 10.8.7.1 Sodium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Na

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 1 0.0100 0.0100 0.0100 0.0000

Means 1 0.0100 0.0100 0.0100 0.0000

333
10.9. MAGNESIUM IN ALL POWDERS

10.9.1 Mass Spectroscopy

Table 10.9.1.1 Magnesium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mg

Method: 5

# of Minimum

LAB # Values Value

Maximum Average

Value Value

Standard

Deviation

8 0.0001 0.0001 0.0001 0.0000

Means 0.0001 0.0001 0.0001 0.0000

Table 10.9.1.2 Magnesium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Mg

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 0.001 0.001 0.001 0.000

Means 0.001 0.001 0.001 0.000

Table 10.9.1.3 Magnesium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Mg

Method: 5

# of

LAB # Values

Minimum Maximum Average Standard

Value Value Value Deviation

8 0.003 0.003 0.003 0.000

Means 0.003 0.003 0.003 0.000

334
10.9.2 Atomic Absorption Spectroscopy

Table 10.9.2.1 Magnesium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mg

Method: 1

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

14 2 0.0080 0.0082 0.0081 0.0001

16 6 0.0060 0.0070 0.0065 0.0005

24 3 0.0200 0.0360 0.0267 0.0083

Means 3 0.0065 0.0267 0.0138 0.0112

Table 10.9.2.2 Magnesium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mg

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0010 0.0010 0.0010 0.0000

24 2 0.0090 0.0130 0.0110 0.0028

Means 2 0.0010 0.0110 0.0060 0.0071

335
Table 10.9.2.3 Magnesium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Mg

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

10 1 0.0016 0.0016 0.0016 0.0000

16 2 0.0002 0.0002 0.0002 0.0000

Means 2 0.0002 0.0016 0.0009 0.0010

Table 10.9.2.4 Magnesium Concentration (wt . %) in Si Powder

Material: Silicon

Property: Mg

Method: 1

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

1 1 0.0020 0.0020 0.0020 0.0000

16 2 0.0030 0.0030 0.0030 0.0000

19 9 0.0020 0.0032 0.0026 0.0004

Means 3 0.0020 0.0030 0.0025 0.0005

Table 10.9.2.5 Magnesium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Mg

Method: 1

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0009 0.0011 0.0010 0.0001

19 8 0.0100 0.0100 0.0100 0.0000

24 3 0.0050 0.0050 0.0050 0.0000

Means 3 0.0010 0.0100 0.0053 0.0045

336
10.9.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.9.3.1 Magnesium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mg

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

1 2 0 0060 0 0060 0.0060 0 0000

5 1 0 0063 0 0063 0.0063 0 0000

6 1 0 0065 0 0065 0.0065 0 0000

7 6 0 0073 0 0080 0.0076 0 0003

13 11 0 0100 0 0200 0.0109 0 0030

15 1 0 0071 0 0071 0.0071 0 0000

20 1 0 0002 0 0002 0.0002 0 0000

22 4 0 0030 0 0040 0.0033 0 0005

Means 8 0 0002 0 0109 0.0060 0 0032

Table 10.9.3.2 Magnesium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mg

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0002 0.0002 0.0002 0.0000

17 1 0.0083 0.0083 0.0083 0.0000

20 1 0.0014 0.0014 0.0014 0.0000

Means 3 0.0002 0.0083 0.0033 0.0044

337
Table 10.9.3.3 Magnesium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Mg

Method: 2

LAB #

# of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

15

20

1

2

0.0003

0.0110

0.0003

0.0170

0.0003

0.0140

0.0000

0.0042

Means 0.0003 0.0140 0.0072 0.0097

Table 10.9.3.4 Magnesium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Mg

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

6

15

20

1

1

2

0.0042

0.0037

0.0029

0.0042

0.0037

0.0074

0.0042

0.0037

0.0052

0.0000

0.0000

0.0032

Means 0.0037 0.0052 0.0044 0.0007

Table 10.9.3.5 Magnesium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Mg

Method: 2

# of

LAB # Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

1 2 0,.0010 0,,0010 0,.0010 0,,0000

6 1 0..0093 0..0093 0,.0093 0,,0000

15 1 0,.0060 0,,0060 0,.0060 0.,0000

17 1 0..0030 0,,0030 0,.0030 0,,0000

Means 0.0010 0.0093 0.0048 0.0036

338
10.9.4 Arc Emission Spectroscopy

Table 10.9.4 Magnesium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mg

Method: 7

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

7 1 0.0080 0.0080 0.0080 0.0000

23 1 0.0100 0.0100 0.0100 0.0000

Means 2 0.0080 0.0100 0.0090 0.0014

10.9.5 DC Plasma - Emission Spectroscopy

Table 10.9.5.1 Magnesium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mg

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.0074 0.0074 0.0074 0.0000

17 2 0.0070 0.0070 0.0070 0.0000

25 1 0.0075 0.0075 0.0075 0.0000

Means 3 0.0070 0.0075 0.0073 0.0003

339
Table 10.9.5.2 Magnesium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mg

Method: 17

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

14 1 0.0004 0.0004 0.0004 0.0000

Means 1 0.0004 0.0004 0.0004 0.0000

Table 10.9.5.3 Magnesium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Mg

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 4 0.0001 0.0004 0.0003 0.0001

Means 1 0.0003 0.0003 0.0003 0.0000

Table 10.9.5.4 Magnesium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Mg

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

3 4 0.0050 0.0050 0.0050 0.0000

Means 1 0.0050 0.0050 0.0050 0.0000

340
Table 10.9.5.5 Magnesium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Mg

Method: 17

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 0.0020 0.0020 0.0020 0.0000

Means 1 0.0020 0.0020 0.0020 0.0000

10.10. POTASSIUM IN ALL POWDERS

10.10.1 Mass Spectroscopy

Table 10.10.1 Potassium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: K

Method: 5

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

8 3 0.0002 0.0002 0.0002 0.0000

Means 1 0.0002 0.0002 0.0002 0.0000

10.10.2 Neutron Activation Analysis

Table 10.10.2 Potassium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: K

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.0006 0.0006 0.0006 0.0000

Means 1 0.0006 0.0006 0.0006 0.0000

341
10.10.3 Atomic Absorption Spectroscopy

Table 10.10.3.1 Potassium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: K

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 2 0.0020 0.0022 0.0021 0.0001

Means 1 0.0021 0.0021 0.0021 0.0000

Table 10.10.3.2 Potassium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: K

Method: 1

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 1 0.0003 0.0003 0.0003 0.0000

Means 1 0.0003 0.0003 0.0003 0.0000

Table 10.10.3.3 Potassium Concentration (wt. %) in Si Powder

Material: Silicon

Property: K

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.0100 0.0100 0.0100 0.0000

16 2 0.0005 0.0007 0.0006 0.0001

Means 2 0.0006 0.0100 0.0053 0.0066

342
Table 10.10.3.4 Potassium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: K

Method: 1

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 3 0.0050 0.0050 0.0050 0.0000

Means 1 0.0050 0.0050 0.0050 0.0000

10.10.4 Gravimetrv

Table 10.10,4 Potassium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: K

Method: 20

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 1 0.0100 0.0100 0.0100 0.0000

Means 1 0.0100 0.0100 0.0100 0.0000

343
10.11. TITANIUM IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.11.1 Mass Spectrometry

Table 10.11.1 Titanium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ti

Method: 5

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 1 0.0001 0.0001 0.0001 0.0000

Means 1 0.0001 0.0001 0.0001 0.0000

10.11.2 X-ray Fluorescence Spectrometry

Table 10.11.2 Titanium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ti

Method: 12

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

10 1 0.0060 0.0060 0.0060 0.0000

Means 1 0.0060 0.0060 0.0060 0.0000

344
10.11.3 Atomic Absorption Spectroscopy

Table 10.11.3.1 Titanium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ti

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

14 1 0.0015 0.0015 0.0015 0.0000

Means 1 0.0015 0.0015 0.0015 0.0000

Table 10.11.3.2 Titanium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Ti

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

19 9 0.0006 0.0008 0.0007 0.0001

Means 1 0.0007 0.0007 0.0007 0.0000

345
10.11.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.11.4.1 Titanium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ti

Method: 2

# of Minimum Maximtim Average Standard

LAB # Values Value Value Value Deviation

7 6 0.0028 0.0030 0.0029 0.0001

15 1 0.0030 0.0030 0.0030 0.0000

18 1 0.0500 0.0500 0.0500 0.0000

Means 3 0.0029 0.0500 0.0186 0.0272

Table 10.11.4.2 Titanium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ti

Method: 2

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 1 0.0149 0.0149 0.0149 0.0000

18 1 0.0300 0.0300 0.0300 0.0000

Means 2 0.0149 0.0300 0.0224 0.0107

Table 10.11.4.3 Titanium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ti

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0047 0.0047 0.0047 0.0000

15 1 0.0043 0.0043 0.0043 0.0000

20 2 0.0010 0.0010 0.0010 0.0000

Means 3 0.0010 0 . 0047 0.0033 0.0020

346
Table 10.11.4.4 Titanium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Ti

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 2 0.0010 0.0010 0.0010 0.0000

15 1 0.0007 0.0007 0.0007 0.0000

20 2 0.0007 0.0008 0.0008 0.0001

Means 3 0.0007 0.0010 0.0008 0.0002

10.11.5 Arc Emission Spectroscopy

Table 10.11.5 Titanium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ti

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 1 0.0030 0.0030 0.0030 0.0000

Means 1 0.0030 0.0030 0.0030 0.0000

347
10.11.6 DC Plasma - Emission Spectroscopy

Table 10.11.6.1 Titanium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ti

Method: 17

# of Minimum Maximum Average Standard

lAB # Values Value Value Value Deviation

25 1 0.0030 0.0030 0.0030 0.0000

Means 1 0.0030 0.0030 0.0030 0.0000

Table 10.11.6.2 Titanium Concentration (wt. %) in SIC Powder

Material: Silicon Carbide

Property: Ti

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

25 6 0.0032 0.0044 0.0038 0.0004

Means 1 0.0038 0.0038 0.0038 0.0000

348
10.12. CHROMIUM IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.12.1 Mass Spectroscopy

Table 10.12.1 Chromium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Cr

Method; 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.0002 0.0003 0.0003 0.0001

Means 1 0.0003 0.0003 0.0003 0.0000

10,12.2 Neutron Activation Analysis

Table 10.12.2 Chromium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Cr

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.0006 0.0006 0.0006 0.0000

Means 1 0.0006 0.0006 0.0006 0.0000

349
10.12.3 Atomic Absorption Spectroscopy

Table 10.12.3 Chromium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Cr

Method: 1

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

19 9 0.0001 0.0003 0.0002 0.0001

Means 1 0.0002 0.0002 0.0002 0.0000

10.12.4 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.12.4.1 Chromium Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Cr

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0003 0.0003 0.0003 0.0000

Means 1 0.0003 0.0003 0.0003 0.0000

Table 10.12.4.2 Chromium Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Cr

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0005 0.0005 0.0005 0.0000

Means 1 0.0005 0.0005 0.0005 0.0000

350
Table 10.12.4.3 Chromium Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Cr

Method: 2

# of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

15 1 0.0023 0.0023 0.0023 0.0000

Means 1 0.0023 0.0023 0.0023 0.0000

Table 10.12.4.4 Chromium Concentration (wt. %) in Si Powder

Material: Silicon

Property: Cr

Method: 2

y/ of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0004 0.0004 0.0004 0.0000

Means 1 0.0004 0.0004 0.0004 0.0000

351
10.13. MANGANESE IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.13.1 Neutron Activation Analysis

Table 10.13.1 Manganese Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mn

Method: 6

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

2 1 0.0000 0.0000 0.0000 0.0000

Means 1 0.0000 0.0000 0.0000 0.0000

10.13.2 Atomic Absorption Spectroscopy

Table 10.13.2.1 Manganese Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mn

Method: 1

of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 6 0.0005 0.0008 0.0006 0.0001

Means 1 0.0006 0.0006 0.0006 0.0000

352
Table 10.13.2.2 Manganese Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mn

Method: 1

// of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

16 1 0.0003 0.0003 0.0003 0.0000

Means 1 0.0003 0.0003 0.0003 0.0000

Table 10.13.2.3 Manganese Concentration (wt. %) in Si Powder

Material: Silicon

Property: Mn

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.0010 0.0010 0.0010 0.0000

16 2 0.0007 0.0007 0.0007 0.0000

19 9 0.0007 0.0008 0.0007 0.0000

Means 3 0.0007 0.0010 0.0008 0.0002

10.13.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.13.3.1 Manganese Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mn

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0007 0.0007 0.0007 0.0000

19 1 0.0006 0.0006 0.0006 0.0000

Means 2 0.0006 0.0007 0.0006 0.0001

353
Table 10.13.3.2 Manganese Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Mn

Method: 2

# of Minimiam Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0000 0.0000 0.0000 0.0000

19 7 0.0000 0.0001 0.0000 0.0001

Means 2 0.0000 0.0000 0.0000 0.0000

Table 10.13.3.3 Manganese Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Mn

Method: 2

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0001 0.0001 0.0001 0.0000

Means 1 0.0001 0.0001 0.0001 0.0000

Table 10.13.3.4 Manganese Concentration (wt. %) in Si Powder

Material: Silicon

Property: Mn

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 2 0.0010 0.0010 0.0010 0.0000

15 1 0.0006 0.0006 0.0006 0.0000

Means 2 0.0006 0.0010 0.0008 0.0003

354
10.13.4 Arc Emission Spectroscopy

Table 10.13.4 Manganese Concentration (wt . %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Mn

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 1 0.0020 0.0020 0.0020 0.0000

Means 1 0.0020 0.0020 0.0020 0.0000

10.14. NICKEL IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.14.1 Mass Spectrometry

Table 10.14.1 Nickel Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ni

Method: 5

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

8 3 0.0001 0.0004 0.0002 0.0002

Means 1 0.0002 0.0002 0.0002 0.0000

355
10.14.2 Atomic Absorption Spectroscopy

Table 10.14.2.1 Nickel Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ni

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 1 0.0100 0.0100 0.0100 0.0000

Means 1 0.0100 0.0100 0.0100 0.0000

Table 10.14.2.2 Nickel Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ni

Method: 1

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

24 1 0.0280 0.0280 0.0280 0.0000

Means 1 0.0280 0.0280 0.0280 0.0000

Table 10.14.2.3 Nickel Concentration (wt. %) in Si Powder

Material: Silicon

Property: Ni

Method: 1

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

1 1 0.0010 0.0010 0.0010 0.0000

19 9 0.0002 0.0005 0.0003 0.0001

Means 2 0.0003 0.0010 0.0007 0.0005

356
10.14.3 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.14.3.1 Nickel Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: Ni

Method: 2

y/ of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

19 1 0.0003 0.0003 0.0003 0.0000

20 1 0.0005 0.0005 0.0005 0.0000

Means 2 0.0003 0.0005 0.0004 0.0001

Table 10.14.3.2 Nickel Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ni

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

15 1 0.0004 0.0004 0.0004 0.0000

19 7 0.0005 0.0006 0.0006 0.0001

20 1 0.0005 0.0005 0.0005 0.0000

Means 3 0.0004 0.0006 0.0005 0.0001

357
Table 10.14.3.3 Nickel Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: Ni

Method: 2

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

15 1 0.0005 0.0005 0.0005 0.0000

20 2 0.0050 0.0050 0.0050 0.0000

Means 2 0.0005 0.0050 0.0027 0.0032

Table 10.14.3.4 Nickel Concentration (wt . %) in Si Powder

Material: Silicon

Property: Ni

Method: 2

# of Minimum Maximvun Average Standard

LAB # Values Value Value Value Deviation

7 1 0.0010 0.0010 0.0010 0.0000

15 1 0.0004 0.0004 0.0004 0.0000

20 2 0.0005 0.0005 0.0005 0.0000

Means 3 0.0004 0.0010 0.0006 0.0003

10.14.4 Arc Emission Spectroscopy

Table 10.14.4 Nickel Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: Ni

Method: 7

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

7 1 0.0005 0.0005 0.0005 0.0000

Means 1 0.0005 0.0005 0.0005 0.0000

358
10.15. TUNGSTEN IN SILICON NITRIDE

10.15.1 DC Plasma - Emission Spectroscopy

Table 10.15.1 Tungsten Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: W

Method: 17

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

17 i 0.0050 0.0050 0.0050 0.0000

Means 1 0.0050 0.0050 0.0050 0.0000

10.16. BORON IN SILICON NITRIDE. SILICON CARBIDE AND SILICON

10.16.1 Atomic Absorption Spectroscopy

Table 10.16.1.1 Boron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: B

Method: 1

// of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

23 i 0.0020 0.0020 0.0020 0.0000

Means 1 0.0020 0.0020 0.0020 0.0000

359
Table 10.16.1.2 Boron Concentration (wt. %) in Si Powder

Material: Silicon

Property: B

Method: 1

y/ of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

0.0010 0.0010 0.0010 0.0000

Means 0.0010 0.0010 0.0010 0.0000

10.16.2 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.16.2.1 Boron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: B

Method: 2

// of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

i 2 0.0100 0.0200 0.0150 0.0071

15 1 0.0004 0.0004 0.0004 0.0000

Means 0.0004 0.0150 0.0077 0.0103

Table 10.16.2.2 Boron Concentration (wt. %) in SNT Powder

Material: Silicon Nitride, Test Powder

Property: B

Method: 2

# of

LAB # Values

Minimum Maximum Average Standard

Value Value Value Deviation

15 0.0002 0.0002 0.0002 0.0000

Means 0.0002 0.0002 0.0002 0.0000

360
Table 10.16.2.3 Boron Concentration (wt. %) in SiC Powder

Material: Silicon Carbide

Property: B

Method: 2

# of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

15 1 0.0005 0.0005 0.0005 0.0000

21 3 0.0005 0.0006 0.0006 0.0001

Means 2 0.0005 0.0006 0.0005 0.0000

Table 10.16.2.4 Boron Concentration (wt. %) in Si Powder

Material: Silicon

Property: B

Method: 2

y/ of Minimum Maximum Average Standard

LAB Values Value Value Value Deviation

15 1 0.0014 0.0014 0.0014 0.0000

Means 1 0.0014 0.0014 0.0014 0.0000

10.16.3 Arc Emission Spectroscopy

Table 10.16.2 Boron Concentration (wt. %) in SNR Powder

Material: Silicon Nitride, Reference Powder

Property: B

Method: 7

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

7 1 0.0010 0.0010 0.0010 0.0000

Means 1 0.0010 0.0010 0.0010 0.0000

361
10.17. GALLIUM IN YTTRIA-ZIRCONIA

10.17.1 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.17.1 Gallium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ga

Method: 2

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

6 1 0.0058 0.0058 0.0058 0.0000

Means 1 0.0058 0.0058 0.0058 0.0000

10.18. BARIUM IN YTTRIA-ZIRCONIA

10.18.1 Inductively Coupled Plasma - Emission Spectroscopy

Table 10.18.2 Barium Concentration (wt. %) in YSZ Powder

Material: Zirconia

Property: Ba

Method: 2

y/ of Minimum Maximum Average Standard

LAB y/ Values Value Value Value Deviation

6 1 0.0330 0.0330 0.0330 0.0000

Means 1 0.0330 0.0330 0.0330 0.0000

10.19. STATISTICAL ANALYSIS . R. Munro , NIST

Atomic absorption spectroscopy and inductively coupled plasma emission

spectroscopy were used most often to determine the amount of metallic

impurities in the powders. Results for iron, Figures 103-107, showed

consistently good precision within laboratories, while significant

discrepancies were often found between laboratories.

362
o

V

Q

•d

u

o

•d

d

10

-1

: SigN^CRef.)

^3 10"^4.

a

0)

d

O 10 ^ d

o

10

-4

Atomic

Absorption

l~ ICP --I

ICP

A.A.

1 Within Lab \

{

j

Betw.

Labs

n

•d

. o

Figure 103, Within lab, between lab, and between methods standard

deviations in the measurement of iron content for the

SigN^CRef.) powder as measured by various laboratories using

a variety of methods.

363
o

V

Q

u

(d

d

(/3

2 t

10

-1

:: SigN^CTest)

10""^4.

a

0)

d

O 10 ^.

d

o

10

-4

ICP

A.A.

Atomic

Absorption

1

{ ICP }

1 1 1.

Within Lab \

| j

Betw.

Labs ii

m9

Figure 104, Within lab, between lab, and between methods standard

deviations in the measurement of iron content for the

SisN^CTest) powder as measured by various laboratories using

a variety of methods

364
SiC ICP

ICP

Atomic

Absorption

J- Within Lab -| \ 1 -S

Belw. ^ J Labs "o o

Within lab, between lab, and between methods standard

deviations in the measurement of iron content for the SiC

powder as measured by various laboratories using a variety

of methods.

365
{ Within Lab \

' Betw.^

Labs

Figure 106. Within lab, between lab, and between methods standard

deviations in the measurement of iron content for the Si

powder as measured by various laboratories using a variety

of methods.

366
Atomic

Absorption

A.A.

ICP

ICP

{- Within Lab -] J 1

Betw.

Labs ii

Within lab, between lab, and between methods standard

deviations in the measurement of iron content for the Zr02

powder as measured by various laboratories using a variety

of methods.

367
11. PHASE COMPOSITION ANALYSIS

A. L. Dragoo, NIST

11.1. METHODS FOR X-RAY DIFFRACTION

Introduction

X-ray powder diffraction (XRD) is the principal method for the identification

of the phase composition of crystalline materials-"^'^ . In recent years, there

has been a resurgence of interest in XRD due to the introduction of computer

automation diffractometers and processing of x-ray diffraction spectra.

Diffractometer automation has provided improved diffractometer performance as

well as a reduction in operator time. Computer processing of x-ray data has

greatly facilitated phase identification and quantitative analysis of x-ray

data

Scope

XRD is routinely used for qualitative identification of crystalline phases in

materials, but quantitative determination as well as evaluation of other

material properties, such as crystallite size and residual strain, can be

performed readily with modern automated instruments. Electronic computer

automation of x-ray diffractometers now provides the capability to perform

many aspects of phase identification, quantification, and other property

measurements on-line.

XRD can be applied to solid materials in the form of powders, monoliths,

fibers etc. However, for greatest accuracy in quantitative analysis, a wellmixed powder sample, prepared in a manner to minimize preferred orientation of

grains, is necessary. For quantitative analysis, different approaches for the

treatment of data have been devised.

Outline of Method

In an x-ray diffractometer having the Bragg- Brentano geometry, as illustrated

in Figure 108, an x-ray beam from a source at F irradiates a specimen S with a

divergent, collimated, and sometimes monochromated, beam of x- radiation. The

xrays are diffracted by the crystalline planes of the sample and are received

by a detector (not shown) which is placed beyond the slits SS in the figure.

The angles through which the xrays are scattered are characteristic of the

crystal structure and the intensity of the scattered radiation is

characteristic of the atomic composition and the atomic packing of the

diffracting planes of atoms.

The detector which is mounted on a goniometer is scanned through a range of

angles, measured in units of 26, with respect to the source, and

simultaneously an angle 9 with respect to the sample. The x- radiation used is

the characteristic radiation derived from electron bombardment of a metal such

as Fe, Cr, Cu, or Mo. The most commonly used radiation is Cu Ka. This

368
369
radiation consists of two Ka wavelengths due to the al-a2 doublet and a weaker

KB wavelength which is removed by use of a Ni filter. The source radiation

may be further monochromatized to remove the Ka2 wavelength, resulting in high

quality incident radiation with nearly a Gaussian line-shape.

Several types of detectors are now in use: Geiger-Muller , scintillation, solid

state and position sensitive detectors (PSD) . Most detectors are designed to

measure the radiation entering through a very small window in Id ; consequently, the time required to scan a range of 2B may require a half an

hour or more, depending on the range of 26 traversed and the scan rate.

However, PSD's which were introduced in recent years, use an array of

sensitized wires or quartz fibers which are precisely located in the detector

to simultaneously record the x-ray beam over a wide range of 29. With a PSD,

scans of the 26 spectrum in times less than 15 minutes are now possible.

Qualitative analysis depends on the precise determination of diffraction line

positions and, to a lesser extent, on the determination of relative line

intensities, for which determination of peak heights usually suffices.

Quantitative analysis requires that line intensities also must be accurately

measured.

Quantitative Analysis (QXRD)

Quantitative x-ray diffraction (QXRD) analysis of the phase composition of a

powder requires careful preparation of samples to minimize the effects of

preferred orientation, texture, particle size broadening, and other material

effects. Preferred orientation of grains causes erroneously enhanced or

reduced intensities with respect to different crystallographic orientations.

If coarse particles (> 10 ^m) are present, peak intensities may be reduced and

ragged due to detection of a statistically insufficient number of diffracting

grains. Particle size broadening results if grains are finer than 0.1 /xm,

leading to a reduction in observed peak height and broadening of diffraction

lines. Spray-drying of samples is the optimum method for the preparation of

well -mixed samples which do not exhibit preferred orientation, particularly if

primary particles are highly acicular. Loading of samples into a sample

holder by side-drifting'^ may be used successfully if particles have a regular

shape. Packed samples should not be used.

The use of integrated line intensities is preferred over the use of peak

heights for quantitative analysis. However, integrated intensities often are

not used due to the additional experimental difficulty in performing the

integration; a task which is frequently encumbered by overlap of significant

peaks. Instead, relative concentrations of two or more phases are estimated

from heights of one or more isolated peaks of each of the phases present. The

peak height method may be further refined by incorporation of a correction

factor for one of the phases . Such correction factors may be based on

theoretically or empirically obtained coefficients. The fraction, , of the

ith phase can be expressed as

Wi = Kili/SKjlj ,

370
where is the intensity (peak height) for phase i and is a coefficient to

be determined. Mencik, Short and Peters* developed a method for the analysis

of silicon nitride which included the phases a-SisN^, fi-SisN/,, Si20N2, Si and

Si02 (a-cristobalite)

.

Automated processing can now be carried out on the entire electronically

collected X-ray diffraction pattern, Rietveld refinement methods are being

developed which in addition to material parameters, such as strain, yield the

relative concentrations of the crystalline phases.

Quantitative methods used in the present round- robin are summarized in Table

11.1.1.

Standards

Several Standard Reference Materials are available from the National Institute

of Standards and Technology for the calibration of x-ray diffraction analyses.

These SRM's were reviewed by Dragoo^ in 1986. The SRM's are of two types:

(1) Certified materials for x-ray diffractometer calibration,

(2) Certified materials for use as line intensity and quantitative

analysis standards.

In addition, the JCPDS - International Centre for Diffraction Data^ maintains

and disseminates the Powder Diffraction File , which can be accessed

electronically, and which provides reference diffraction data (d-spacings,

intensities, crystal parameters, etc.) for many phases of interests in

ceramics, metallurgy, foresenic science, organic and polymer chemistry, and

mineralogy.

^JCPDS - International Centre for Diffraction Data, 1601 Park Lane,

Swarthmore, PA 19801.

371
Table 11.1.1 Procedures for Analysis of X-ray Diffraction Data Obtained

in lEA/ANNEX II Powder Characterization Round-Robin.

CODE PROCEDURE

1 Peak scan, qualitative

2 Peak scan, quantitative, single phase

3 Ratio of peak heights

4 Ratio of integrated intensities

a. Zr02: Method of Garvie and Nicholson^

5 Modified ratio equation, either peak heights or integrated

intensities

a. a.fi-SiaN^: Method of Mencik, Short and Peters^

b. a,ii-Si3N4: calibration curve

c. a,fl-Si3N4: Method of Gazzara and Messier^

d. Zr02: Modified Garvie -Nicholson method

(1) Method of Toraya et al.^

(2) Method of Schmid^

6 Least squares, matrix of intensities

a. SiC: Peak areas, Lorentzian shape assumed, 8x4 system of

coefficients equated to 8 peak areas-"^"

7 Whole pattern methods, e.g., Rietveld refinement

Discussion of Results

Data are summarized in the following section.

The results of phase composition determinations by various QXRD methods are

summarized in Table 11.1.2. Within the estimated errors of the measurements,

little difference is apparent between the various methods used, with the

exception of the determination of the Jl-phase content of the SNT powder using

the Rietveld refinement technique. The reason for this difference is not

apparent, and further testing of the method, comparisons with other methods,

and examinationa of the powder are requii ad to explain the difference.

372
Table 11.1.2 Phase Compositions (wt . %) Determined by Various QXRD

Methods Uncertainties are Expressed as ± one Standard

Deviation as Determined by the Fitting Procedures of Table

11.1.1

MATERIAL PHASE 1

METHOD

3

BY CODE

4

(SEE TABLE

5

11.1 1)

6 7

SNR B 6 8±1.6 4.8±.2 5.8± 7 5 .0+ 2

5.9± 2(a)

a Balance

SNT ii 3 .

0

4 6±. 9 2 . 7±.

2

3.0± 8 3 . 1± .

1

9 . 6± 1

SiC 6H t; -3 (b) 80+5

15R 35 13±4

4H 11 5+1

3C Balance

YSZ Tetr

.

80±2 85±2 81±5

Mono Balance

Calibration curve.

Unspecified method.

373
11.2.

11.2.1.

Statistical Data on X-ray Diffraction Analysis

Silicon Nitride Reference Powder (SNR)

Table 11.2.1.1 Beta Phase Content (%) by Ratio of Peak Heights

Material: Silicon Nitride, Reference Powder

Method: XRD

Procedure: Ratio of peak heights

Phase: Beta^

# of Minimum Maximum Average Standard

LAB # Values Value Value Value Deviation

16 6 7.10 8.00 7.47 0.40

21 1 3.00 3.00 3.00 0.00

24 1 7.00 7.00 7.00 0.00

Means 3 3.00 8.00 6.85 1.60

Table 11.2.1.2 Beta Phase Content (%) by Ratio of Intensities

Material: Silicon Nitride, Reference Powder

Method: XRD

Procedure: Ratio of Intensities

Phase: Beta^

# of Minimum Maximum Average Standard

LAB // Values Value Value Value Deviation

20 2 5.000 5.000 5.00 0.00

22 3 4.566 5.000 4.72 0.24

Means 2 4.566 5.000 4.83 0.23

^ The remainder of the crystalline phases was identified as

alpha- SisN^

374
Table 11.2.1.3 Beta Phase Content (%) by Modified Ratio Equation

Material

:

Silicon Nitride

,

Reference Powder

Method: XRD

Procedure : Modified ratio equation

Phase

:

Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

2b 1 5.10 5.10 5.10 0.00

1 5.00 5.00 5.00 0.00

5 2 6.20 6.30 6.20 0.07

6 1 5.00 5.00 5.00 0.00

13 11 6.00 7.00 6.18 0.40

15 1 6.00 6.00 6.00 0.00

25 3 4.30 4.70 4.53 0.21

Means 7 4.30 7.00 5.76 0.74

^ The remainder of the crystalline phases was Identified as

alpha- SijN^, with the exception of Lab No. 2

^ 0.4% SizONz also reported

^ Fraction of alpha- SisN^ calculated by independent formula

Table 11.2.1.4 Beta Phase Content (%) by Calibration Curve

Material: Silicon Nitride, Reference Powder

Method: XRD

Procedure: Calibration Curve

Phase: Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

9 8 5.60 6.10 5.88 0.18

Means 1 5.60 6.10 5.88 0.18

^ The remainder of the crystalline phases were identified as

alpha-SijN^ plus SizONgCtrace) and free Si(0.4%)

375
Table 11.2.1.5 Beta Phase Content (%) by Rietveld Refinement

Material: Silicon Nitride, Reference Powder

Method: XRD

Procedure: Whole pattern anal., Rietveld

Phase: Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

23 4 4.80 5.21 4.97 0.20

Means 1 4.80 5.21 4. 97 0.20

^ The remainder of the crystalline phases was identified as

alpha-SigNz,

11.2.2. Silicon Nitride Test Powder (SNT)

Table 11.2.2.1 Beta Phase Content (7«) by Qualitative Scan of Peak

Heights

Material: Silicon Nitride, Test Powder

Method: XRD

Procedure: Peak Scan, Qualitative

Phase: Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

23 1 3.00 3.00 3 .00 0.00

Means 1 3.00 3.00 3.00 0.00

376
Table 11.2.2.2 Beta Phase Content (%) by Ratio of Peak Heights

Material: Silicon Nitride, Test Powder

Method: XRD

Procedure: Ratio of peak heights

Phase: Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

14 1 3.10 3.10 3.10 0.00

16 6 4.80 5.50 5.07 0.30

21 1 3.00 ,3.00 3.00 0.00

24 2 5.00 5.00 5.00 0.00

Means 4 3.00 5.50 4.65 0.87

^ The remainder of the crystalline phases was identified as

crystalline alpha- SisN^,

Table 11.2.2.3 Beta Phase Content (%) by Ratio of Intensities

Material: Silicon Nitride, Test Powder

Method: XRD

Procedure: Ratio of Intensities

Phase: Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

20 1 3.00 3.00 3.00 0.00

22 4 2.45 2.83 2.60 0.16

Means 2 2.45 3.00 2.68 0.23

^ The remainder of the crystalline phases was identified as

alpha- SigNj^

377

1
Table 11.2.2.4 Beta Phase Content (%) by Modified Ratio Equation

O ^ Q V" T O 1 " ^ !L X i.COn IN 1 CL XQe , 1 cS L. Jt OWUc JT

i ic UI llJ u

IT I. U I- c LI LI i. c . riULlXXXcLl LdLXU cCJUaUJ-OIl

PhssDc Uci

$ of Minimum Maximum Average Standard

T A u <: LJ\D 9 Values Value Value Value Deviation

2 1 3.00 3.00 3.00 0.00

4 2 2.00 2.00 2.00 0.00

5 2 3.30 3.60 3.45 0.21

6 1 4.00 4.00 4.00 0.00

15 1 4.00 4.00 4.00 0.00

25 1 2.50 2.50 2.50 0.00

Means 6 2.00 4.00 3.05 0.82

^ The remainder of the crystalline phases was identified as

alpha-Si3N,

Table 11.2 .2.5 Beta Phase Content (%) by Matrix of Intensit

MaterialSilicon Nitride, Test Powder

Method: XRD

ProcedureLeast squares, matrix of intensities

PhaseBeta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

23 2 3.00 3.20 3.10 0.14

Means 1 3.00 3.20 3.10 0.14

^ The remainder of the crystalline phases was identified as

alpha- SisN^

378
Table 11.2.2.6 Beta Phase Content (%) by Rietveld Refinement

Material: Silicon Nitride, Test Powder

Method: XRD

Procedure: Whole pattern anal ., Rietveld

Phase : Beta^

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

23 4 9.49 9.80 9.62 0.14

Means 1 9 .49 9 . 80 9.62 0 . 14

The remainder of the crystalline phases was identified as

alpha- SigN^

11.2.3. Silicon Carbide (SiC)

Table 11.2.3.1 Phase Content (%) by Matrix of Intensities

Material: Silicon Carbide

Method: XRD

Procedure: Least squares, matrix of intensities

Phase: 6H

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

4 2 76.5 77.3 76.9 0.56

6 1 85.0 85.0 85.0 0.00

Means 2 76.5 85.0 79.6 4.69

379
Phase

15R

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

4 2 13.8 16.4 15.1 1.84

6 1 9.0 9.0 9.0 0.00

Means 2 9.0 16.4 13.1 3.75

Phase4H

S of M 1 n T mi im M^i V 1 mi 1 m r\ V c 1. d tc LAB $ Values Value Value Value Deviation

4 2 4.0 5.5 4.8 1.06

6 1 6.0 6.0 6.0 0.00

Means 2 4.0 6.0 5.2 1.04

Table 11.2.3.2 Phase Content by Unspecified Method

Material

:

Silicon Carbide

Method: XRD

ProcedureNot specified

Phase6H

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

2 1 53.00 53.00 53.00 0.00

Means 1 53.00 53.00 53.00 0.00

380
Phase

15R

$ of Minimum Maximvim Average Standard

LAB $ Values Value Value Value Deviation

2 1 35 .0 35.0 35.0 0.00

Means 1 35.0 35.0 35.0 0.00

Phase

4H

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

2 1 11.00 11.00 11.00 0.00

Means 1 11.00 11.00 11.00 0.00

11.2 .4. Yttria-Stabilized Zirconia CYSZ)

Table 11 .2.4.1 Phase Content (%) by Ratio of Peak Heights

Material

Zirconia

Method: XRD

Procedure

Ratio of peak heights

Phase

Tetragonal

$ of Minimum Maximum Average Standard

LAB $ Values Value Value Value Deviation

2 1 82.0 82.0 82.0 0.0

14 1 80.0 80.0 80.0 0.0

24 3 78.0 81.0 79. 3 1.5

Means 3 78.0 82 .0 80.0 1.6

381
Phase

Monoclinic

LAB $

$ of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

2

14

24

1

1

3

18.0

20.0

19.0

18.0

20.0

22.0

18.0

20 .

20.7

0.0

0 .

1.5

Means 3 18.0 22.0 20.0 1.6

Table 11.2.4.2 Phase Content by Ratio of Intensities

Material

Method:

Procedure

Phase

Zirconia

XRD

: Ratio of intensities

Tetragonal

LAB $

$ of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

9

22

3

1

84.40

87.92

84.90

87.92

84.57

87 . 92

0.29

0 . 00

Means 2 84.40 87.92 85.40 1.69

PhaseMonoclinic

LAB $

$ of

Values

Minimum

Value

Maximum

Value

Average

Value

Standard

Deviation

9

22

3

1

15.10

12.08

15.60

12.08

15.43

12.08

0.29

0.00

Means 2 12.08 15.60 14.60 1.69

382
Table 11.2.4.3 Phase Content by Modified Ratio Equation

Material

:

Zirconia

Method: XRD

Procedure : Modified ratio equation

Phase

:

Tetragonal

$ of Minimum Maximum Average o tanaaro.

LAB $ Values Value Value Value Deviation

6 1 90. 6 90.6 0.00

Id 1 83. 0 83 .0 o J . U U . UU

18 6 75. 9

Q n n ou . u 78.6 1.76

Means 3 75. 9 on 80.7 4.54

Phase

:

Monoclinic

$ of Minimum Maximum Average Standard

LAB $ Values Val ue Value Value Deviation

6 1 9. 4 9.4 9.4 0.00

' 15 1 17. 0 17.0 17.0 0.00

18 6 20. 0 24.1 21.4 1.76

Means 3 9. 4 24.1 19.3 4. 54

383
11.3. References

1. Klug, H. P.; Alexander, L. E. X-ray Diffraction Procedures for

Polycrystalline and Amorphous Materials . 2nd Ed. New York: John Wiley;

1974.

2. Schwartz, L. H. , Cohen, J. B. Diffraction from Materials . New York:

Academic Press; 1977.

3. Jenkins, R. X-ray Technology, Norelco Reporter . 31 [2XR]: 18-26; 1984.

4. McMurdie , H. F. ; Morris, M. C; Evans, E. H.; Paretzkin, B., Wong-Ng, W. ; Hubbard, C. R. Methods of Producing Standard X-ray Diffraction Powder

Patterns, Powder Diffraction . 1 [1]: 40-43; 1986.

5. Mencik, Z.; Short, M. A.; Peters, C. R. Quantitative Phase Analysis of

Synthetic Silicon Nitride by X-ray Diffraction, Advances in X-ray

Analysis . Vol. 23. Ed. by Rhodes, J. R. New York: Plenum Publishing

Corp. ; 1980. pp. 375-79.

6. Dragoo, A. L. Standard Reference Materials for X-ray Di-.f fraction. Part

I. Overview of Current and Future Standard Reference Materials, Powder

Diffraction . 1 [4]: 294-98; 1986.

7. Garvie, R. G.; Nicholson, P. S. Phase Analysis in Zirconia Systems, J

Am. Ceram. Soc . 55 [5]: 303-05; 1972.

8. Gazzara, Ch. P.; Messier, D. R. Am. Ceram. Soc. Bull. 56: 777-80; 1977.

9. Toraya, Hideo; Yoshimura, Masahiro; Somiya, Shigeyuki . Calibration Curve

for Quantitative Analysis of the Monoclinic-Tetragonal Zr02 System by Xray Diffraction, Commun. Am. Ceram. Soc . C119-21; June 1984.

10. Schmid, H. K. Quantitative Analysis of Polymorphic Mixes of Zirconia by

X-ray Diffraction, J . Am. Ceram. Soc. . 70 [5]: 367-76; 1987.

11. Peters, C. Anal. Sci. Div. , Ford Motor Co., Inc. Private Communication.

384
12. THERMAL ANALYSIS

A, L. Dragoo and S. G. Malghan, NIST

Introduction

Thermal analysis includes a variety of techniques to measure thermochemical

and thermomechanical properties of materials , such as differential thermal

analysis (DTA) , calorimetry, dilatometry and thermal gravimetric analysis

(TGA) . For this study, a very few laboratories reported results obtained

using TGA to measure the amount of volatile components in the powders.

12.1. Results

The amounts of volatile components of the powders are illustrated here with

the results reported by Lab 4.

Table 12.1 TGA Mass Loss (%) as Determined by Lab 4. Heating rate

5 °C/min; ambient air; sample on Pt pan

SAMPLE SAMPLE

rUWUCiK WT . , mg CnAKALi i hKi b i i (j D T, C MAbb LUbb

SNR 63.7 Granules 150 0.28

400 No change

42.7 Granules 400 0.23

400 No change

SNT 102.8 Large granule 150 0.14

250 0.17

43.7 Large granule 150 0.19

SiC 110.8 Loose pellet 150 0.14

350 0.27

Si 65.8 Not specified 150 0.07

YSZ 74.3 400 0.54

385
APPENDIX I - Physical Properties

Table I.l lists the methods, code numbers, and units used in the measurement

of density and specific surface area of the powders. The code numbers

identify the methods tabulated in Table 1.2 (density) and in Table 1.3

(specific surface area)

.

Table I.l. Methods and Codes for Physical Property Measurements

Method Code Units

Single Point Surface Area 1 m^/g

Multi Point Surface Area 2 m^/g

Tap Density 3 g/cm^

He gas pycnometer 4 g/cm^

Liquid pycnometer, hydrocarbon 6 g/cm^

Density, Hg Intrusion 13 g/cm^

386
1.2.1.

Table 1.2 Density

Silicon Nitride Reference Powder

Lab lEA

# Vial #

5 9001

5 9004

6 9019

15 9013

15 9013

17 225

17 1898

17 1898

18 9024

21 9007

25 9010

17 980102

17 980102

17 980102

17 980102

17 980102

17 2410338

17 2410338

17 2410338

17 2410338

17 2410338

17 3770991

17 3770991

17 3770991

17 3770991

17 3770991

17 7757988

17 7757988

17 7757988

17 7757988

17 7757988

17 9461894

17 9461894

17 9461894

17 9461894

17 9461894

23 16

23 16

23 16

23 377

23 377

23 377

23 16010813

Method Tap Bulk Liquid

Code Density Density Density

3 0.74

3 0.78

3 0.87

3 0.77

3 0.77

3 1.46

3 1.47

3 1.48

3 0.74

3 0.71

3 0.79

4 --- 3.130

4 --- 3.150

4 --- 3.130

4 --- 3.130

4 --- 3.150

4 --- 3.140

4 --- 3.120

4 --- 3.130

4 --- 3.120

4 --- 3.130

4 --- 3.180

4 --- 3.180

4 --- 3.160

4 --- 3.180

4 --- 3.160

4 --- 3.130

4 --- 3.130

4 --- 3.130

4 --- 3.120

4 --- 3.120

4 --- 3.124

4 --- 3.124

4 --- 3.124

4 --- 3.137

4 --- 3.137

4 --- 3.132

4 --- 3.152

4 --- . 3.136

4 --- 3.131

4 --- 3.146

4 --- 3.157

4 --- 3.141

387
Table 1.2 Density (Continue)

1.2.1. Silicon Nitride Reference Powder

Lab lEA Method Tap Bulk Liquid

y/ Vial # Code Density Density Density

21 9007 6 --- --- 0.56

25 9010 6 --- --- 0.48

388
1.2.2. Silicon Nitride Test Powder

Lab lEA Method

# Vial # Code

6 18 3

14 LSM06 3

14 LSM07 3

15 LSM09 3

18 26 3

21 LSM05 3

25 LSM03 3

17 1350810 4

17 1350810 4

17 1350810 4

17 1350810 4

17 1350810 4

17 1350810 4

17 1350810 4

17 1471273 4

17 1471273 4

17 1471273 4

17 1471273 4

17 1471273 4

17 1800522 4

17 1800522 4

17 1800522 4

17 1800522 4

17 1800522 4

17 2831011 4

17 2831011 4

17 2831011 -1— v_/ _i_ _i_ 4

17 2831011 4

17 2831011 4

17 3410361 4

17 3410361 4

17 3410361 4

17 3410361 4

17 3410361 4

17 3410361 4

17 8400644 4

17 8400644 4

17 8400644 4

17 8400644 4

17 8400644 4

17 11571041 4

Tap Bulk Liquid

Density Density Density

0.76

0.67

0.65

0.66

0.71

0.66

0.71

3.150

3.130

3.160

3.180

3.180

3.180

3.180

3.160

3.140

3.140

3.160

3.160

3.160

3.160

3.160

3.160

3.160

3.160

3.190

3.180

3.160

3.130

3.160

3.190

3.170

3.200

3.170

3.170

3.160

3.150

3.150

3.160

3.150

3.160

389
Silicon Nitride Test Powder

Lab lEA Method Tap Bulk T 1 mi 1 H

V Vial ^/ Code lyC^lLO J- Density T\c^Y\ x/ciioO "1X f~\7' ^ y

1 7 11'i71041 A 3 160

1

J- 7/ / XWH-X AH- 3 160

1 7 1XX^1 <S71/ XWH-X DAI AH" 3 150

1J. 7/ 11571 XXw' / Xv7*-tX 041 A•t 3 180

1

J- 7/ 19 571 940 A*+ 3 150

1 7 1 9 571 940 A 3 160

17 12571240 4 3 150

17 12571240 4 3 160

17 12571240 4 3 160

1 Ql A 3 144

23 U0904 4 3 170

23 U0904 4 3 164

23 U0904 4 3 144

23 U1913 4 3 138

23 U1913 4 3 152

23 U1913 4 3 136

25 LSM03 6 0.43

390
1.2.3. Silicon Carbide Powder

Lab TEA

Vial #

Method

Code

Tap

Density

Bulk

Density

Liquid

Density

6

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

15

18

21

21

21

25

1003

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1018

1012

1009

1011

1011

1011

1016

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

3

0.83

0.71

1

1

1

1

1,

1,

1,

1,

1,

1,

1,

1,

1.

1.

1.

72

71

71

72

71

76

76

77

76

76

80

79

79

77

78

0.77

0.68

0.76

0.75

0.75

0. 78

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

1160117

1160117

1160117

1160117

1160117

1200119

1200119

1200119

1200119

1200119

1210118

1210118

1210118

1210118

1210118

1220123

1220123

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

3

3

3

3

3

3

3

3

3

3,

3,

3

3,

3,

3,

3,

3.

170

180

150

180

150

130

130

120

120

110

150

150

160

160

150

110

080

391
Silicon Carbide Powder

Lab lEA Method Tap Bulk Liquid

y/ Vial # Code Density Density Density

17 1220123 4 3 .130

17 1220123 4 3 .130

17 1220123 4 3 .130

17 1330134 4 3 .140

17 1330134 4 3 .124

17 1330134 4 3 .124

17 1330134 4 3,,171

17 1330134 4 3,.155

17 1353637 4 3,.160

17 1353637 4 3,.160

17 1353637 4 3,.160

17 1353637 4 3,.170

17 1353637 4 3..150

17 1390138 4 3..160

17 1390138 4 3..120

17 1390138 4 3,.150

17 1390138 4 3,.150

17 1390138 4 3..190

17 1390138 4 3.,180

23 1005 4 3,.160

23 1005 4 3,,160

23 1005 4 3,,160

23 1005 4 3,,160

23 1005 4 3,.160

23 1005 4 3,,140

23 1005 4 3.,140

23 1005 4 3.,140

23 1005 4 3.,140

23 1005 4 3.,140

23 1005 4 3.,140

23 1005 4 3.,140

23 1005 4 3. 158

23 1005 4 3. 124

23 1005 4 3. 137

23 1703 4 3. 136

23 1703 4 3. 151

23 1703 4 3. 157

25 1016 6 --- --- 0.40

392
1.2.4. Silicon Powder

Lab lEA

Vial #

Method

Code

Tap Bulk Liquid

Density Density Density

6

15

17

17

17

18

1003

1016

43

43

44

1015

3

3

3

3

3

3

1.08

1.03

1.47

1.48

1.46

0.78

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

17

86087

86087

86087

86087

86087

88089

88089

88089

88089

88089

91092

91092

91092

91092

91092

1170128

1170128

1170128

1170128

1170128

1180119

1180119

1180119

1180119

1180119

1270116

1270116

1270116

1270116

1270116

1300129

1300129

1300129

1300129

1300129

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

2

2

2

2

2

2,

2,

2,

2.

2,

2,

2,

2,

2,

2.

2.

2.

2.

2.

310

310

320

300

310

320

320

320

320

320

330

330

340

330

330

340

340

330

350

2. 340

2

2

2

1.

2,

2,

2,

2,

2,

2.

2,

2,

2.

2.

2.

308

324

300

308

324

350

350

340

350

340

340

330

340

330

330

393
Silicon Powder

Lab lEA Method Tap Bulk Liquid

# Vial # Code Density Density Density

17 1310132 4 2 310

17 1310132 4 2 310

17 1310132 4 2 320

17 1310132 4 ... 2 320

17 1310132 4 2 310

23 1005 4 2 344

23 1005 4 2 336

23 1005 4 2 335

23 2203 4 2 340

23 2203 4 2 330

23 2203 4 2 330

23 2203 4 2 330

23 2203 4 2 330

23 2204 4 2 330

23 2204 4 2 330

23 2204 4 2 330

23 2204 4 2 330

23 2204 4 2 330

23 2204 4 2 330

23 2204 4 2 333

23 2204 4 2 328

23 2204 4 2 342

394
1.2.5. Yttria-Zirconia Powder

Lab lEA

Vial #

Method

Code

Tap Bulk Liquid

Density Density Density

6

14

14

15

18

18

18

OE013

OCOl

OCOl

OE014

259

534

OR012

3

3

3

3

3

3

3

1

1

1

1

1

1

1,

52

50

50

49

48

46

47

17 59

17 59

i /

1 7 i / IdlO

i / 7 C

1 7 101

1 7 101

17 380

17 380

17 510

17 510

17 592

17 592

17 592

18 39

18 OR012

18 OR012

18 OR012

14 OCOl

14 OCOl

22 269

22 269

22 269

22 279

22 279

22 279

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

6

6

13

13

13

13

13

13

5

5

5

5

5,

5,

5,

5,

5,

5,

5,

5,

5,

5,

6.

5.

5.

5.

6

7

7

6

6

7,

666

631

675

700

685

810

734

750

606

631

717

636

650

727

001

910

978

903

467

139

211

020

068

566

1.24

1.22

395
Table 1.3 SPECIFIC SURFACE AREA

1.3.1. Silicon Nitride Reference Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

2 119 1 13 20

3 542 1 11 80

3 556 1 11 60

3 557 1 11 60

4 438 1 13 80

4 438 1 13 90

4 455 1 13 70

4 455 1 13 80

4 455 1 13 90

4 977 1 13 30

4 977 1 13 40

4 999 1 13 17

4

r\ C\ r\ 999 1 13 21

4

r\ r\ r\ 999 1 13 14

4

c\ C\ r\ 999 1 13 1 / 14

4 1003 1 13 1 A 10

4 1003 1 13 1 A 10

4 1003 1 13 11

4 1003 1 13 T / 14

loil 1

1 o iz 4U

o0no/. i 14 U4

00no/. i 14

o0 no/ 1 14 UU

oo no/ yo4 1 14

1 1 11 n A r\ o 9003 1 13 /o

14 100 1 14 O AiU

14 100 1 14 80

14 305 1 13 60

14 307 1 14 20

14 770 1 14 00

15 9013 1 12 90

15 9013 1 13 10

16 638 1 13 70

16 638 1 14 00

16 686 1 13 60

16 686 1 13 80

16 688 1 13 60

16 688 1 13 80

16 688 1 13 80

17 48 1 12 94

396
Silicon Nitride Reference Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

17 48 1 12 .98

17 48 1 13 .13

17 48 1 12 .94

17 48 1 12 .94

17 225 1 13 .18

17 225 1 13 .09

17 225 1 13 .09

17 225 1 13 .36

17 582 1 12 .88

17 582 1 12 88

17 582 1 12 92

17 582 1 12 88

17 582 1 12 79

17 582 1 12 79

17 582 1 12 79

17 582 1 12 74

17 719 1 13 07

17 719 1 12 87

17 719 1 12 99

17 719 1 12 91

17 761 1 12 85

17 761 1 12 80

17 761 1 12 74

17 761 1 12 85

17 987 1 12 55

17 987 1 12 44

17 987 1 12 55

17 987 1 12 44

17 1104 1 13 59

17 1104 1 13 71

17 1104 1 13 59

17 1104 1 13 67

17 1111 1 12 78

17 1111 1 12 89

17 1111 1 12 67

17 1111 1 12 82

17 1117 1 12 82

17 1117 1 12 82

17 1117 1 12 72

17 1117 1 12 82

17 1164 1 12. 72

17 1164 1 12 72

397
Silicon Nitride Reference Powder

Lab lEA Method Single- Multiy/ Vial # Code Point Point

17 1164 1 12 .66

17 1164 1 12 .61

17 1222 1 13 .32

17 1222 1 13 .28

17 1222 1 13 .28

17 1222 1 13 .37

17 1222 1 13 .32

17 1381 1 12 .73

17 1381 1 12 .85

17 1381 1 12 .65

17 1381 1 12 .81

17 1381 1 12 .93

17 1381 1 12 .77

17 1381 1 12 .82

17 1381 1 12 .82

17 1381 1 12 .98

17 1381 1 12 .93

17 1381 1 13 .04

17 1381 1 13 .10

17 1381 1 12,.93

17 1516 1 13,,00

17 1516 1 13,.13

17 1516 1 13,,05

17 1516 1 13,,18

17 1516 1 13,,18

17 1538 1 12.,70

17 1538 1 12,,66

17 1538 1 12,,78

17 1538 1 12,,78

17 1592 1 13,,58

17 1592 1 13,,47

17 1592 1 13.,58

17 1592 1 13,,52

17 1898 1 13.,01

17 1898 1 13.,08

17 1898 1 13.,01

17 1898 1 13.,04

18 1032 1 12. 45

18 1032 1 12. 87

18 1032 1 12. 70

18 1032 1 13. 04

18 1032 1 12. 97

398
Silicon Nitride Reference Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

18 1032 1 12.82

18 1032 1 13.02

18 1032 1 12.93

18 1032 1 13.03

24 244 1 12.00

24 648 1 12.60

24 9005 1 12.08

24 9005 1 12.25

24 9005 1 12.19

25 1213 1 13.10

25 1231 1 13.10

25 1869 1 13.20

1 599 2 --- 14.51

1 1255 2 --- 14.20

5 1631 2 --- 13.20

6 1857 2 --- 12.93

7 302 2 --- 13.47

7 1519 2 --- 13.56

9 159 2 --- 15.35

9 697 2 --- 14.45

9 703 2 --- 13.72

9 1173 2 --- 14.99

9 1752 2 --- 15.13

13 56 2 --- 13.54

13 253 2 --- 14.61

13 375 2 --- 12.80

13 400 2 --- 12.90

13 624 2 --- 12.80

13 1016 2 --- 12.61

13 1113 2 --- 11.29

13 1281 2 --- 13.04

13 1315 2 --- 12.89

13 1880 2 --- 13.10

14 305 2 --- 12.30

14 305 2 --- 12.50

14 307 2 --- 13.00

14 307 2 --- 13.10

20 198 2 --- 13.09

20 637 2 --- 13.23

20 652 2 --- 13.48

20 1241 2 --- 12.92

399
Silicon Nitride Reference Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

20 1394 2 13 .43

20 1394 2 13 .03

20 1695 2 13 .34

21 24 2 13 .61

21 24 2 13 .59

22 130 2 12 .92

22 130 2 13 10

22 130 2 15 53

22 130 2 15 40

22 1449 2 12 91

22 1449 2 12 99

22 1449 2 12 24

22 1449 2 13 59

22 1449 2 13 94

22 1578 2 13 00

22 1578 2 13 11

22 1578 2 12 07

22 1578 2 14 20

22 1578 2 14 15

23 1009 2 13 20

23 1009 2 13 40

23 1009 2 13 49

23 1022 2 13 25

23 1022 2 13 21

23 1022 2 13 27

23 1410 2 13 26

23 1410 2 13 44

23 1410 2 13 62

23 1471 2 13 33

23 1471 2 13 80

23 1471 2 --- 13 65

23 1471 2 12 94

23 1471 2 12 75

23 1471 2 13 83

23 1682 2 13 89

23 1682 2 13. 63

23 1682 2 13. 63

23 1812 2 13. 41

23 1812 2 13. 39

23 1812 2 13. 21

I

400
1.3.2. Silicon Nitride Test Powder

Lab TEA Method Single

# Vial # Code Point

2 446 1 9.10

2 604 1 9.10

3 213 1 8.49

3 1302 1 8.44

4 31 1 9.83

4 31 1 9.81

4 31 1 9.83

4 31 1 9.81

4 730 1 9.83

4 730 1 9.82

4 730 1 9.76

4 730 1 9.72

4 1427 1 9.79

4 1427 1 9.79

4 1427 1 9.79

4 1427 1 9.81

5 818 1 9.20

5 818 1 9.20

5 821 1 9.10

5 821 1 9.10

8 223 1 10.33

8 223 1 10.28

8 223 1 10.34

8 353 1 10.21

8 353 1 10.24

8 353 1 10.24

8 353 1 10.21

8 1417 1 10.43

8 1417 1 10.30

8 1417 1 10.30

14 1182 1 11.00

14 1182 1 11.00

14 1182 1 9.00

15 LSM09 1 8 . 70

16 1036 1 9.25

16 1036 1 9.29

16 1036 1 9.25

16 1199 1 8.92

16 1199 1 8.88

16 1199 1 9.03

17 312 1 9.22

17 312 1 9.30

401

MultiPoint
Silicon Nitride Test Powder

Lab lEA Method Single- Multiy/ Vial # Code Point Point

1 7 1 / J XQ 1 7 . X J

1 7 1 / J XZ XQ OA

i /

11Q 0 ^ y . ZtD

T 7 i / n 0 1X O . D /

1 7 1 /

1X

8 Q A

1

J. 7/ J LZ.

1X

R R o . o J

1 7 J xz 1XRo . A7O /

1 7 JOH- 1X

Q /i /i

1 7 JO'+ R/l 1X y . OO

1 7 1 /

1X Q /i R

T 7 1 / J ot 1X y . '+'4

1 7 1 / O oU 1X

RO . D Z9

1 7 1 /

1X

R 7 7 o . / J

1 7 1 / D OU 1XR R

1 7 J. / D OU X Ro . 0 Ro

1 7 7 .J o1X Ro , QQy y

1 7 -/JO 1X R Rfi

1 7 7 J o1X R If,

1 7 -/JO 1X 8 9fi

1 7 -/JO 1X -/ . V7 J

1 7 -/JO 1X ft(J . QQy y

1 7 -/JO 1

X.

1X 7/ 3? J O1

J. 8 99

1X 7/ X _> X J1X 9 1 3

1X 7/ X J X J1X q^ . 1X fto

1X 7/

1X 31J J S1 1X 9-/ . 16X U

1X 7/

1X

"^1 J X Js 1X 9 1 n

1 7 X /

1 A 1 Q 1X

Q OA

17 1419 1 9.04

17 1419 1 9.13

17 1419 1 9.13

17 1419 1 8.84

17 1419 1 8.92

17 1419 1 8.96

17 1419 1 8.84

17 1419 1 8.96

18 597 1 9.50

18 597 1 9.83

18 597 1 9.65

18 597 1 9.47

18 597 1 9.31

18 597 1 9.21

I 402
Silicon Nitride Test Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

18 597 1 9.46

18 597 1 9.50

18 597 1 9.53

20 193 1 10.15

20 193 1 10.00

25 432 1 9.55

25 758 1 9.53

6 889 2 --- 9.31

7 564 2 --- 9.89

7 564 2 --- 10.63

7 564 2 --- 10.49

7 976 2 --- 9.83

7 976 2 --- 10.62

7 976 2 --- 10.53

9 23 2 --- 9.77

9 23 2 --- 10.04

9 23 2 --- 9.86

9 23 2 --- 9.17

9 200 2 --- 9.68

9 200 2 --- 10.09

9 200 2 --- 9.90

9 200 2 --- 9.33

9 1044 2 --- 9.64

9 1044 2 --- 9.99

9 1044 2 --- 9.81

9 1044 2 --- 8.97

9 1152 2 --- 10.02

9 1152 2 --- 9.81

9 1152 2 --- 9.84

9 1152 2 --- 9.39

9 1156 2 --- 10.07

9 1156 2 --- 10.09

9 1156 2 --- 9.87

9 1156 2 --- 9.36

14 323 2 9.50

14 323 2 --- 9.50

14 1182 2 --- 8.80

14 1182 2 --- 9.20

20 252 2 --- 10.00

21 LSM05 2 --- 9.84

21 LSM05 2 --- 9.77

403
Silicon Nitride Test Powder

..ab lEA Me thod S ingle

Multi-

# Vial # Code Point Point

21 LSM05 2 10 . 03

22 915 2 10 . 01

22 915 2 ~ *" 10 . 21

22 915 2 ~ ~ — 10 . 00

22 915 2 ~ ~ ~ 9 . 95

22 1168 2 ~ ~ ~ 9 . 87

22 1168 2 ~ ~ ~ 9 . 81

22 1168 2 ~ ~ ~ 10 . 09

22 1168 2 ~ ~ ~ 10 . 04

23 259 2 ~ ~ ~ 9 . 52

23 259 2 9 . 54

23 259 2 9.67

23 371 2 9.75

23 371 2 9.81

23 371 2 9 . /5

23 508 oI

n "7 T 9 . /i

23 6U8 n ^ o y . OZ

23 608 2 9 . 90

23 632 2 9.83

23 632 2 9.64

23 632 2 9.71

23 654 2 9.53

23 654 2 9.46

23 654 2 9.52

23 1012 2 9.47

23 1012 2 9.69

23 1012 2 9.69

404
1.3.3. Silicon Carbide Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

1 241 1 12 .40

1 241 1 12 .53

1 243 1 12 .36

1 243 1 12 .50

2 22 1 12 .80

3 4 1 12 .40

3 4 1 12 .30

3 4 1 12,.60

3 7 1 12,.70

3 7 1 12,.80

3 7 1 12,.90

3 9 1 12,.90

3 9 1 12,.90

3 9 1 12,.90

3 11 1 12,,80

3 11 1 12,.70

3 11 1 12 ,70

4 73 1 13,.75

4 73 1 13,.77

4 73 1 13,,79

4 73 1 13.,74

4 76 1 13,.70

4 76 1 13..69

4 76 1 13,,63

4 76 1 13.,66

4 77 1 13,,68

4 77 1 13,,68

4 77 1 13,,79

4 77 1 13,.78

8 268 1 16,.69

8 268 1 16,.49

8 268 1 16,.79

8 271 1 15,.49

8 271 1 15,.46

8 271 1 15,.41

15 1012 1 11,,92

16 78 1 12,,60

16 82 1 12,.60

16 LSM1013 1 12,,90

17 148 1 13,,00

17 148 1 12,,96

17 148 1 13,,00

405
Silicon Carbide Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

17 148 1 13 .00

17 149 1 13 .00

17 149 1 13 .04

17 149 1 13 .00

17 149 1 13 .00

17 150 1 12 .96

17 150 1 13 .10

17 150 1 13 . 19

17 150 1 13 .19

17 150 1 12 .96

17 152 1 13 .12

17 152 1 13 .12

17 152 1 13 .20

17 152 1 13 .20

17 153 1 13 .06

17 153 1 13 .09

17 153 1 13,.06

17 153 1 13 .09

17 154 1 12,.99

17 154 1 12,.94

17 154 1 12,.94

17 154 1 12,.99

17 154 1 12,.99

17 154 1 13,.07

17 154 1 13,.07

17 154 1 13,,07

17 154 1 13,,09

17 154 1 12,,99

17 154 1 13,.04

17 154 1 13,,04

18 94 1 12.,36

18 94 1 14,,05

18 94 1 13,,15

18 94 1 13.,38

18 94 1 14.,00

18 94 1 13.,27

18 94 1 13.,27

18 94 1 13. 82

18 94 1 13. 10

20 90 1 .14. 31

25 1016 1 13. 70

406
Silicon Carbide Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

1 241 2 13 . 66

1 241 2 13 . 85

1 243 2 13 . 58

1 243 2 13 . 77

5 100 2 11 . 67

7 248 2 16 . 38

7 248 2 15 . 92

7 248 2 16 . 30

9 255 2 14 . 71

9

/ICC 255 2 --- 14 . 58

9

o c c 255 2 14 . 68

9 256 2 14 . 78

9

o c ^ 256 2 14,. 66

y 256 2

1 / 14,. dz

y 26i 2 14

,

. DU

y Z6i 2 14

,

0 Q

y Z6 i 2 14

,

. 4Z

1 n jy 2 1 J ,. 14

1 r\ /. "i 2 1-) .. \jI

iU 2 Id .. 4i

1 "J Li 1iU J 2 1 J .

1 1

i-i iU4 2 li , /. 0

. 4o

i J iU5 2 1 J . 0 /.

, o4

1 "J iU6 2 lo

.

. ol

i J iU / 2 1 J ,. ZD

Zi 1005 2

1 / 14

,

. 94

Zl 1005 2 14,. 68

21 1005 2 14

,

, 69

22 171 2

1 c 15

,

, 48

22 171 2 15,. 67

22 1/3 2 14,, 93

22 173 2 15,, 00

23 188 2 14,,34

23 188 2 14,,18

23 188 2 14,,26

23 206 2 14.,29

23 206 2 14. 38

23 206 2 14.,51

23 224 2 14. 11

23 224 2 14. 23

23 224 2 14. 27

23 227 2 13. 80

23 227 2 14. 41

23 227 2 14. 47

407
1.3.4. Silicon Powder

Lab TEA Method Single- Multi-

# Vial # Code Point Point

1 166 1 1.83

1 166 11 1 . 88

1 171 1 1 . 63

1 171 1 1.78

2 15 1 1 . 80

3 5 1 1 . 90

3 5 1 1 . 90

3 5 1 1 . 90

3 8 1 1 . 80

3 8 1 1 . 90

3 8 1 1 . 90

3 59 1 2 . 00

3 59 1 1 . 90

3 59 1 2 . 00

3 61 11 1 . 80

3 61 1 1 . 80

3 61 1

n OA 1 . oO

4 69 1

0 AO

4 by 1 z . Uz

4 by 1 Z . Oi

4 by 1

0 n 1 Z . 01

4 70 1 1 . oO

4 70 1 1 . /9

4 70 1 1 . / y

4 70 1 1.79

4 71 1 2 . 03

4 71

-11 2 . 02

4 71 1

0 A A

2 . 00

4 71 1 2 . 01

5 20 1 1.70

5 20 1 1.70

5 56 1 1.90

5 56 1 1.90

8 237 1 2.33

8 237 1 2.30

8 237 1 2.32

8 238 1 2.36

8 238 1 2.32

8 238 1 2.34

15 1016 1 1.50

16 74 1 1.99

16 74 1 1.96

408
Silicon Powder

Lab TEA Method Single- Multi-

# Vial # Code Point Point

1 6 1

L. 1i , Qfi ^ o

J. u

1

J. i . ^ o

1 6 1 '-r 1

J.

1J- 7/ 40 1

J. 1 99

40 1

J. 1X , 99^ y 17 40 1 2 00

17J- / 40 1J- 1 99

17 40 1 2 . 00

17 40 1X 1 99

1J. 7/ 40 1X 2 00

1 7 40 1X 9c, , 00\J\J 17 41 1X 2 OS

17-A- / 41 1X 2 04

17 41 1X 2 05

17 41 1 2 . 04

17 42 1 2 . 01

17 42 1 2 . 02

17 42 1 1 . 99

17 42 1 1 . 98

17 42 1 1 . 99

17 43 1 1 . 96

17 43 1 1 . 96

17 43 1 1 . 97

17 43 1 1 . 99

17 43 1 1 . 99

17 44 1 2 . 03

17 44 1 2 . 01

17 44 1 2 . 04

1 7 1X 17 218 1 1.98

17 218 1 1.98

17 218 1 1.97

17 218 1 1.97

17 219 1 2.00

17 219 1 1.99

17 219 1 2.00

17 219 1 2.00

18 38 1 1.90

18 38 1 1.99

18 38 1 1.99

18 38 1 1.85

18 38 1 1.87

409
Silicon Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

18 38 1 1.84

18 38 1 1.92

18 38 1 1.93

18 38 1 1.90

20 35 1 2.25

1 166 2 --- 1.98

1 166 2 --- 2.02

1 171 2 --- 1.78

1 171 2 --- 1.95

6 81 2 --- 1.71

9 201 2 --- 2.18

9 201 2 --- 2.16

9 201 2 --- 2.19

9 242 2 --- 2.20

9 242 2 --- 2.57

9 242 2 --- 2.21

9 243 2 --- 2.19

9 243 2 --- 2.16

9 243 2 --- 2.61

22 95 2 --- 1.98

22 95 2 --- 1.98

22 95 2 --- 4.67

22 95 2 --- 4.25

22 96 2 --- 1.95

22 96 2 --- 1.95

22 96 2 --- 5.32

22 96 2 --- 4.50

23 105 2 --- 1.90

23 105 2 --- 1.98

23 105 2 --- 2.04

23 106 2 --- 1.93

23 106 2 --- 2.01

23 106 2 --- 1.99

23 703 2 --- 2.03

23 703 2 --- 2.00

23 703 2 --- 2.06

23 1027 2 --- 1.78

23 1027 2 --- 1.97

23 1027 2 --- 2.00

410
1.3.5. Yttria-Zirconia Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

1 496 1 17 .04

1 496 1 16 .93

2 9 1 15 .40

2 OB017 1 15 .70

4 8 1 18 .90

4 8 1 18 .90

4 8 1 19 .20

4 8 1 18 .90

4 8 1 18 .90

4 8 1 19 .20

4 583 1 18 .90

4 583 1 19 .30

4 583 1 19 .50

4 583 1 19 .40

4 583 1 18 .90

4 583 1 19 .30

4 583 1 19 .50

4 583 1 19 .40

4 622 1 18 .70

4 622 1 18 .80

4 622 1 19,.00

4 622 1 19,.00

4 622 1 19,.00

4 622 1 18,.70

4 622 1 18,.80

4 622 1 19.,00

4 622 1 19,,00

4 622 1 19,,00

6 661 1 17.,12

11 162 1 14.,10

11 AC015 1 16, 30

14 430 1 17.,00

14 603 1 16. 50

14 603 1 16. 10

15 OE014 1 15. 80

16 94 1 17. 20

16 94 1 17. 40

16 94 1 18. 80

16 94 1 19. 00

16 239 1 17. 40

16 239 1 18. 10

16 325 1 17. 40

411
Yttria-Zirconia Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

16 325 1 18.10

16 325 1 18.90

16 325 1 19.00

16 657 1 17.70

16 657 . 1 18.00

17 59 1 16.36

17 59 1 16.57

17 59 1 16.23

17 59 1 16.28

17 76 1 16.21

17 76 1 16.31

17 380 1 16.05

17 380 1 16.05

17 380 1 16.15

17 380 1 16.31

17 510 1 16.26

17 510 1 16.15

17 510 1 16.21

17 510 1 16.26

17 592 1 16.99

17 592 1 17.05

17 592 1 16.99

17 592 1 16.90

18 48 1 17.60

18 48 1 18.40

18 152 1 18.31

18 152 1 18.89

18 549 1 18.05

18 549 1 18.47

18 OR012 1 18.90

18 OR012 1 19.57

18 OR012 1 19.72

18 OR012 1 19.42

18 OR012 1 18.83

18 OR012 1 18.61

18 OR012 1 19.45

18 OR012 1 19.80

18 OR012 1 19.48

18 0R012 1 19.34

18 0R012 1 19.40

20 109 1 17.10

20 169 1 17.16

412
Yttria-Zirconia Powder

Lab lEA Method Single- Multi-

# Vial # Code Point Point

20 0 1/ 214 1 16 90

24 AFOl 7 1 15 30

24 OFOlo 1 16 50

24 OVOlo 1 15 60

1 496 oz 17 . 67

1 4y o 2 17 . 53

6 66 i 2 1 / . 62

Qo 1 j-J Z1 Q ly . uy

Qo

O 1

"7 0Z

1 Q lo . 6

1

Qo 6U1 Z lo . 64

Q Tin 2 iU 0Z1 Q lo Q Q

. yo

2_)4 Z

1 Q lo Q Q

. yy

Qy Z1 Q lo . y 1

1 /. 16 z lo ZU

1 /. 16 0Z lo /. r\ 40

1 Q iy Jl Z1 Q lo Zo

1 Q iy 0Z1 Q lo IZ

1 Q iy z1 Q lo 1 /

1 Q iy 0 Q 7 zy / z1 Q lo U J

1 Q iy 7 Q J y D Z1 8 1 o 14

iy 42o z

1 o lo 44

19 582 2 18 09

19 593 2 18 45

19 OC013 2 18 39

22 269 2 19 68

22 269 2 19 82

22 269 2 18 30

22 269 2 19 10

22 269 2 19 90

22 279 2 18 33

22 279 2 18 77

22 279 2 18 70

22 279 2 18 30

22 279 2 19 40

22 279 2 18 88

413
APPENDIX II- Particle Size and Morpholopv

The methods used for particle size measurement and their code numbers are

given in Table II. 1.

Table II. 1 Methods for Particle Size and Particle Size

Distribution Measurement

Method Code

Electrical Sensing Zone 7

Gravitational Sedimentation (Sedigraph) 9

Centrifugal Sedimentation 10

Light-Scattering, Fraunhofer-Mie Type 13

Light -Scattering, Photon Correlation 15

Scanning Electron Microscopy

Waddel Diameter 17

Max. Particle Diameter 18

414
Table II. 2 Particle Size Data Organized by Powder and Measurement Method

II. 2.1 Silicon Nitride Reference Powder

Gravitational Sedimentation (Sedigraph)

b lEA Method Expt

.

yu ' Din , Dqo/Dio y u/ lu Vial # Code Mean um um

/im Dsn

1 493 9 0.96 5 00 0 26 4 94

1 493 9 0.98 5 10 0 28 4 92

1 603 9 1.08 7 20 0 31 6 38

1 603 9 1 . 10 7 30 0 31 6 35

1 700 9 1.12 7 00 0 34 5 95

1 700 9 1.00 6 20 0 28 5 92

1 1109 9 0.88 4 10 0 25 4 38

1 1358 9 0.92 5 00 0 25 5 16

1 1423 9 0.96 7 70 0 24 7 77

1 1423 9 0.94 5 10 0 27 5 14

1 1423 9 0.87 4 90 0 24 5 36

3 542 9 1.30 4 00 0 67 2 56

3 543 9 1.35 7 30 0 62 4 95

3 1362 9 1.40 4 00 0 65 2 39

3 1369 9 1.25 3 20 0 61 2 07

4 1007 9 0.85 3 25 0 36 3 40

4 1007 9 0. 77 2 25 0 37 2 44

4 1007 9 0. 77 2 10 0 37 2 25

4 1007 9 0.86 4 10 0 36 4 35

4 1007 9 0. 79 2 60 0 36 2 84

4 1007 9 0.79 2 60 0 36 2 84

4 1007 9 0.59 2 00 0 24 2 98

4 1347 9 0.76 3 00 0 27 3 59

4 1347 9 0.69 2 50 0 27 3 23

4 1347 9 0.42 1 70

4 1347 9 0 . 64 1 90

4 1347 9 0.50 1 70

4 1353 9 0.58 2 70

4 1353 9 0.57 2 25

6 449 9 0. 80 2 80 0 17 3 29

6 1427 9 0.95 5 00 0 35 4 89

9 159 9 1.14 5 20 0 34 4 26

9 159 9 1.20 6 20 0 37 4 86

9 697 9 1.10 4 85 0 35 4 10

9 697 9 1.12 4 90 0 34 4 07

9 1173 9 1.18 5 90 0 34 4 71

9 1173 9 1.18 6 00 0. 34 4 80

9 1752 9 1.15 5 80 0 34 4 75

9 1752 9 1.10 5 40 0 34 4 60

415
Silicon Nitride Reference Powder

Gravity Sedimentation (Sedigraph)

Lab lEA Method Expt.

# Vial # Code Mean

/xm

15 9013 9 1 . 00

16 720 9 0 . 78

16 9025 9 0.77

17 225 9 0.82

17 761 9 0.68

17 1111 9 0. 90

17 1538 9 0. 70

17 1538 9 0. 75

17 1538 9 0. 72

18 161 9 0 . 80

23 28 9 0 . 88

23 28 9 0 . 79

23 28 9 0 . 90

23 256 9 0.69

23 256 9 0.63

23 360 9 0. 74

23 360 9 0 . 70

23 362 9 0 . 79

23 362 9 1 . 07

23 362 9 0 . 76

23 362 9 0.76

23 468 9 0 . 92

23 468 9 0.88

23 468 9 0.85

23 468 9 0.83

23 469 9 0 . 95

23 469 9 0 . 97

23 544 9 0 . 71

23 544 9 0.64

23 544 9 0.61

23 544 9 0.75

23 544 9 0. 74

23 544 9 0.66

23 654 9 0.72

23 654 9 0.70

23 1064 9 0.86

23 1064 9 0.81

23 1064 • 9 0.80

23 1064 9 0.84

23 1064 9 0.62

23 1064 9 0.80

23 1169 9 0. 70

^90 . Dio, D90/D10

D50

5.

- 00 0.

- 30 4 .70 —

-

3 .25

-

0 .33 3 —

.56

3 —.50 0 .29 3 .57

3 .05 0 .22 4 .04

3 .45 0 .21 4 .32

3 .15 0 .20 4 .10

4 .90 0 .23 5 .84

3 .75 0 .25 3 .98

2 .97 0 .27 3 .42

4 .00 0 .26 4 .15

3 .40 — —

3 .10

4 . 30 —

3 .25 — —

4 .50 —

4 .20 0 .25 3 .69

4 .20 0 .21 5,.25

3 . 50 0 .19 4,. 36

6,.40 0 .36 6,.57

3,.97 0 . 32 4,.15

2,,80 0 . 32 2,.92

3

,

.00 0 .31 3..24

3,,57 0 .31 3..43

3

,

, 51 0,.29 3,. 32

3.. 60

3,.10

3.,10

3.,60 0,.19 4.,55

4.,00 — —

2.,90

4.,10

3.,50

3. 68 0.,26 3. 98

2. 61 0,,24 2. 92

2. 56 0. 26 2. 88

3. 02 0. 27 3. 28

1. 70 0. 23 2. 37

3. 10 0. 26 3. 55

3. 15 0. 20 4. 21

416
Silicon Nitride Reference Powder

TEA Method Expt

.

^90 > Dio> Dgo/Dio

# Vial # Code Mean lj,m

)uni

23 1169 9 0.79 3.85 - 23 1270 9 0. 70 4. 10 - 23 1270 9 0.70 3.80 - 23 1373 9 0.81 4.20 0.22 4 91

23 1373 9 0.79 3.50 0. 18 4 20

23 1584 9 0.87 3.15 0.28 3 30

23 1584 9 0.74 2.27 0.23 2 76

1 1109 10 1.01

1 1109 10 1.06

1 1109 10 1.14

1 1358 10 0. 91

1 1358 10 1.02

1 1358 10 1.09 - —

1 1423 10 0.97 - - -

1 1423 10 1.00 —

1 1423 10 1.00 —

5 1741 10 0.68 4.00 0.29 5 46

5 1848 10 0. 70 5 .00 0 . 26 6 77

5 1852 10 0. 67 3 . 80 0. 30 5 22

11 9003 10 0.57 2 . 90 0. 20 4 74

13 56 10 1 . 32 —

13 56 10 1.42 —

13 253 10 1.37 • —

13 253 10 1 . 37 • —

13 375 10 1 . 67 _ _ _ _ _ _ 13 375 10 1 . 64 ~ ~ ~ _ _ _ —

13 400 10 1.48 —

13 400 10 1.61 — - —

13 624 10 1.44 - - - ... 13 624 10 1. 21 _ - - - - - - - 13 1016 10 1 . 25 - - - _ _ _ - - 13 1016 10 1 . 31 — - - - 13 1113 10 1 . 39 —

13 1113 10 1.46

13 1281 10 1. 36

13 1281 10 1.35

13 1315 10 1.39

13 1315 10 1. 38

13 1880 10 1. 36

13 1880 10 1. 36

14 96 10 0.98 4. 30 0.29 4. 09

19 1171 10 1.51

7 1576 13 1.35

417
Silicon Nitride Reference Powder

Lab TEA Method Expt. Dgg , Diq, Dgo/Dig

# Vial // Code Mean fim /zm

7 1576 13 1 .34

7 1576 13 1 .33

7 1576 13 1 .35

7 1576 13 1,.35

8 984 13 1,.19

8 984 13 1,.24

8 984 13 1,.19

8 984 13 1 .19

8 984 13 1 .18

8 984 13 1,.17

8 984 13 1 .25

8 984 13 1 .13

8 1478 13 1 . 15

8 1478 13 0,.98

8 1478 13 1 ,07

8 1478 13 1,. 10

8 1478 13 1,. 15

8 1478 13 1,.10

8 1478 13 1,.15

8 1478 13 1,,14

8 1478 13 1,.13

8 1478 13 1,,15

8 1478 13 0,,98

8 1478 13 1,,11

8 1478 13 1,,07

8 1478 13 1,,10

8 1478 13 0.,99

8 1478 13 1,,15

8 1478 13 1,,10

8 1478 13 1.,12

8 1478 13 1,,15

8 1478 13 1,,14

9 159 13 1.,23

9 159 13 1,,22

9 159 13 1,,31

9 159 13 1.,24

9 159 13 1,,26

9 159 13 1.,27

9 697 13 1.,28

9 697 13 1. 20

9 697 13 1. 29

9 697 13 1. 25

6.06 0,.42 4,.74

7.33 0,.42 5,.57

6.19 0 .43 4,.84

6.38 0 .42 5,.01

5.58 0 .41 4,.38

5.72 0 .41 4 .54

6.44 0 .41 4 .82

4. 70 0 .40 3 .81

5.16 0 .40 4 .14

3.45 0 .41 3 .10

5.23 0,.40 4,.51

5.27 0,.40 4,.43

5.06 0,.41 4,.04

4.74 0 .40 3,.95

5.21 0,.40 4,.18

5.46 0,.41 4,.43

4.99 0,.42 4,.04

5.16 0,.40 4,.14

3.45 0,,41 3,.10

4.42 0.,40 3,.62

5.23 0.,40 4.,51

5.27 0,,40 4.,43

3.51 0,,40 3.,14

5.06 0,,41 4,,04

4.74 0,,40 3,,95

5.02 0.,41 4,,12

5.21 0,,40 4.,18

5.46 0.,41 4.,43

6.40 0.,36 4,,91

6.40 0.,36 4.,95

7.27 0. 36 5.,27

6.68 0. 36 5.,10

6.49 0. 36 4. 87

6.53 0. 35 4. 87

7.24 0. 36 5. 38

6.31 0. 36 4. 96

7.35 0. 36 5. 42

6.68 0. 36 5. 06

418
Silicon Nitride Reference Powder

Lab lEA Method Expt. Dgo , D^o , D90/D10

# Vial y/ Code Mean /zm /um

/zm D50

0 by /

1 "3 1

9 C

. Zb b . 4z U . ib 4

0

1

. oi

Q by / i9 9

. z z

tr J

7 Q

. / 0 U . jb 4 . 44

Qy 117 7 i i / J1 T 19. Zb 0Q Q

. y 0 U

"3

. J b

cJ

9 ^

. Z J Qy 117 7 i i / J

1

"5 1i

9. Z b

7 9 9

. Z J U

9 7

. J / cJ . 44

y

1 1 7 Q 1 "3 1

9 0

. zo

r0

0 0

. 00 (J 9 C 5 A n

. uy

y

117 7 1 i / J

1 "3 i

9 n

. zy 7

. JZ (J . jb cJ

/ A

. 4U

y

117 7 ii / J i J i

Q c:

. J J

7

/ . J i U ,. jb cJ . 15

y

1 1 7 T ii / J1 Q i

9 9

. ZZ J

C 7

. 6 / L) , 9 c:. JJ 4

9 C

. ib

y

1 7 9

1 / DZ 1 "i i

1 /. cJ (J , 9 /.

. j4 4

/. 7

. 4 / y

1 7 c; 9 1 / JZ 111 0 cJ7 0

. /o r\U ,. ib 4 . 59

y

1 7 c 0 1 / JZ 11 ,. 1 / cJ7 A

U ,, i5 4

,

. 5 / y

1 7 Q 9 i / JZ 1 "3 i ,

c: J

7 Q

. / J U . 9 ^

, ib 4 ,. jy

y

1 7 R 9 1 / JZ 1

"3 i , 1 Q

. io cJ 0 Pi

. yu U , 9 ^;

. ib 4 ,, b y

y

1 7 9 i / J Z1

"3 i , 9 r>

. zU IT J . b4 U . 9. ib 4 ,, 4U

1 /i 1 b 0 b1

"3 U ,. / J z . uu A

U . 9

1

. i 1 z , 9 ^

. Z J ib 0 b

1

"3 U , 7 7

0zun 1 Q P iyo 1

"3 i , 9

. J Z

1 n Q Q

. 0 0 u

.

9 Q

. iy b . Q A . yu zu 1 Q 8 1 7 0

1

"3 i J

1 n Q . uy cJ . iJ U . 9 7 , i /

1. 4 . 9 Q , iy

z u 0 0/ 1

"3 1

"3 7 00 , R , 0 0 u , 9 8 , J 0 b ,, Ub

zu9 n A R 9 0 J Z

1

"3 1 3/1 p0 ,, J'+ u . 9 Q , J y

cJ . Q 9 , y i zu90 1 9/1 1 1

"3 1

. 'JJ

1 1 ^ 9 . JZ u

.

, It'tUn 7/ . 7 . b / zu9n 1 J y '4- 1

"3 1

, J b

7 Q Q . y y u

.

9 Q , i y

cJ ,. jy

9nzu 1ibyA Q ^J1

"3 1 "3 1 7 Q "3 u . 9 Q , iy cJ ,. b 0

9

1

Z i- y uu J

1

"3 u . 7 Q •3J , 9 n . ZU u . 9Zo8 •3i ., / u

9 9 z z1

"3 i J u

.

7 C

, / J

11 , Q 1

. y 1 u

.

9 1 i 1

0z

,

1 9 , 1 i

9 9 z z1 /. Q 1

"3 A

u

.

7 9 11 .

. 00 Au

.

9 1 i 1

nZ . 1 9

, iz

9 9 z z1 /, Q 1 "3 U . 7 9

/ J i . Q 7 . 0 / A

U . 9 1 i 1

0Z . 1 /.

, i4

9 9 z z1 /. Q 1 "3 U . 7 9 /z 1 ., ob AU . 9 9 iz 0z

.

14

0 0 zz 148 13 . 0

.

74 1 ., 89 0 . 31 2

.

14

22 148 13 0. 77 2,.01 0. 31 2 . 21

22 148 13 0. 73 2.,16 0. 31 2. 53

22 148 13 0. 74 2.,05 0. 31 2. 35

22 148 13 0. 73 2,,20 0. 31 2. 59

22 148 13 0. 73 2, 29 0. 31 2. 71

22 148 13 0. 74 2. 29 0. 32 2. 66

22 148 13 0. 74 2. 31 0. 32 2. 69

22 630 13 0. 89 2. 46 0. 34 2. 38

22 630 13 0. 87 2. 37 0. 35 2. 32

22 630 13 0. 88 2. 58 0. 35 2. 53

22 630 13 0. 89 2. 46 0. 35 2 . 37

22 630 13 0. 88 2. 51 0. 34 2 . 47

22 630 13 0. 88 2. 41 0. 34 2. 35

419
Silicon Nitride Reference Powder

Lab lEA Method Expt. Dgo , D^o, Dgo/Dio

# Vial # Code Mean /im /xm

fim D50

22 630 13 0,, 84 2

,

. 58 0,, 34 2

,

. 67

22 630 13 0

,

, 86 2, 55 0

,

, 34 2

,

. 57

22 630 13 0

. 84 2

,

, 55 0

.

, 35 2

,

. 62

22 630 13 0

,

. 84 2, 55 0

.

, 35 2

,

, 62

22 630 13 0

,

. 83 2

. 55 0

,

, 35 2

,

. 65

22 630 13 0

,

, 86 2. 43 0

.

, 35 2

,

. 42

22 630 13 0

, 88 2

,

, 31 0

,

, 35 2

, 23

22 630 13 0

,

, 90 2, 30 0

,

, 34 2

,

. 18

22 630 13 0

,

, 86 2, 49 0

.

, 36 2. 48

22 630 13 0,,87 2

,

. 31 0., 35 2,.25

22 630 13 0,.90 2,,27 0,,33 2,,16

22 630 13 0,,89 2,, 34 0,,35 2,,24

22 630 13 0,,74 2..06 0,,32 2,,35

22 630 13 0.,75 2,.18 0.,32 2,,48

22 630 13 0,,75 2..20 0.,33 2,,49

22 630 13 0,,76 2,.16 0. 32 2.,42

22 630 13 0,,75 2,.16 0. 32 2,,45

22 630 13 0.,74 2,.05 0. 31 2,,35

24 244 13 0.,40 2,.90 0.,10 7,,00

24 667 13 0.,85 9.,60 0.,24 11,,01

25 281 13 0.,80 2,,91 0.,33 3,,23

25 289 13 0.,77 2.,78 0.,32 3,,19

25 1226 13 0.,73 2.,61 0.,32 3,,14

420
II. 2. 2. Silicon Nitride Test Powder

ab lEA Method Expt

.

Dio. D90/D10

// Vial // Code Mean /im

D50

1 694 9 0 .55 0 .91 0 .33 1 .05

1 694 9 0 .58 0 .98 0 .36 1 .08

3 213 9 0 .69 1 .15 0 .43 1 .04

3 1302 9 0 .69 1 .10 0 .41 1 .00

4 544 9 0 .48 0 .71 0 .28 0,.90

4 544 9 0 .48 0 .71 0 .28 0 .90

4 950 9 0 .51 0 .74 0 .32 0 .83

4 950 9 0 .49 0,.70 0 .27 0,.88

4 1375 9 0 .53 0,.84 0 .30 1,.02

6 306 9 0 .64 1,.03 0,.38 1,.02

9 200 9 0 .62 1,.05 0 .32 1,.18

9 200 9 0 .71 1,.10 0,. 37 1,.03

9 1044 9 0 .70 1,,10 0,.40 1,,00

9 1044 9 0,.72 1,,09 0,.39 0,.97

9 1152 9 0 .71 1,, 10 0,.38 1,.01

9 1152 9 0,.64 1,.06 0,,32 1,, 16

9 1156 9 0,,71 1,,10 0,.40 0..99

9 1156 . 9 0,.69 1,,12 0,. 35 1,.12

9 LSM23 9 0,, 70 1,,08 0,, 36 1.,03

9 LSM23 9 0,,72 1,,10 0,,44 0,,92

15 LSM09 9 0,,42 0.,90 0.,33 1,,36

16 196 9 0., 54 . —

16 LSMOI 9 0.,42 . —

17 181 9 0,,64 0,,97 0,,42 0,,86

17 938 9 0,,59 0.,90 0,, 39 0,,86

17 938 9 0,,57 0,,87 0,,37 0.,88

17 1314 9 0..54 0.,82 0,, 36 0.,85

17 1463 9 0.,67 1.,04 0., 38 0.,99

17 1463 9 0.,64 1.,00 0., 37 0.,98

18 626 9 0.,27 0.,64 . _ _ . — _ 23 774 9 0., 50 1.,00 0., 28 1.,44

23 774 9 0.,43 0.,82 0,,20 1.,44

23 1165 9 0,,42 0., 71 0,,23 1.,14

23 1166 9 0.,44 0.,78 0.,26 1. 18

23 1187 9 0,,40 0.,72 0. 22 1. 25

23 1187 9 0..43 0. 96 0. 22 1. 72

23 1210 9 0,,35 0. 54 0. 19 1. 00

23 1210 9 0.,46 0. 78 0. 27 1. 11

23 1221 9 0.,45 0. 86 0. 24 1. 38

23 1344 9 0. 41 0. 69 0. 22 1. 15

23 1441 9 0.,42 0. 69 0. 25 1. 05

421
Silicon Nitride Test Powder

Lab lEA Method Expt. D90 , D^o, D90/D10

y/ Vial Code Mean /im /xm

lim D50

1

1

5

5

5

5

14

14

14

19

19

19

19

19

19

19

19

19

19

694

694

163

167

871

871

1178

1178

1178

101

101

217

621

621

959

1061

1324

1470

1470

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

10

0.77

0.78

0.53

0.56

0.53

0.53

0.56

0.55

0.66

1.10

0.89

0.89

0.93

0.85

0.83

0.77

0.84

0.93

0.78

1,

1,

1.

1,

1,

1.

1,

18

89

14

20

20

22

81

0.25

0.24

0.25

0.25

0.27

0.27

0.34

1

2

1

1

75

95

68

79

1.66

1.73

2.23

7

7

7

7

7

7

7

7

7

7

8

8

8

8

8

8

8

8

8

8

8

8

564

564

564

564

564

976

976

976

976

976

223

223

223

223

223

223

223

223

223

223

223

223

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

13

0.63

0.63

0.62

0.62

0.62

0.62

0.61

0.63

0.63

0.62

0.71

0.71

0.71

0.69

0.70

0.70

0.66

0.66

0.66

0.65

0.65

0.65

1.50

1.52

1.51

1.48

1

1

1,

1

1

1

1,

1,

51

50

41

39

38

36

39

37

0.37

0.37

0.37

0. 37

0. 37

0.37

0.36

0.36

0.36

0. 35

0.35

0.36

1,

1.

1.

1.

1.

1,

1,

1,

1,

1,

1,

1.

59

62

61

61

63

61

59

56

55

55

60

55

422
Silicon Nitride Test Powder

Lab lEA Method Expt.

# Vial # Code Mean

8 353 13 0 71

8 353 13 0 70

8 353 13 0 72

8 353 13 0 69

8 353 13 0 69

8 353 13 0 70

8 353 13 0 68

8 353 13 0 68

8 353 13 0 68

8 353 13 0 67

8 353 13 0 67

8 353 13 0 67

8 1417 13 0 69

8 1417 13 0 69

8 1417 13 0 67

8 1417 13 0 67

8 1417 13 0 68

8 1417 13 0 66

8 1417 13 0 67

8 1417 13 0 67

8 1417 13 0 65

8 1417 13 0 66

8 1417 13 0 66

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 200 13 0 61

9 1044 13 0 61

9 1044 13 0 60

9 1044 13 0 61

9 1044 13 0 61

9 1044 13 0 61

9 1044 13 0 61

9 1044 13 0 61

Dio. Dgo/Dio

fj,m

D50

1 53 0 37 1 63

1 52 0 37 1 64

1 57 0 37 1 67

1 45 0 36 1 58

1 47 0 37 1 59

1 53 0 37 1 66

1 46 0 36 1 62

1 46 0 36 1 62

1 47 0 36 1 63

1 43 0 36 1 60

1 43 0 36 1 60

1 Al 0 36 1 57

1 43 0 37 1 54

1 47 0 37 1 59

1 44 0 36 1 61

1 45 0 37 1 61

1 44 0 37 1 57

1 42 0 36 1 61

1 46 0 36 1 64

1 45 0 36 1 63

1 39 0 36 1 58

1 39 0 36 1 56

1 41 0 36 1 59

1 28 0 30 1 61

1 27 0 30 1 59

1 30 0 30 1 64

1 26 0 30 1 57

1 25 0 30 1 56

1 24 0 30 1 54

1 34 0 30 1 70

1 37 0 30 1 75

1 38 0 31 1 75

1 37 0 30 1 75

1 40 0 30 1 80

1 35 0. 30 1 72

1 31 0 29 1 67

1 26 0. 29 1 62

1 24 0 30 1 54

1 29 0 30 1 62

1 28 0. 30 1 61

1 29 0 30 1 62

1 34 0. 31 1 69

423
Silicon Nitride Test Powder

ab Me tnoQ Expt. Dio, Dgo/Dio

ji T 7 • „ T J/ Viai if Code Mean /xm

D50

y ii U . bi o o

. io 0 . 31 1

"7 C

. 75

Qy 1

r\U . oi i . i J u

Q A . iU 1 . 7z

y 1U . D i

1

. ib (J 0 AiU 1

—J /

. 74

y 1U . O i

1i0 "7

. i / U . i 1 1 . 74

y

1 M /. A 1 Q 1 J U . DZ i . iy U . ii 1

-J /

. 74

y 1 J nU

C A

1 . zi 0 . 29 1 . 57

y

T 1 c: o

1 J U

C A

1 . ZD 0 . iO 1 . 58

y liDZ 1 J 0 . 62 i . 4i (J . iO 1 79

y

1 1 c: O ii JZ 1 J 0 . 60 1 . ZD 0O A

. iO 1 58

n

y iibz ii 0 . 60 1 . z4 0 . 30 1 57

y iibz ii u

C A

. 6U 1 . 25 0 29 1 60

Qy1 1 ^; iiJD 1 i UC A i . Z4 AU zy 1

c 0 Do

Qy 1 i J o 1 i AU (^r\

. dU 1

0 0 . zz

A

u

0 Q zy 1

c c DO

Qy X J AU . DZ 1

A Q . M-y

A

u iU 1 yz

Qy X X J D X J A

U . oU X

1 Q . 10 A

U iU 1

A 7 4 / y XXDd X i Au . oU 1 . Z i A

u

0 Q zy 11 J / Qy XX JO X J Au . DU 1 . Z i AU

1 AiU 1

c c J J

Q X X J 0 X J Au . dZ i i / AU i 1

11

-7

/ i

Q X X J D X J Au . D Z 1 J D A

U iU 1 / 1

Q XX JD X J A

U . D Z 1 4 i AU iz 11

7 Q / y

y

1XXDD 1 '^C X i A

U . DZ 1 4z A

U i 1 1

7 Q/y

Qy XX JD 1 i A

U . DZ i

A 1 41 A

U

"3 1 i 1 1 / / y 11 JD 1 i A

U DZ i ib A

U

1

i 1

11 by

Q T CMO T LorlZ J 1 i AU . oi 1 i / AU1 1 i 1 1 bo

Qy libflZ J 1 i AU . DZ 1

iU AU iz 1

Q JO

Qy liOflZ J 1 i A

U DZ 1 i J AU

T AiU 11 by

QyTliOrlZ CMO J1 T 1 i Au DZ 1 iz A

U iz 1

CIbl

Qy

T CtuTO T libriz J

11 i A

u D i 1 zb AU i 1 1 j1

y librLz J 1 i AU . DZ 1

T A i4 A

U i 1 1 bb

Qy librlZ J ii A

u

^; 1 b 1 1A A Au1 1 i 1 17 Q/y

Qy

T CMO 1 1 i Au b i 1

0 Q zy

A

u

7 Aiu 1 bz

y Lbrlz J 1 i Au b 1 1

/. A A(J Q Ai(J 1

Q AoU

Qy LbiyiZ J1 "J 1 i 0 61 i io A "3 AiU 1

-7 -7

9 LSM23 13 0 60 1 40 0 28

-11 87

9 LSM23 13 0 62 1 40 0. 30 1. 77

14 222 13 0 53 1 50 0. 17 2. 51

14 222 13 0 57 1 25 0. 23 1. 79

14 960 13 0 55 1. 60 0. 22 2. 51

14 960 13 0 52 1. 33 0. 22 2. 13

20 193 13 0 58 1. 10 0. 32 1. 34

20 538 13 0 58 1. 09 0. 32 1. 33

20 850 13 0 58 1. 11 0. 32 1. 36

424
Silicon Nitride Test Powder

lEA Method Expt

.

Dgo , Dio- D90/D10

# Vial # Code Mean /xm /xm

/xm D50

22 94 13 0 .58 1 .24 0 31 1 .60

22 94 13 0 .57 1 .10 0 31 1 .39

22 94 13 0 .58 1 .21 0 31 1 55

22 94 13 0 .57 1 .18 0 31 1 53

22 94 13 0 56 1 .02 0 30 1 29

22 94 13 0 58 1 24 0 31 1 60

22 94 13 0 58 1 20 0 31 1 53

22 94 13 0 56 1 06 0 30 1 36

22 94 13 0 56 1 08 0 30 1 39

22 94 13 0 56 1 05 0 31 1 32

22 94 13 0 57 1 24 0 30 1 65

22 94 13 0 56 1 19 0 30 1 59

22 94 13 0 60 1 26 0 32 1 57

22 94 13 0 60 1 32 0 32 1 67

22 94 13 0 59 1 23 0 31 1 56

22 94 13 0 58 1 13 0 31 1 41

22 94 13 0 59 1 17 0 31 1 46

22 94 13 0 59 1 29 0 32 1 64

22 502 13 0 58 1 13 0 31 1 41

22 502 13 0 58 1 20 0 31 1 53

22 502 13 0 57 1 11 0 31 1 40

22 502 13 0 57 1 05 0 31 1 30

22 502 13 0 57 1 03 0 31 1 26

22 502 13 0 57 1 10 0 31 1 39

22 502 13 0 57 0 99 0 32 1 18

22 502 13 0 56 0 99 0 30 1 23

22 502 13 0 56 1 08 0. 30 1 39

22 502 13 0 56 1 00 0 30 1 25

22 502 13 0 56 1 13 0. 30 1 48

22 502 13 0 56 1 01 0. 30 1 27

24 298 13 0 73 1 51 0. 34 1 61

24 298 13 0 77 1 72 0. 41 1 70

24 895 13 0 75 2 01 0. 34 2. 23

24 895 13 0 69 1 92 0. 32 2. 32

25 432 13 0 54 1 00 0. 30 1. 30

25 432 13 0. 55 0. 99 0. 30 1. 25

25 758 13 0. 55 1. 01 0. 30 1. 29

425
II. 2. 3. Silicon Carbide Powder

..ab lEA Method Expt

.

D90/D10

Vial f/ Code Mean fJ,TD. D50

1 237 9 0 . 75 1

,

. 20 0

,

, 53 0 . 89

1 237 9 0 . 76 1

,

. 20 0

,

, 52 0 . 89

1 243 9 0 . 76 1

,

. 50 0

.

, 53 1 . 28

3 4 9 4 . 00 7

,

. 20 4

,

. 10 0 . 78

3 4 9 4 . 80 6 ,. 50 3 ,, 90 0 . 54

3 4 9 4 . 80 6 ,, 60 3 ,. 90 0.56

3 4 9

/

. zU 6 ,. 00 2

.

. 80 0.76

i

"77 y

/. 4

,

. jU 6 , ^ A

. 60 3 . Ci A. 90 A /"A 0 . 60

/ ny 4 ,. 4(J

rO , A A

, UU 3 , C A . 50 A C "7 0.5/

/ y 4

,

. uu 5 , O A. 8U 2 . n A

. 90 A "7 0 0 . /3

3 9 9 4 ,. 60 6 ,. 40 3

.

. 80 0 . 57

3 y 9 4 . 40 5 ,. 90 3 ., 70 0 . 50

3 9 9 4 . 20 6 ,. 40 3 ,. 50 0 . 69

3 11 9 5 . 00 6 ,. 70 4

.

, 40 0 . 46

3 11 9 4 . 40 6 ,, 20 3

.

, 90 0 . 52

3

1 1 11 9 4 . 10 6

,

, 00 3

,

, 80 0 . 54

4 69 9 0

,

. 65 0

,

. 95 0

,

, 46 0 . 75

4 69 9 u

,

. 57 0

,

. 88 0

.

, 43 0 . 79

4 y u . 49 u

,

O A u

,

. JO A OA u . yu

6 99 9 u

O O

. 82 1

,

, 30 0

.

, 62 A 00 0 . 83

9

O C C 255 9 0

,

. 59 1

,

, 12 u

,

O A

, 20 1.55

9

o c c 9 u . -Do 1

,

T r-

. 15 u

,

, 21 1.62

n

y

O c: /; ZDD n

y U ,

c; 0

. JO 1

,

T A U . O A i . j4

O c: ^ /_)D y

(-\ 0

. JO 1

,

n c

. ij A O A 1i . 0 J

y Zbi y U .

c; 0

. JO 1 ,. ZD AU . O A , ZU 1 Q A 1 . 8U

y zoi y U ,. ji 1 . A C AU . O A , zU 1 cr\ 1 . bU

y Zbi y U ,. 52 1 , A c; AU . i . b J

iU iUZD 9 (J ,. yu i , C A

T r lb 1012 9 0

,

. 55 1 , A A

u

.

O A , 2U 1 . 4D

16 o o o2 9 0

,

. 53 1 , A A, 00 0

,

, 19 1 . 5 J

16 LSM1013 9 0 ,. 46 0 . o c, 85 A0

,

O A

, 20 1 . 41

23 187 9 U ,

~7 A

. /O 1

.

O A

. 20 A

0

,

, 51 A n n u . y y 23 187 9 0

,

. 74 1

.

. 55 A

0 , C A, 50 1 . 42

23 190 9 0,. 55 0

.

, 98 0

,

, 35 1 . 14

23 190 9 0,,71 1,, 55 0,, 35 1.69

23 201 9 0,.65 1,,45 0.,45 1.54

23 201 9 0.,63 1., 35 0.,45 1.43

23 201 9 0.,60 1,,05 0.,41 1.07

23 201 9 0,,59 1.,05 0.,39 1.12

23 202 9 1,,03 2.,15 0. 55 1.55

23 202 9 0.,70 1.,61 0. 46 1.64

23 225 9 0,, 92 2.,00 0.,51 1.62

426
silicon Carbide Powder

Lab lEA Method Expt. Dgo, D^o , D90-D10

// Vial # Code Mean /xm /zm

jllR D50

23 225 9 0.99 1.78 0.55 1.24

23 225 9 0.62 1.32 0.41 1.47

23 228 9 0.76 1.45 0.51 1.24

23 228 9 0.75 1.35 0.55 1.07

23 228 9 0.72 1.35 0.50 1.18

23 229 9 0.74 1.45 0.51 1.27

23 229 9 0.67 1.25 0.48 1.15

23 234 9 0.69 1.40 0.45 1.38

23 234 9 0.80 1.50 0.49 1.26

23 234 9 0.98 1.80 0.50 1.33

1 236 10 0.68 1.88 0.40 2.18

1 240 10 0.71 1.50 0.45 1.48

1 243 10 0.83 2.06 0.45 1.94

1 243 10 0.64 1.80 0.32 2.31

1 243 10 0.58 1.72 0.29 2.47

1 243 10 0.70 1.76 0.38 1.97

2 13 10 0.40 0.86 0.11 1.87

13 103 10 0.63

13 103 10 0.65

13 104 10 0.71

13 104 10 0.70

13 105 10 0.66

13 105 10 0.67

13 106 10 0.67

13 106 10 0.65

13 107 10 0.65

13 107 10 0.68

7 250 13 0.44 0.67 0.29 0.86

7 250 13 0.39 0.64 0.23 1.05

7 250 13 0.44 0.67 0.29 0.86

8 268 13 0.52 1.00 0.30 1.35

8 268 13 0.52 1.00 0.30 1.35

8 268 13 0.52 0.99 0.30 1.33

8 268 13 0.51 0.99 0.30 1.35

8 268 13 0.51 0.99 0.30 1.35

8 268 13 0.52 1.01 0.30 1.37

8 268 13 0.51 0.98 0.30 1.33

8 268 13 0.51 0.99 0.29 1.37

8 268 13 0.51 0.99 0.30 1.35

8 268 13 0.51 0.99 0.30 1.35

427
Silicon Carbide Powder

Lab lEA Method Expt. D90 , Diq, D90/D10

# Vial 4 Code Mean /xm /xm

Mm D50

8 268 13 0 .51 0 .99 0,.30 1 .35

8 268 13 0 . 51 1 .00 0,.29 1 .39

8 271 13 0 . 51 0 .99 0,.30 1 .35

8 271 13 0 .51 0,.99 0,.30 1 .35

8 271 13 0,.51 0,.99 0..30 1 .35

8 271 13 0 .51 0 .98 0..30 1 .33

8 271 13 0,.51 0,.98 0,.30 1 .33

8 271 13 0 .51 0,.98 0,.29 1 .35

8 271 13 0 . 51 0,.99 0,.30 1 .35

8 271 13 0,.51 0,.98 0,.30 1 .33

8 271 13 0,.50 0,.99 0,, 29 1 .40

8 271 13 0,.51 0,.98 0,, 30 1 .33

8 271 13 0,. 51 0,.99 0,, 30 1 . 35

8 271 13 0,. 52 0,.99 0.,30 1,.33

10 39 13 0,.49 0,.99 0.,23 1 .55

10 40 13 0,.50 1,.52 0.,23 2,.58

10 43 13 0,,48 1,.03 0,,23 1,.67

10 1018 13 0,,48 1,,24 0,,23 2,.10

20 90 13 0..72 1.,61 0,,35 1,.75

21 1005 13 0,,57

22 171 13 0,,64 1.,50 0,,33 1,.83

22 171 13 0., 63 1.,41 0.,29 1,.78

22 171 13 0., 59 1,,32 0,, 30 1,.73

22 171 13 0., 58 1.,42 0., 30 1,,93

22 171 13 0,,58 1,,25 0., 31 1,,62

22 171 13 0,, 57 1.,17 0., 30 1,,53

22 171 13 0,,66 1.,41 0.,36 1,,59

22 171 13 0.,61 1,,24 0. 35 1,,.46

22 171 13 0. 60 1.,30 0. 33 1,,62

22 171 13 0.,60 1,,20 0. 34 1,,43

22 171 13 0. 59 1.,23 0. 32 1,,54

22 171 13 0. 59 1.,23 0. 33 1,,53

22 171 13 0. 65 1.,37 0. 35 1,,57

22 171 13 0. 59 1. 00 0. 35 1. 10

22 171 13 0. 61 1. 31 0. 33 1,,61

22 171 13 0. 59 0. 98 0. 35 1. 07

22 171 13 0. 59 1. 18 0. 34 1. 42

22 171 13 0. 57 0. 98 0. 33 1. 14

22 171 13 0. 64 1. 35 0. 35 1. 56

22 171 13 0. 60 1. 23 0. 33 1. 50

22 171 13 0. 59 1. 19 0. 32 1. 47

22 171 13 0. 58 1. 11 0. 32 1. 36

428
Silicon Carbide Powder

icLD TT7A lie UIIOU Expt

.

^90 > ^10 . r> /Pi

If V 1 a X L>(JLLfci Mean f 1 m

n^50

99 1 71 X J n . -> o 1X

1 R X n ^9J z 1X A^

99 1X 71/ J. 1X J n J o

1X 1XM-Zl n\j

,

^9^ z 1X A1M- X

99£.1. 1X 7A/ M- 1X o n 1X ^7 0\j . 1X S7

9 9 1 IL 1

'\ X ^ nu fil . O X 1X 99z z n 1X AA

99 1X 7A/1X J fin 1X 1X Q!7 n 1X A9M-Z 9 9 1X 7A/ 'I 1X J n X

1xyQ n 1X AA

£.1. 9 9 1X 7A/ H- 1X J J o

1X nQ n 1X J 1X

99 1X 7A/

1

X -J J o

1X 1X fio n 1X A'^ 9 9 X / M- X -J n O J

1X n 1X 71/ X

9 9 Z Z1 7/i X / X J nU fin D U

1X ZM- U . 1X AR

ZZ9 9 1 7/i X / X J nu SQ 1X nR o ^A 1X Z9 JR 9ZZ9 1 7Zl X / X -3 n JSQy

1X 99z z n J 9z1X D J

99z z 1 IL 1X 0 n o

1X nR n "^A 1X 9Rz o 99 1X 74/ 1

'\ X J 0 S7 1 09 0 1X 33

99 1 74 nu fi9 D Z 1 64 0

.

31•J X 2 15X ^

z99z 1X IL/ M- J_ J 0 56 0 Q1J- n 1

J. 09

22 174 13 0 58 1 09 0. 33 1 31

22 174 13 0 57 1 18 0. 31 1 53

22 174 13 0 55 1 29 0. 30 1 80

22 174 13 0 62 1 41 0. 33 1 74

22 174 13 0 59 1 32 0. 32 1 69

22 174 13 0 57 1 15 0. 31 1 47

22 174 13 0 60 1 53 0. 32 2 02

22 174 13 0 55 1 13 0. 30 1 51

22 174 13 0 57 0 99 0. 33 1 16

25 1016 13 0 53 1 17 0. 29 1 66

429
II. 2. 4. Silicon Powder

Lab lEA Method Expt. Dgg , D^q , Dgo/Dio

Vial # Code Mean /zm /im

/iin D50

16 74 -77 5 . 30 9 . 90 1

,

A 0

. 08 1 . 66

16 74 -7 rb . 20 9

,

. 60 1

.

A ~7

. 07 1 . 64

16 "7 /. /4 -7 c3 . 2U . 6U 1 , A a 1 . 64

16 74 "7 c. 40 10

,

. uu 1 , A 0. 08 1 . 65

16 "7 y. "7 cD , q A 1 AiU ,. UU 1 ,. 15 1

,

. 61

1 c 16 LbMlUl

J

-7 cD , Q A

1 166 c 1 A 12 , C A. DU 1

,

. 75 11

,

/" A

. 60

1 166 9 6 ,, 70 12 , A A

. 00 1

,

n A

. 90 1

,

. 51

1 168 9 6 ,. 80 12 , 0 A

. 80 1

,

. 85 1

,

. 61

3 5 y

c 0 r\

. 80 10

,

C A

. 50 2 , 1 A. 10 1

,

. 45

J

c n

y

cb

,

0 A

. 8U 1 A10 , C A. 50 1 , n A . yo 1 .. 48

0 cD yc /. A

y

,

C A . jU 1 ,/, A , 4U 1 , C A

. jU

i

000

y

cD , n A . yu 1 AiU , 0 A . oU 1 .. y 511 , C A , jU

0 00 y

cJ , n A

. yu 1 AlU , 0 A . oU i , 0 0. oZ 1 , c 0. JZ

J

00 y

cD , n A . yu 1 AiU , C A , 6U i .. fa J

1i , c 0

, JZ

J y fa , Q A . jU 1 AiU , q A , jU z

,

Q A , jU 1 "3 A . jU

0 Qy

cJ , 7 A . /u 1 AiU , q A , jU i , 7 A . /U ^

. J'*

0 jy Qy

cJ , 7 A , /u 1 AiU , A . jU 1i

,

c c

. J J i

,

c 7

oJ D i

Qy

cJ ,. oU 1 AiU ,. 4-U z ,. lU 11

,

0J fa i

Qy

cJ , Q A lU ,, ^U 1 Q, y J

1

. M-fa

1, Q fay Qy

cJ , /i n 1 n . jU 1 n 1^ 1

J.

,

71

A Q fa yQy

c;J , . jU 1

, U L

1 7 9 . / Z

7 T

/

1

Qy

cJ .. / u 1 n , jU 1

. JJ 1

. 0 1

/, / iQy

cJ , ^ A iU , 1 n . lU 1 7. ^ 11 , Q . jy

7 0 n

y

qJ , Q A . yu 1iUA .. cSU 1 c. c

. J J

1 7 0 n

y

cJ , Q A . yu 1 AiU .. OU i , c c

. J J

1i , c 7

6 82 9 5 . 0 A

. 80 1 A10 . A "7

. 07 1 ,. 55 1 . /

-7

. 4/

9 201 9 6,.50 11,.50 2,.00 1,.46

9 201 9 6,.60 11,.50 2,.50 1,,37

9 242 9 6..50 11..50 2..35 1,.41

9 242 9 6.,70 12,.00 2..00 1,.49

9 243 9 6,,80 12..30 2.,50 1,.44

9 243 9 6.,60 11,.50 2.,30 1,.39

15 1016 9 6.,20 10. 50 2. 00 1,.37

16 32 9 5.,65 9. 67 2. 03 1,,35

16 LSM1013 9 5. 58 9. 52 2. 13 1.,32

17 40 9 7 . 20 13, 00 1. 80 1.,56

17 40 9 7. 20 13, 00 1. 80 1. 56

17 40 9 7. 30 13. 00 1. 90 1. 52

17 42 9 7 . 50 13. 80 2. 00 1. 57

17 42 9 7 .,50 13. 80 2. 00 1. 57

430
Silicon Powder

lEA Method Expt

.

Dio. D90/D10

# Vial # Code Mean

D50

17 42 9 7 .40 13,,50 1 .80 1 .58

17 42 9 7.20 13,,50

17 42 9 7 .00 13.,00 1 .75 1 .61

17 90 9 6.70 12.,50 1 .55 1 .63

17 90 9 6.70 12,,00 1 .55 1 .56

17 128 9 7.60 13.,70 2 .00 1 .54

17 128 9 7.60 14.,20 2 .00 1 .61

17 128 9 7.40 13. 50 2 .00 1 . 55

18 36 9 5.60 10.,00 1 .50 1 .52

23 48 9 6 . 50 12

.

, 30 2 .05 1 . 58

23 101 9 6.20 13. 00 1,.60 1,.84

23 102 9 6.90 12. 30 2,.25 1,.46

23 102 9 6 . 80 13

.

50 1

,

. 50 1

,

. 76

23 1022 9 6 . 20 12

.

00 1,. 80 1,. 65

23 1024 9 6 . 30 13

.

30 1,. 70 1,. 84

23 1024 9 6 . 30 13. 00 1,, 70 1

,

. 79

23 1026 9 6 . 10 12. 20 1

,

. 50 1,, 75

23 1032 9 6.50 13. 30 2.. 30 1,.69

23 1032 9 6 . 10 13. 30 1,, 30 1..97

23 1034 9 5 . 70 14. 20 1., 35 2.,25

1 166 10 4. 15 7

.

49 1..40 1..47

1 166 10 4.29 7

.

06 1

,

, 95 1

,

, 19

1 166 10 4.09 7

.

35 1

.

, 95 1

.

, 32

2 65 10 6 . 60 9

.

80 0

,

,43 1

,

,42

5 1 10 5 . 00 11. 80 0

,

, 56 2

,

, 25

5 24 10 4.90 11. 70 0.,56 2 ,,27

19 227 10 4.79 — —

19 228 10 5 . 30 " ~ - - . - - 19 229 10 4 . 96 - - . - - 19 230 10 4. 85 ' " - . - - —

19 231 10 5 . 39

19 232 10 6.05

19 233 10 4.62

19 244 10 5.03

19 1005 10 4.74

5 1 13 6.50 11. 70 1. 60 1. 55

5 24 13 6.50 11. 80 1. 60 1. 57

8 237 13 7.31 13. 99 2. 57 1. 56

8 237 13 7.58 15. 01 2. 55 1. 64

8 237 13 7.51 14. 39 2. 52 1. 58

431
Silicon Powder

J TFA i IC L.L IL^ U

Vial V/ Moan ^111 f / m

^111 ^50

fio 1 3 7 34 1X 3J 94 z9 . JS8o1X . J J

Qo 1 3 7 S S 1XHZl . *+

J

9z 6 S 1X . J D

Qo I. ~> 1 1 3 7 S8 1XM-L 1 . XD 9z

c;i

. J X

1X SA

QO L ~J 1 1X o3 7 ZiO 1X J . MJ

z9 60 1X A7

QO Z -J / 1X J 7 78 XM- OA. z9 . O X1X AA

Qo J / 1X .J3 /.JO 1

'\ X J 98 z9 . J ~> 1X

Qo z. J / 1X 3J 7/ . 9z 9^ 1X J 70 9z . 69u z1X . JS9z

QO

9*^7 1X J 7 Zl9 / . M- Z 1X J 9fi . Z D 9z . 71/ X

1X A9

QO 9 "^7 Z J / 1X 3J 7/ . 9AZM- 1X J . 9z 7/ 9z

6"^ 1X LI

QO 9 "^8 Z -) o 1X ^ 7 Zl9 1XH-1± A9 9z S8 1X S 9 . J y

QO 9Z J 8o 1

'\ X J 7 ^^7 1X J , O J 9z . JSIX

1X . JSIX

QO 9Z J 8o 1

'\ X ^ 7/ . 98z o 1X J 90 9z LI 1X S7

Qo 9Z J 8o 1X J3 7/ . 1X 9z 1

'\ X J . 77/ / z9 A8 1X . -JS9y «o 9 "^8 Z -) o 1X 3^ 7 9 9 1X LH- 00 9z . LL 1X S9

«u 9 38 1 3 7 56 1X*-r4 , 59 9 80 1X SS

8 938 1 3 7 33 1 4 30 9z. , 63 1X , 59

8 238 13 7 35 14 . 19 2 . 60 1 . 58

8 238 13 7/ 23Z- 13 , 60 2 . 66 1X I. 51

8 238 13J- —

7 19 13 . 62 2 . 63 1 .53

8 938 13J- ^ 7 1 2 12 84 2 . 40 1 47

8 238 13J- ^ 7 39 14 > 41^ X 2 , 64 1X .. 59

9 201 ^ V/ J. 1X 3J 7 40 1X ~J3 , 70 9 85 1X < 47

9 201 1X 3>^ 7 47 1 4 05 9 96 1X < 48

9 201 1X -J3 7/ • 44*-r'-r 1X'-r4 , 39 9 . 91x X

1X 1 54

9 201 1X ^3 7 49 1XH-4 . 08 9 99 1X 1 49

Q 901 Z W X 1X 3J 7 L'\ 1XH-4 , 04 9 99 1X . 50

Q 901 Z v/ J- 1X D 7 Zi7 1XM-L ,. 96z o 9 99 1X . 52

Q-/ 901 Z X 1X 3 X J . 70 9 85 1X . 47

QV zu± 901 1

'\ X 7 Zl7 XH- , OS 9 96 1X .I 48H- KJ q Z901W X 1X ^3 XH- . 39 9 91 1X . 54

9 901 1X ^3 7 49 1XH-4 , 08 9 92 1X 1 49

9 901 Z W X 1X 3J 7 Zi.'^ / . H J 1XH-4 , 04 z9 ,, 92y z 1X . 50

Q zU 1 ± J7 /i 7 1 /i

, ZD Z ., Q9y Z

1X ,. J z

9 242 13 7.42 14.,03 2.,81 1.,51

9 242 13 7.43 14, 06 2 . 87 1.,51

9 242 13 7 .40 13. 74 2. 83 1.,47

9 242 13 7.52 13. 92 2 . 89 1.,47

9 242 13 7.47 14. 08 2. 96 1. 49

9 242 13 7.41 14. 00 2. 84 1. 51

9 242 13 7.42 14. 03 2. 81 1. 51

9 242 13 7.43 14. 06 2. 87 1. 51

9 242 13 7.40 13. 74 2. 83 1. 47

432
Silicon Powder

Lab lEA Method Expt.

# Vial # Code Mean

y z4z Li 1 9

. JZ

n

y

o /. o Z4Z 1 Q i J 1/. 7

. 4 / y z4z 13 1 . 41

y z4 i 13 1 . 34

y z4i 1

J

1 . jy

y z4 J 1

J

—11

.

T 7

y

9 /. T z4 J1 "J 1

J

-j1

.

. 4b

n

y

O /. Q z4 J 13 1

.

. ol

y

O /. 0 z4j 13 1

.

9 Q

. jy

y

O A Q z4 J 13 1 . 9 /.

. -54 y

9 /. "3 Z4 J 1

J

1 . 1 Q. jy

y

O /. Q z4 J 1

J

-J1 . Q 7

y

9 /. T z4 J1 "3 1 J-J

. 4d

y

O /. T z4 J 1 J 1 ., b 1

y

9 /. 1 z4 J1

"3 1 J

7 T Q

, jy

J J

1

"3 1

J

7

/ ,

"3 C . jb

z Z

Q 1 y J1

"3 1 J

QO . 1 n . lU

z z Q 1 y J

1

"3 7 8 1 zz Q 1 y J

1

"3 1

J

7 Q , by

z z

Qy J1

"3 7 , J y Z Z

Q 7 i J7 , O J

9 9 Z ZQ "3 1

J

7/ ,, 0'+ 9 9 Z Z

Q 'X y J1

"3 1

J

7/ , "3 "3

, J J

9 9 Z Z Q T 1

"3 1

J

7 / 7 , 4 / 9 9 ZZ Q "3 1

"3 1

J

7 /. Q , 4y

o o ZZ 93 13 1 ., 34

22 93 13 7,,68

22 93 13 7,,63

22 94 13 7,,09

22 94 13 7.,22

22 94 13 7,,28

22 94 13 7. 19

22 94 13 7. 37

22 • 94 13 7.,25

22 94 13 7. 63

22 94 13 7.,59

22 94 13 7. 91

22 94 13 7. 83

22 94 13 7. 90

22 94 13 7. 70

^90 > Dio. D90/D10

/xm

1

"3 1

J

Q 9 . y z z8 Q . oy 1A 7 . 4 /

1 / 14 n Q . UO 0z . yb 11/ Q . 4y

1 /, 14 . UU 0za A . cS4 1 . J 1

1

"3 1 J

nZ

a 1

. 0

1

1 . ju

1

"3 1 J ,. bU 0Z

a ^ . Ob 11A. 4D

1

"3 1 J , a. O J

0Z

a . Ob 11 . 4y

14 ,, UU 0Z

a a . 00 11 . 4y

14 ,. Lb 0 n 9. Uz 1

/i C

. 4b

13 ,. 96 0z

7 0

. / 3 1 . 53

13 , O A 0z . ol 1 . 5U

13 ., bU 0z

0 c

. OD 1 ,. 4D

13 , o c. OD z

0 c

. 00 1

A n

. 49

14 ,. UU 0z

Q 0

. 00 1 . 4y

14 , 1 a

. lb 3 r\ 9. Uz 1

A C . 4b

1 J , Q

. yo

0z

7 "3 19 . JZ

1

"3 1 -5 . a Q , 0 y 0z , 7n . /U 1 , 1^ 9 . Dz

1 /. 14 , a 7 , o / z . 1 a . 10 11 . c 7

114/i

. z

,

, Uo 1 , c 7

14 , 8 9 , oz z

,

1 7 . 1 /

11 , ft A , b4

1 /i L'-V , 1 1 ,11 z . 1 c.

, 1

J

11 ,. J 0

14 , Q7 . y 1 oz ,, Lj 1 ,

"3

1 J . 1 A . 14 0z ,. lb 11 ,, bb

1

"3 1 J . Q a , yo 0z ., DU 1 . c 7

1

"3 1 J , Q A , yb z ,

"3 9 , JZ 1 .. J b

1

"3 1 J . 8 a 0z

,

/ 9 . 4Z 11 , 9

. J J

1

"3 1j , HQ , uy 0z ,. Ub 1 ., JU

14 . A 1^, 4D z . 1 Q . ly 1 ., bU

1

"3 1 J . a /. o4 z , 1 a , lo 11 . 9

, J J

1 9 Iz . a noU 0z

,

"3 9 . JZ 1 , A a , 4o

1 J ., jU 0z .

"3 9 , JZ 1 . c c

, J J 13 . 44 02 ., 61 1 .. 49

12. 90 2.,21 1.,49

13. 45 2,,12 1. 54

13. 68 2,,17 1.,59

12. 86 2.,70 1. 33

12. 61 2.,68 1. 31

13. 71 2.,53 1. 41

13. 69 2. 94 1. 37

13. 75 2. 61 1. 41

13. 58 2. 74 1. 41

433
II. 2. 5. Yttria-Zirconia Powder

Lab lEA Method Expt. Dqq , D^o , D90/D10

y/ Vial # Code Mean /xm

4 313 9 0 . 17 3 . 20 •m — ~ ~ 4 9 2 . 60 ... 4 y U . ij 0 A A

1 /. Q 0

y U . 1j 0 A A

4

/. 0 "7 y U . iJ 0 "7 A Z . /U

4 y

0 OA z . zU

A4

/. O "7 y U . jz /. A A 4 . UU

4

n

y U . ZO Q Q A J . jU

b

/. "7 n y U0 A . zU Q OA J . zU

1 c i J

/~\ T? 1 /. y U , 0 A . zU /. A A 4 . UU

1 / Dy y U . Z4

1 -7 17 y u1 0

. lo

1 /

"7 ^ /D y U

1 0

T

-7 i / 7 C 1 D Qy U

1 7

T

-7 i / 7/ 0 Qy U . Lb

1 7 1 / z / J nU 4 . UU

1 7 1 / 0 9 R Q AV . Z4- J . / U

1 7 joU Qy u 1 Q . Ly

1 7 joU Q u

T 7 i / ion J oU Qy

Au

^ 7

1 7 joU QyA

u

^ c

. i J

1 7 i / joU Qy

A

u

1 Q

. io

1 7 1 / Q Au

9 n . ZU

1 7 1 / J oU Q Au . 9nZU

1 7 J OU Qy

Au 9

1

. z 1

17 380 9 0 .19 _ _ _ 17 380 9 0 .19

1 7 1 / Qy

A

u

.

7 a 7n 0 . /U

1 7 i /

•PT 7 D I? 1 Qy A

u

.

^U 7 9n / . ZU

1 / lUBE#z y

A £ A 0 C A 0 . 5U

17 TUBE#3 9 0. 31 6.60 0.16 20.78

18 48 9 0 .15 10. 50

18 101 9 0 . 50 11.00

18 549 9 0 . 15 12.00

18 0R12 9 0. 15 11.00

18 0R12 9 0. 17 14.00

23 46 9 0 .15

23 46 9 0 .18

1 731 10 1 .54

1 731 10 1 .44

1 731 10 1 .47

434
Yttria-Zirconia Powder

Lab lEA Method Expt. Dgo , D^o , D90/D10

# Vial # Code Mean /im jim

1 731 10 1.62

1 731 10 1.54

1 731 10 1.38

11 162 10 0.56 2.90 0.18 4.86

14 462 10 1.73 7.30 0.29 4.05

19 31 10 1.50

19 31 10 1.50 --- --- 19 .82 10 1.34

19 82 10 1.43

19 224 10 1.59

19 224 10 1.54

19 297 10 1.40

19 297 10 1.47

19 396 10 1.41

19 396 10 1.21

19 428 10 1.58

19 428 10 1.62

19 582 10 1.69

19 582 10 1.61

19 593 10 1.50

19 593 10 1.49

19 0C013 10 1.38

19 0C013 10 1.34

11 AC015 13 2.90 9.20 0.37 3.04

,14 232 13 2.20 9.50 0.40 4.14

14 562 13 2.30 9.50 0.40 3.96

14 567 13 2.30 9.80 0.40 4.09

20 109 13 4.06 11.33 0.51 2.67

20 169 13 4.17 11.80 0.50 2.71

20 214 13 4.19 11.49 0.50 2.62

22 269 13 0.62 2.60 0.15 3.95

22 269 13 0.66 2.87 0.15 4.12

22 269 13 0.72 2.55 0.15 3.33

22 269 13 0.95 2.72 0.15 2.71

22 269 13 0.82 2.50 0.15 2.87

22 269 13 0.78 2.38 0.15 2.86

22 269 13 0.83 2.96 0.15 3.39

24 AF017 13 1.50 7.70 0.13 5.05

24 0F018 13 1.80 8.60 0.14 4.70

24 0V018 13 1.40 7.60 0.13 5.34

435
Yttria-Zirconia Powder

Lab lEA Method Expt. D90 , Djo , D90/D

# Vial y/ Code Mean /xm /xm

/im D50

Q 9 1 n 1

c; i-j nU . Z91J_ Q 9 1 n i. J nu . z99z Q 9 1 n 1 c: nu . z9nu

Q 9Z 1lUn J. J nw . Z91J_ Q z 1 u n 1 Q

Q 9Z 1lUn Du . z9nvj Q 9Z

1lUn J. J u . xy

Q 9 1 n Z lU 1 CL nu . 1xyQ

Q Z ID nu . 9nzu

Q Z DM1 c ID nu 1 q . ly

Qy 9z jm^ SZi 1±DS n 90

qy 9 1 s n 1 Q

qy Z9 JHSZi 1 q J. ^ D 1 Q

q 9Z S^. q 9 SA. 0 19

q 9 54 0 19

q 376 15 0.22

q 376 15J- -J 0.22

qy J / D

1 5 J. D n 91

9 376 15 0.22

9 376 15 0.19

9 376 15 0.19

9 376 15 0.19

9 376 15 0.18

23 46 15 0.18

23 46 15 0.18

23 46 15 0.18

23 46 15 0.19

23 46 15 0. 18

23 46 15 0.18

23 46 15 0. 18

23 46 15 0. 18

23 46 15 0. 18

436
Table II. 3 PARTICLE MORPHOLOGY - DATA TABLES

II. 3.1 Silicon Nitride Reference Powder . Number Distribution

Lab lEA Method

Code

Expt. Mean

Geom.

Std. Dev,

23 609 17 0.4

13

13

13

13

13

13

13

13

13

13

13

56

253

375

400

624

1016

1113

1281

1315

1880

LSM 9012

18

18

18

18

18

18

18

18

18

18

18

0.80

0.86

0.81

0.69

0.72

0.81

0.98

0.76

0.79

0.78

0.62

II. 3.2 Silicon Nitride Reference Powder, Mass Distribution

Lab lEA Method

Code

Expt. Mean

Geom.

Std. Dev,

23

12

609

9011

17

18

1.39

1.50

2.29

II. 3.

3

Silicon Nitride Test Powder . Number Distribution

Lab lEA Method

Code

Expt. Mean

Geom.

Std. Dev.

23 284

23 284

17

17

0.5

0.4

437
II. 3. 4. Silicon Nitride Test Powder . Mass Distribution

Geom.

Lab lEA Method Expt. Mean Std. Dev.

# # Code urn o

23 284 17 1.03 1.83

23 284 17 1.06 2.02

12 LSM 16 18 1.20

II. 3.5. Silicon Carbide Powder . Number Distribution

Geom.

Lab lEA Method Expt. Mean Std. Dev.

# # Code /xm

23 191 17 0.32 1.96

23 191 17 0.35 1.78

23 191 17 0.41 1.64

II. 3. 6. Silicon Carbide Powder . Mass Distribution

Geom.

Lab lEA Method Expt. Mean Std. Dev.

y/ // Code . /im

23 191 17 0.79 1.75

23 191 17 0.83 1.61

23 191 17 0.90 1.69

438
II. 3. 7. Silicon Powder . Number Distribution

Lab

#

23

23

23

23

23

23

12

II. 3. 8.

Lab

23

23

23

23

23

23

II. 3.9.

Lab

18

18

18

18

18

18

Geom

.

lEA Method Expt. Mean Std. Dev.

# Code fim

47 17 1.16 2.29

47 17 1.16 2.15

47 17 1.16 2.33

47 17 1.23 2.27

1028 17 1.11 2.10

1028 17 1.06 2.26

1012 18 2.10

Silicon Powder . Mass Distribution

Geom

.

lEA Method Expt. Mean Std. Dev.

# Code /im

47 17 6.65 1.93

47 17 6.15 1.94

47 17 6.53 1.98

47 17 7.15 1.78

1028 17 5.47 1.98

1028 17 4.89 2.04

Yttria-Zirconia Powder . As-Received, Number Distribution

lEA Method Expt. Mean

# Code /im Std. Dev.

OR012 18 39.36 17.04

OR012 18 31.10 17.87

OR012 18 36.16 20.23

215 18 34.95 16.28

48 18 34.83 17.97

549 18 27.49 16.31

439
II. 3.10. Yttria-Zirconia Powder . Dispersed, Number Distribution

Geom

.

Lab lEA Method Expt. Mean Std. Dev.

// y/ Code /xm a„

23 198 17 0.3

II. 3. 11. Yttria-Zirconia Powder , Dispersed, Mass Distribution

Geom.

Lab lEA Method Expt. Mean Std. Dev.

y/ # Code /zm og

23 198 17 2.27 4.39

12 30306403 18 1.50

12 30306403 18 1.80

440
APPENDIX III - Chemical Composition

Table III.l lists the methods and their code numbers for

identification of these methods in the following data tables.

Table III.l Chemical Analysis Methods and Codes

Method UOQe

Atomic Absorption/Emission (AA/AE) 1

Inductively Coupled Plasma (ICP) 2

Ion Chromatography 3

Specific Ion Electrode 4

Mass Spectrometry (MS) 5

Neutron Activation Analysis (NAA) 6

Optical Emission Analysis 7

Combustion 8

X-Ray Fluorescence (XRF) 12

Potentiometric Titration 13

Argentometric (Coulometric) T. 14

Kjeldahl Analysis 15

Coulometric Titration 16

Directly Coupled Plasma (DCP) 17

Gravimetric 20

Not specified 21

441
III. 2.1.

Table III. 2 Major Chemical Component

Silicon Nitride Reference Powder (SNR)

Lab lEA Method Si N Si

# Vial # Code % % (free)

%

14 103 1 59.50

14 593 1 59.50

1 396 2 58.50

1 396 2 56.30

6 1677 2 58.07

15 965 2 59.38

21 634 2 59.92

21 634 2 59.65

21 634 2 58.68

21 634 2 59.43

1 373 8 --- 38.33

1 373 8 --- 38.63

1 1878 8 --- 38.45

1 1878 8 --- 38.67

1 1878 8 --- 38.57

1 1878 8 --- 38.40

3 525 8 --- 38.30

3 525 8 --- 38.30

3 527 8 --- 38.20

3 527 8 --- 38.20

3 535 8 --- 38.20

3 535 8 --- 38.20

3 538 8 --- 38.20

3 538 8 38.20

5 1620 8 --- 38,50

6 106 8 --- 38.40

6 106 8 --- 38.50

6 756 8 --- 37.70

6 756 8 --- 37.80

13 56 8 --- 40.85

13 253 8 --- 40.57

13 375 8 --- 40.50

13 400 8 --- 40.56

13 624 8 --- 40.20

13 1016 8 --- 40.03

13 1113 8 --- 40.72

13 1281 8 --- 41.32

13 1315 8 --- 41.23

13 1880 8 --- 41.52

13 9012 8 --- 41.26

442
Silicon Nitride Reference Powder

Lab lEA Method

# Vial # Code

14 103 8

18 577 8

18 885 8

19 1171 8

21 634 8

21 634 8

21 634 8

24 244 8

24 1704 8

24 9005 8

5 1309 12

25 188 12

24 244 13

24 244 13

24 1186 13

15 965 15

25 1869 15

1 396 17

1 396 17

1 814 17

1 814 17

1 1368 17

1 1368 17

3 527 17

18 885 17

3 525 18

3 527 18

3 535 18

3 538 18

13 56 20

13 253 20

13 375 20

13 400 20

13 624 20

13 1016 20

13 1113 20

Si N Si

% % (free)

%

38.00

32.10

37.58 --- 37.72

38.30

38.10

38.20

40.50

39.30

38.30

59.90

59.40

40.50

32.07

37.59

38.91

38.40

58.00

59.40

57.40

58.10

60.30

61.40

59.10

59.41

0.13

0.14

0.10

0.13

59.62

59.05

59.41

59.33

59.60

59.53

59.40

443
Silicon Nitride Reference Powder

Lab lEA Method Si N Si

# Vial # Code % % (free)

13 1281 20 59.38

13 1315 20 59.76

13 1880 20 59.56

13 9012 20 59.61

18 577 20 58.74

24 31 20 60.20

24 244 20 60.00

24 9005 20 58.10

444
III. 2. 2. Silicon Nitride Test Powder (SNT)

Lab lEA Method

# Vial # Code

14 1380 1

6 1426 2

15 381 2

21 1385 2

21 1385 2

21 1385 2

21 1385 2

16 353 4

16 361 4

16 507 4

16 507 4

16 507 4

1 824 8

1 824 8

1 1063 8

1 1063 8

5 441 8

5 785 8

5 1234 8

5 1235 8

6 383 8

6 383 8

14 1380 8

15 381 8

18 98 8

19 101 8

19 217 8

19 621 8

19 959 8

19 1061 8

19 1324 8

19 1470 8

21 1385 8

21 1385 8

21 1385 8

21 1385 8

21 1385 8

21 1385 8

24 82 8

Si N Si

% % (free)

%

60.00

59.10

60.15

60.40

59.90

59.60

60.00

0.021

0.022

0.028

0.028

0.029

37.40

37.90

38.40

38.30

39.30

39.10

38.80

38.40

38.50

39.00

38.50

38.10

32.30

38.02

37.88

38.27

38.57

38.59

38.53

39.20

38.80

38.90

38.70

38.80

38.90

38.90

39.50

445
Silicon Nitride Test Powder

Lab lEA Method

# Vial # Code

24 82 8

24 82 8

24 82 8

24 82 8

24 82 8

24 82 8

24 731 8

24 731 8

24 731 8

24 731 8

24 731 8

24 731 8

24 731 8

21 1385 9

21 1385 9

. 5 1279 12

5 1279 12

5 1279 12

5 10870 12

5 10870 12

5 10870 12

25 629 12

25 629 12

25 629 12

25 629 12

25 629 12

25 629 12

24 1278 13

24 1278 13

5 785 15

5 785 15

5 1234 15

5 1234 15

15 381 15

25 432 15

25 432 15

25 432 15

25 432 15

Si N Si

% % (free)

%

38.70

39.30

38.50

39.70

39.30

40.50

39.70

40.70

39.70

40.10

38.80

39.60

41.00

0.070

--- --- 0.090

59.80

59.70

59.80

59.60

59.90

59.70

59.41

59.20

59.32

59.18

59.35

59.43

38.40

37.90

39.10

38.80

38.70

38.90

39.04

38.84

38.97

38.95

38.93

446
Silicon Nitride Test Powder

Lab lEA Method SI N Si

# Vial # Code % % (free)

%

25 432 15 --- 38.79

25 432 15 --- 39.00

1 1063 17 61.60

1 1063 17 62.60

18 1480 17 58.89

18 98 20 59.46

24 90 20 59.40

24 90 20 59.10

447
III. 2. 3. Silicon Carbide Powder (SIC)

Lab lEA Method Si C

# Vial # Code % (total)

%

6 102 2 63.73

15 65 2 70.11

21 2 2 69.20

21 2 2 69.30

21 2 2 69.00

1 238 8 ~ ~ ~ 29.012

1 238 8 28.928

1 238 8 28.984

1 238 8 28.897

6 101 8 31.460

6 101 8 31.450

7 251 8 30.100

7 251 8 ~ ~ ~ 30.100

8 264 8 28 . 960

8 265 8 29.450

15 65 8 29.340

18 91 8 29.700

25 53 12 69.64

25 53 12 69 . 56 - - - 25 53 12 69. 11 - - - 25 53 12 69 . 78

25 53 12 69 .42

25 53 12 69 . 36 ...

10 1025 16 29.970

21 1 16 30.100

21 1 16 30. 100

21 1 16 30.040

25 55 16 30.070

25 55 16 30.070

25 55 16 30.010

25 55 16 29.970

25 55 16 30.010

25 55 16 30.050

8 262 20 65.86

8 263 20 68.63

18 91 20 68.49 29.700

448
silicon Powder (Si)

lEA Method Si

Vial // Code %

167 1 99.40

80 2 94.06

11 2 98.59

2 20 98.90

2 20 98.80

2 20 98.60

58 20 98.80

58 20 98.90

58 20 98.80

204 20 98.19

205 20 94.77

37 20 99.00

449
III. 2. 5. Yttria-Zirconia Powder (YSZ)

Lab lEA Method Zr Y

% u

1r V X d X f

0

y/'a

18 54 1 67 00

18 65 1 67 10

18 OR012 1 67 20

1L OZ z D J

ftn

1L D Joz D J nn

C.D Z DO 7 8 / o

1 c: 1 J 9Z

1 7 J7Z 9Z

Li. •J 0Z

7 T / i

i. i. 0Z

71 / n

2 73 6

0 9 Z Z

•3J

1 9 xZ D O

22 3 12 68 50

22 3 12 68 50

22 75 12 68 53

22 75 12 68 54

22 75 12 68 49

24 AF017 12

24 0F018 12

24 0V018 12

14 559 17

17 592 17

4.50

4.33

4.54

3.92

3.88

3.48

4.11

4.52

4.60

4.60

4.30

4.23

4.18

4.19

4.15

4.15

4.19

4.52

4.52

4.52

4.20

4.41

450
Table III .3 Major Nonmetallic Impurities (concentration > 100 ppm by weight)

III. 3.1. Silicon Nitride Reference Powder

Lab lEA Method CO F

# Vial # Code (total) % %

%

24 244 3 --- --- 0.128

24 646 3 --- --- 0.110

24 9005 3 --- --- 0.150

25 205 3 --- --- 0.170

6 1640 4 --- --- 0.150

6 1677 4 --- --- 0.164

23 261 6 --- 2.060

23 290 6 --- 2.370

23 340 6 --- 2.410

23 439 6 --- 2.310

23 746 6 --- 2.090

23 750 6 --- 2.150

23 868 6 --- 2.330

23 1001 6 --- 2.050 --- 23 1209 6 --- 2.290

23 1456 6 --- 2.200

23 1470 6 2.220

23 1788 6 --- 2.110

1 373 8 0.170 2.568

1 373 8 0.170 2.548

1 373 8 0.170

1 1878 8 0.150 2.561

1 1878 8 0.160 2.449

1 1878 8 0.160 2.563

1 1878 8 --- 2.491

3 525 8 --- 2.320

3 525 8 --- 2.320

3 527 8 --- 2.310

3 527 8 --- 2.310

3 535 8 --- 2.310

3 535 8 --- 2.310

3 538 8 --- 2.330

3 538 8 --- 2.330

5 1620 8 --- 1.900

5 1620 8 0.120

6 106 8 0.146 2.040

6 106 8 0.148 2.110

6 106 8 0.154

6 756 8 0.160 2.180

451
Silicon Nitride Reference Powder

T T? A Metnod c 0

T 7

- „ T J/ Vial # Code (total)

%

0/

6 756 8 0 159 2 . 200

7 29 8 0 loO ~ ~ ~

7 29 8 0 160 ~ — *

7 29 0

8 0 150

7 29 8 0

T "7 r\ 1/0

7 29 8 0 l30

-77 29 0 0 1 jO

-77

00 0 130

-71 0 iM^O —

1 zy 0 IbO

7

0 0 "7 2o7 8 0

1 'J A 130

7

0 0 ~7 287 8 0 loO

7

0 0 ~7 287 8 0

1 '3 A 130

7

0 0 ~T 287 8 0 loO

-77

0 0 ~7 287 n8 0 130

7

0 0 ~7 287 08 U

1IIU1 n

7

7

0 0 ~7 287 08 u

1 'XC\ 1 jU

"77

0 0 ~7 28 7 08 u Tin 1 lU

-7 "7 Q 0

/ OZ Q 0 1 on z . lyo

•7 "7 Q 0

/ oZ Q0 z . z jO

-7 7 Q 0

/ OZ Q z . z jO

-7/ iU J J

Q 0 Ton Z . JZO

-7/ Q0

0 0 7 n z . Z / 0

7

/ iU33 Q 0 Tin z . 310

i J JO Q 0 1 1 n z . 110

0 tr "3 2 53 8 2 . 150

13 0 "7 C 375 08 2 . 130

li / f\c\ 400 08

0 OTA 2 . 210

13 624 8 2.230

13 1016 8

0 1 0 rv 2 . 130

13 1110 1113 08 2 . 120

13 1 0 0 T 1281 08 2.230

13 1315 00 2 . 130

13 1880 8 2 . 200

13 9012 8 2.280

14 103 8 0 160

14 593 8 0 160 2.000

15 965 8 0. 150

15 1062 8 2.400

16 512 8 0. 150 1.800

16 512 8 0. 160 2.040

16 1664 8 0. 150 1.750

452
Silicon Nitride Reference Powder

Lab TEA Method CO F

# Vial # Code (total) % %

%

1 6 1A- 664 \J \J '-T 8 0 1X 70/ w . 010

1 7 643 8 0 1 50 230

J- / 875 8 0 1 90 0 Z.91X 0w

J- U 577 8 0 1 30 1 30

1 s 577 8 0 1X 30-J V/

J- U 885 8 0 1X 60u w 9 050 Vy J w

1J- 9-/ 1171 8 0 1 90 ? 090

634 8 0 970

21 634 8 2 250

21 634 8 2 220

21 634 8 2 230

21 634 8 2 370

21 634 8 2 180

22 262 8 0 180

22 262 8 0 170

22 262 8 0 180

22 262 8 2 130

22 262 8 2 170

22 262 8 2 220

22 262 8 2 230

22 262 8 2 210

22 898 8 0 170

22 898 8 0 170

22 898 8 0 170

22 898 8 2 140

22 898 8 2 170

22 898 8 0

.

150

901 6 8 9 390

22 9016 8 2 390

22 9016 8 2 420

22 9016 8 2 350

22 9016 8 2 280

22 9016 8 0 150

22 9016 8 0 150

22 9016 8 0 150

24 244 8 2 080

24 1704 8 2 100

24 1709 8 0. 170

25 1213 8 2 510

25 1226 8 2 690

25 1231 8 2 600

25 1877 8 0. 180

453
Silicon Nitride Reference Powder

Lab lEA Method CO F

# Vial # Code (total) % %

%

5 1620 13 --- --- 0.120

14 103 13 --- --- 0.120

14 593 13 --- --- 0.120

21 634 13 --- --- 0.076

21 634 13 --- --- 0.080

24 244 13 0.052

24 1041 13 0.030

24 9005 13 0.027

24 9005 13 0.032

2 1888 16 --- 1.780

2 1888 16 --- 1.980

2 1888 16 --- 1.930

3 525 16 0.270

3 527 16 0.250

3 535 16 0.280

3 538 16 0.260

21 634 16 0.330

21 634 16 0.300

21 634 16 0.310

(

454
III. 3. 2. Silicon Nitride Test Powder

Lab lEA Method

# Vial # Code

24 1272 3

24 876/1272 3

24 876/1272 3

24 876/1272 3

25 1060 3

25 1060 3

25 1060 3

25 1060 3

25 1060 3

25 1060 3

6 1426 4

8 171 5

8 1328 5

8 1360 5

23 156 6

23 297 6

23 300 6

23 346 6

23 437 6

23 1400 6

23 1401 6

23 1406 6

1 824 8

1 824 8

1 824 8

1 824 8

1 1063 8

1 1063 8

1 1063 8

1 1063 8

5 441 8

5 441 8

5 785 8

5 785 8

5 1234 8

5 1234 8

5 1235 8

5 1235 8

CO F

(total) % %

%

0.002

0.002

0.002

0.002

0.007

0.007

0.008

0.007

0.008

0.008

0.011

0.000

0.000

0.000

1.100

1.170

1.220

1.130

1.100

1.110

1.240

1.220

1.550

1.550

0.100

0.100

2.580

2.590

0.160

0.160

1.190

1.130

0.090

0.100

0.090

0.100

1.120

1.080

455
Silicon Nitride Test Powder

Lab lEA •Method c 0

JLIf Vial f/ Code (total)

%

o/L

b

T Q T JO Jo0 U no . uy J 1 . i jU

b

T Q T JO JQO nU . uy J

1 / O f\

b

Q 0 T J 0 J

QO U . uy J

-7/ 443 oo

1 D ^ A 1 . jdU

-71 oo 1 . jdU

1 44 J

oo 1 . 340

1

1 o "7 r\ Iz /(J oo nU

1 on . lyu

-7/

1 o "7 n iz /U oo U

1 on . lyu

/

1 o ~7 n IZ /(J oo n 9 nn . ZUU

-7/ 12 /U oO nU

9 nn . ZUU

7

1 o ~7 r\ Iz /u o0 n 9 9 n . ZZU

14 o n "7 o0 nU

1 nn . lUU

14 iioU oo 1 . 100

Joi oo n

u ,. IUj 1 . z40

lb Jzl o8 nu ,. 119 1 iz

ib oo n\j ,. 1 J J ib JZ 1

oo nu

.

. 191 1 Z 1

lb n1 jZI Qo n , lift J- X o XD J Z 1 QO n 1 "^9

, X J ^

1XD J Z 1

OO n . X J J

J Z 1

QO

1 9 t;i 1 . Z J 1

-3 Z 1

QO

1 ISA 1 . 104

1lb 0 1 J Z 1QO1 1 n7 1 . lU / lb J Z 1

QO

1 1 ^7 1 . lb / lb J Z i QO

1 9 1 1 . Z J J

1 c lb jZ i QO1 9 1 Q 1 . z ly

lb 1 ly u

Q0 nu

.

1 "^1

, 1 J

1

lb lion 1 lyu oo nu

.

11 9QZ 7 lb iiyu oo nu . 114Z/ 9

lb lion liyu oo nU . 11 77J / lb iiyu QO n 14b

lb lion 1 ly u

Q0 0. 161

lb 1 1 Qn 1 ly u

Q0 1 . ZD J

16 1190 8 1 . 249

16 1190 8 1.212

16 1190 8 1.193

16 1190 8 1.203

16 1190 8 1.191

18 98 8 0. 120 1.250

18 1480 8 0. 160 1.200

19 101 8 0. 130 1.230

19 217 8 0. 140 1.190

456
Silicon Nitride Test Powder

Lab lEA Method CO F

# Vial # Code (total) % %

%

19 621 8 0 .110 1 .220

19 959 8 0 . 160 1 .230

19 1061 8 0 .120 1 .230

19 1324 8 0 .120 1 .230

19 1470 8 0 .120 1 .260

21 1385 8 — 1 .170

21 1385 8 — 1 .180

21 1385 8 — 1 .210

21 1385 8 1 .160

21 1385 8 — 1 .180

21 1385 8 — 1 .170

22 786 8 0,,110 —

22 786 8 0,.110 —

22 786 8 0.,110 —

22 786 8 — 1,,280

22 786 8 — 1,.250

22 1154 8 0.,130 —

22 1154 8 0.,130

22 1154 8 0.,140 —

22 1154 8 — 1.,270

22 1154 8 — 1.,250

24 32 8 0. 120 —

24 32 8 0. 120

24 32 8 0. 110

24 32 8 0. 100 —

24 32 8 0. 120 —

24 32 8 0. 110 —

24 32 8 0. 110 —

24 32 8 0. 140

24 82 8 1. 040

24 82 8 1. 150

24 82 8 1. 180

24 82 8 1. 150

24 82 8 1. 110

24 82 8 1. 100

24 82 8 1. 150

24 731 8 1. 100

24 731 8 1. 090

24 731 8 1. 070

24 731 8 1. 130

24 731 8 1. 100

24 731 8 1. 140

457
Silicon Nitride Test Powder

Lab lEA Method

# Vial # Code

24 731 8

25 75 8

25 75 8

25 75 8

25 75 8

25 75 8

25 75 8

25 919 8

25 919 8

25 919 8

25 919 8

25 919 8

5 785 13

5 785 13

5 1234 13

5 1234 13

14 1108 13

14 1380 13

21 1385 13

21 1385 13

24 90 13

24 90 13

24 598 13

24 598 13

21 1385 16

21 1385 16

21 1385 16

21 1385 16

18 98 20

CO F

(total) % %

%

1.100

0.120

0.120

0.130

0.130

0.140

0.140

1.338

1.333

1.303

1.378

1.353

0.004

0.004

0.004

0.004

0.006

0.006

0.005

0.005

0.063

0.059

0.045

0.046

0.110

0.100

0.120

0.100

0.120

458
III. 3. 3. Silicon Carbide Powder

Lab lEA Method C N 0 F

# Vial # Code (free) % % %

%

6 102 4 --- --- --- 0.073

8 266 6 --- --- 1.370

8 267 6 --- --- 1.580

23 184 6 --- --- 0.760

23 185 6 --- --- 0.730

23 186 6 --- --- 0.730

23 189 6 --- --- 0.750

23 231 6 --- --- 0.780

23 232 6 --- --- 0.760

23 233 6 --- --- 0.750

23 235 6 --- --- 0.740

2 20 8 --- --- 0.675

2 21 8 --- --- 0.675

6 101 8 --- 0.086 0.749

6 101 8 --- 0.078 0.733

6 101 8 --- 0.081 0.737

7 246 8 --- --- 0.730

7 246 8 --- --- 0.740

10 39 8 0.690

10 43 8 0.697

10 47 8 0.709

10 47 8 --- 0.145 0.825

15 65 8 --- 0.080 0.450

18 91 8 --- 0.065

21 1 8 --- 0.069 0.690

21 1 8 --- 0.071 0.710

21 1 8 --- 0.071 0.700

22 169 8 --- 0.080 0.645

22 172 8 --- 0.075 0.640

25 57 8 --- --- 0.765

25 57 8 --- --- 0.739

25 57 8 --- --- 0.748

25 57 8 --- --- 0.746

25 57 8 --- --- 0.720

25 57 8 --- --- 0.744

25 57 8 --- --- 0.722

25 57 8 --- --- 0.738

25 59 8 --- --- 0.716

25 59 8 --- --- 0.749

459
Silicon Carbide Powder

Lab

# Vial

lEA

#

Method

Code (free)

C N

%

OF

% %

%

25 59 8 --- --- 0.728

25 59 8 --- --- 0.733

25 59 8 --- --- 0.755

21 1011 13 --- --- --- 0.042

21 1011 13 --- --- --- 0.040

21 1011 13 --- --- --- 0.040

10 1025 16 0.270

21 1 16 0.570

21 1 16 0.580

21 1 16 0.580

21 1 16 0.600

22 169 20 0.660

22 172 20 0.630

460
III. 3. 4. Silicon Powder

Lab lEA

Vial #

Method

Code

C

%

N

%

0

%

Al

%

Fe

%

1

16

16

18

19

19

19

19

19

19

19

19

19

167

28

31

37

227

228

229

230

231

232

233

234

1005

1

1

1

1

1

1

1

1

1

1

1

1

1

0.006

0.025

0.025

0.030

0.025

0.025

0.021

0.024

0.021

0.027

0.028

0.025

0.024

0.045

0.038

0.038

0.050

0.043

0.042

0.042

0.044

0.042

0.047

0.043

0.042

0.043

5

5

5

5

6

7

7

7

7

15

17

20

20

22

22

22

22

22

22

22

22

20

20

51

51

80

162

163

163

164

11

220

33

34

99

99

99

99

100

100

100

100

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

0.570

0.570

0.017

0.017

0.016

0.017

0.035

0.033

0.032

0.040

0.024

0.028

0.031

0.030

0.032

0.013

0.028

0.029

0.027

0.029

0.030

0.036

0.036

0.034

0.034

0.046

0.049

0.047

0.040

0.040

0.040

0.042

0.052

0.054

0.052

0.050

0.054

0.050

0.054

0.053

8

8

204

205

0.015

0.015

8

8

23

236

235

45

6

6

6

1.820

1.570

0.630

461
Silicon Powder

Lab lEA Method C N 0 Al Fe

# Vial # Code 7= % % % %

23 46 6 --- --- 0.650

23 49 6 --- --- 0.650

23 50 6 --- --- 0.650

23 1019 6 --- --- 0.660

23 1020 6 --- --- 0.560

23 1021 6 --- --- 0.690

23 1025 6 --- --- 0.610

1 167 7 --- --- --- 0.020 0.030

1 165 8 0.080

1 165 8 0.080 --- --- --- . ---

2 16 8 --- --- 0.510

2 66 8 --- --- 0.510

3 6 8 --- 0.060 0.543

3 7 8--- 0.060 0.540

3 19 8 --- 0.070 0.552

3 60 8 --- 0.070 0.556

5 52 8 --- --- 0.490

5 52 8 --- --- 0.500

5 52 8 0.057

5 52 8 0.055

5 53 8 0.053

5 53 8 0.050

5 53 8 --- --- 0.550

5 53 8 --- --- 0.490

6 79 8 0.080 0.010 0.480

6 79 8 0.080 0.010 0.550

6 79 8 0.080 0.010 0.470

6 79 8 --- 0.020 0.490

7 160 8 0.076

7 160 8 0.078

8 206 8 0.015

8 207 8 0.028

15 11 8 0.050 0.060 0.540

16 29 8 0.084

16 29 8 0.117

16 29 8 0.095

16 29 8 0.088

16 29 8 0.127

16 29 8 0.087

16 29 8 0.096

462
Silicon Powder

Lab lEA Method C N 0 Al Fe

# Vial # Code % % % % %

16

16

16

16

16

16

16

18

22

22

22

22

22

22

22

22

22

22

29

29

74

74

74

74

74

37

99

99

99

99

99

100

100

100

100

100

8

8

8

8

8

8

8

8

8

8

8

8

8

8

8

8

8

8

0.089

0.091

0.210

0.069

0.071

0.072

0.069

0.069

0.071

0.010

0.516

0.534

0.548

0.529

0.549

0.490

0.520

0.520

0.520

0.510

3

3

3

3

6

7

19

60

16

16

16

16

0.060

0.063

0.058

0.062

3

3

3

3

6

7

19

60

17

17

17

17

0.043

0.042

0.042

0.044

0.044

0.050

0.063

0.043

463
III. 3. 5. Yttria-Zirconia Powder

Lab lEA Method C N S CI

# Vial # Code (total) % % %

%

6 403 2 --- --- 0.116

6 403 3 --- --- --- 0.018

6 630 3 --- --- 0.031 0.860

24 AF017 3 --- --- 0.021 0.025

24 0F018 3 --- --- 0.017 0.028

24 0V018 3 --- --- 0.016 0.025

8 117 5 --- --- 0.200

8 372 5 --- --- 0.200

8 395 5 --- --- 0.200

2 73 6 --- --- --- 0.034

14 166 8 --- --- 0.090

14 166 8 --- --- 0.090

15 314 8 0.037 --- 0.091

17 5924 8 0.035 --- 0.100

22 3 8 0.033

22 3 8 0.031

22 3 8 --- 0.025

22 3 8 --- 0.028

22 3 8 --- 0.023

22 3 8. --- 0.032

22 75 8 0.036

22 75 8 0.039

22 75 8 0.038

22 75 8 --- 0.022

22 75 8 --- 0.025

22 75 8 --- 0.026

22 75 8 --- 0.031

14 166 14 --- --- --- 0.022

464
Table III. 4 Data Tables on Major Metallic Impurities

III. 4.1. Silicon Nitride Reference Powder

lEA Method Al Ca Fe

II Vial # Code % /o %

1 814 1 0 .0300 0 0200 0.0100

14 103 1 0 .0445 0 .0200 0.0155

14 593 1 0 .0450 0 .0205 0.0157

16 717 1 0 .0380 0 0090 0.0200

16 717 1 0 .0420 0 01 1 0 0.0260

16 1667 1 0 .0350 0 0070 0.0200

16 1667 1 0 .0390 0 0080 \J \J \J \J 0.0220

16 1747 1 0 .0360 0 . 0060 0.0190

16 1747 1 0 .0390 0 . 0080 0.0220

18 885 1 0 .4600 0 . 0200 0.2700

24 244 1 0 0980 0.0300

24 1182 1 nd 0 . 0680 0.0300

24 9005 1 0 0500 0.0350

1 396 2 0,.0300 0 . 0100 0.0100

1 1358 2 0,.0400 0 . 0100

1 1358 2 0,.0400 0 . 0100

5 1309 2 0 .0380 0 . 0079 0.0180

6 1640 2 0,,0478 0 . 0142 0.0491

6 1677 2 0..0360 0 . 0100 0.0194

7 683 2 0,,0460 0 . 0100 0.0220

7 683 2 0..0460 0 . 0100 0.0230

7 1235 2 0,.0440 0 . 0100 0.0220

7 1235 2 0,.0430 0 . 0090 0.0210

7 1235 2 0.,0450 0 . 0100 0.0220

7 1235 2 0,,0460 0 . 0100 0.0220

13 56 2 0.,0400 0 0200 0.0100

13 253 2 0.,0200 0 01 00

13 375 2 0,,0400 0 01 00 0.0100

13 400 2 0.,0400 0 01 00 0.0100

13 624 2 0. 0400 0 m no 0.0100

13 1016 2 0. 0400 0,,0200 0.0100

13 1113 2 0. 0200 0,,0100

13 1281 2 0

.

0400 0.,0400 0 . 0100

13 1315 2 0. 0400 0.,0100

13 1880 2 0. 0300 0,,0200 0.0100

13 9012 2 0. 0400 0,,0100

15 965 2 0. 0415 0,,0089 0.0212

19 1171 2 0. 0433 0.,0089 0.0203

20 1394 2 0. 0015 0,,0015 0.0064

21 634 2 0. 0430 0,,0120 0.0230

21 634 2

• 0. 0450 0.,0120 0.0240

465
Silicon Nitride Reference Powder

1_ lEA Method Al Ca Fe

if Vial # Code % ^

21 634 2 0

,

, 0440 U . OizU 0 A O / A

. UZ40

21 634 2 0

.

. 0450 0 .0110 0 .0240

22 262 2 0 .0100 0 .0290

22 898 2 0,.0530 U

n r\ ~7 A 0 A O C A

22 898 2 0

.

, 0510 0 .0060 0 .0260

22 898 2 0,,0490 0 .0060 0 .0290

22 898 2 0,,0510 0 .0060 0 .0290

22 898 2 0,,0380 0 .0010 0 .0110

22 898 2 0.,0280 U . UUiU AU

A 1 0 A . UizU

22 898 2 0

,

, 0290 (J . UUiU AU

A 1 1 A . UiiU

22 898 2 0

,

, 0340 U

A A 1 A . UUiU Au A 1 0 A . UiZU

22 1100 2 U

Al 1 A . U i iU AUAl 7A . Ui /U

22 9015 2 U

A 1 0 A . UiZU AUr\o art

. UZ bU

7 1681 7 0

.

, 0600 0 .0300

23 1744 7 0,,0100 0 .0200

5 1309 12 0.,0380

3 52538 17 0,,0400 0 .0300 0 .0400

14 593 17 0,,0427 0 .0081 0 .0222

17 643 17 0.,0400 0 .0070 0 .0200

17 875 17 0.,0400 0 .0100 0 .0200

25 293 17 0,,0417

25 1869 17 0 .0094 0 .0233

466
III. 4. 2. Silicon Nitride Test Powder

Lab TEA Method Al Ca Fe

JiIt V X a. X /o

X X ^ o

1X w 001 9 0W , 0056 W W J D

X O V/ 1X . 001 WW X 0w 0W , 0039 W W -> <L 0W . 0053 W W _/ J

1J. fiyJ 994 1X 0W . 0038 W W J o

JS98O

1X 0W . 0450 WM- _) W 0W , 0300 W _) w w

-/ o

1X 0 0990 0W . 03W O J50w

9 . 0003 W W W J 0W , 0005 W W W J 0W . 0036 W W u 994 n 0003 0 0007 0 0036

1 090 9 n , 0003 W W W J 0 00"^ S

^Xw090-/ VJ 0 n .WWW-) 0003 0 OO'^S

o XM- ^ U 9 0 00S9

71 79 9 0 009ft

7 79 9 0 OO'^S

7 79 9 0 00*^9

^ O X 9 0 0009 0 OO'^Q

1 7 J W*-+ 9 n 5049 0 019'^ 0W , 01VJ X RQo ^

1 480 9 0 . 9000 z. w w w 0 01 00 0 9000

1X 01\J X 9 . 0009 w wwz. 0w . 0009 w w w z. 0 004'^

1 9 917 ^ X / 9 n 0009 0 0003 0 0039

1X 9J 691Z. X 9 0 . 0009 W W W Z. 0 0003 0Vy . 0049 \J \J'-r £.

1X 9J 959 0C 0 0009 0 0003 0 0041

19 1061 9Z. 0 0009 0 0009 0 0046

1X 9J 1 "^94 9 0 0003 0 0009 0 0043

19X J 1 470 9 0 . 0003 \J \J\J 0 0003 0 0041

z.9 _^'S9z. 9 0 0001 0 0001 0 0009

21 1385 J_ ^ u _y Z.9 0 0049

21^ J- 1385 Z.9 0 0051

^ X 1 "^85 X ^ U 9 0 0048

^ X 1 "^85 9 0 0050

21^ X X ^ o ^ 9 0W , 001 W W X 6u

9 1 1 ft i J O J U . wU X J

21 1385 2 0.0015

21 1385 2 0.0015

22 786 2 0.,0160 0.0010 0.0110

22 786 2 0.,0200 0.0020 0.0100

22 786 2 0. 0220 0.0110

22 786 2 0. 0170 0.0100

22 1154 2 0. 0210 0.0100

22 1154 2 0. 0220 0.0110

22 1154 2 0. 0210 0.0100

22 1154 2 0. 0210 0.0110

467
Silicon Nitride Test Powder

Lab lEA Method Al Ca Fe

# Vial # Code % % %

8 171 5 --- 0.0007 0.0026

8 1328 5 --- 0.0016 0.0078

8 1360 5 --- 0.0005 0.0079

2 428 6 --- --- 0.0037

7 433 7 --- --- 0.0040

14 1108 17 0.0015 0.0030 0.0032

14 1380 17 0.0017 0.0028

25 75 17 --- --- 0.0042

25 75 17 --- --- 0.0044

25 75 17 --- --- 0.0044

25 75 17 --- --- 0.0040

468
III. 4. 3. Silicon Carbide Powder

Lab lEA Method

# Vial # Code

10 46 1

16 79 1

16 80 1

6 102 2

15 65 2

17 132 2

20 88 2

20 89 2

21 2 2

21 2 2

21 2 2

22 169 2

22 169 2

22 169 2

22 169 2

22 172 2

22 172 2

22 172 2

22 172 2

8 262 5 8 263 5

1 238 7

10 1025 12

25 54 17

25 54 17

25 54 17

25 54 17

25 54 17

25 54 17

18 91 21

Al Ca Fe

% % %

u AU AA1 1

(J . UzbU U . UUoz AU

A A 1

~7

. 001/

U . UZDU U AA^ O AL) AA1 C

. UUio

0 .0262 0 .0099 0 .0038

0 .0333 0 .0079 0 .0049

u U

A A "7 A

0 .0190 0 .1200 0 .0600

0 .1000 0 .1500 0 .1900

0 .0440 0 .0060 0 .0014

0 .0470 0,.0058 0 .0014

0 .0460 0,.0061 0 .0014

0 .0640 0,.0130 0 .0100

ou . U j'+U n

u

,

. uuzu Au

,

, U 1 iU

n . U'+OU Au

,

, nouz 7n/ u

Au

,

n , UZ'+VJ u

.

m on Au

,

. UU / u

nu

,

, u jdu nU , Au

,

, U i jU

nu ,. U O D U , UU lU Au

,

. U 1 jU

0.,0260 0,,0190 0.,0040

0.,0660 0,,0200 0.,0100

0,,0050 0.,0040

0,,0040 0. 0060

0.,0100 0. 0100

0. 0260 0. 0020 0. 0140

0. 0451 0. 0075 0. 0027

0. 0415 0. 0082 0. 0025

0. 0436 0. 0072 0. 0028

0. 0464 0. 0088 0. 0030

0. 0432 0. 0076 0. 0034

0. 0420 0. 0078 0. 0016

0. 2600 0. 1900

469
III. 4. 4. Silicon Powder

Lab lEA

Vial #

Method

Code

C

%

N

%

Al Fe

%

1

16

16

18

19

19

19

19

19

19

19

19

19

167

28

31

37

227

228

229

230

231

232

233

234

1005

1

1

1

1

1

1

1

1

1

1

1

1

1

0.006

0.025

0.025

0.030

0.025

0.025

0.021

0.024

0.021

0.027

0.028

0.025

0.024

0.045

0.038

0.038

0.050

0.043

0.042

0.042

0.044

0.042

0.047

0.043

0.042

0.043

5

5

5

5

6

7

7

7

7

15

17

20

20

22

22

22

22

22

22

22

22

20

20

51

51

80

162

163

163

164

11

220

33

34

99

99

99

99

100

100

100

100

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

0.570

0.570

0.017

0.017

0.016

0.017

0.035

0.033

0.032

0.040

0.024

0.028

0.031

0.030

0.032

0.013

0.028

0.029

0.027

0.029

0.030

0.036

0.036

0.034

0.034

0.046

0.049

0.047

0.040

0.040

0.040

0.042

0.052

0.054

0.052

0.050

0.054

0.050

0.054

0.053

8

8

204

205

5

5

0.015

0.015

8

8

23

236

235

45

6

6

6

1.820

1.570

0.630

470
Silicon Powder

Lab lEA Method c N 0 Al

# Vial # Code % % % %

23 46 6 — — 0 650

23 49 6 - - - - 0 650 - - - 23 50 6 - - — 0 650 - - - 23 1019 6 - — - — 0 660 — - 23 1020 6 - - - — 0 560

23 1021 6 ~ ~ — 0 690 ~ —

23 1025 6 0 610 ~ ~ ~

1 167 7 • " ~ " . 0 . 020

1 165 8 0 080 ~ ~ ~

1 165 8 0 080 ~ ~ " — "

2 16 8 0 510 — — —

2 66 8 ~ ~ 0 510

3 6 8 ~ ~ 0 060 0 543 ~ ~ ~

3 7 8 0 060 0 540 ~ ~ ~

3 19 8 0 070 0 552

3 60 8 0 070 0 556 ~ — ~

5 52 8

- — — 0 490 ~ "* ~

5 52 8 " ~ 0 500 ~ ~ ~

5 52 8 0 057 ~ ~ ~

5 52 8 0 055 ~ ~

5 53 8 0 053

5 53 8 0 050 ~ ~ ~

5 53 8 " ~ 0 550 ~ ~ ~

5 53 8

~ ~ ~ 0 490 " ~

6 79 8 0 080 0 010 0 480 " ~ ~

6 79 8 0 080 0 010 0 550

6 79 8 0 080 0 010 0 470 — — —

6 79 8 . . . 0 020 0 490 ~ ~ ""

7 160 8 0 076 * ~ ~ — ~ ~

7 160 8 0 078 — — ~ ~ ~

8 206 8 0 015

8 207 8 0 028

15 11 8 0 050 0 060 0 540

16 29 8 0 084

16 29 8 0 117

16 29 8 0 095

16 29 8 0 088

16 29 8 0 127

16 29 8 0 087

16 29 8 0 096

Fe

%

0.030

471
Silicon Powder

Lab lEA Method C N 0 Al Fe

# Vial # Code % % % % %

16 29 8 0.089

16 29 8 0.091

16 74 8 --- --- 0.516

16 74 8 --- --- 0.534

16 74 8 --- --- 0.548

16 74 8 --- --- 0.529

16 74 8 --- --- 0.549

18 37 8 0.210 0.010 0.490

22 99 8 0.069

22 99 8 0.071

22 99 8 0.072

22 99 8 --- --- 0.520

22 99 8 --- --- 0.520

22 100 8 0.069

22 100 8 0.069

22 100 8 0.071

22 100 8 --- --- 0.520

22 100 8 --- --- 0.510

3 6 16 0.060

3 7 16 0.063

3 19 16 0.058

3 60 16 0.062

3 6 17 --- --- --- 0.043 0.044

3 7 17 --- --- --- 0.042 0.050

3 19 17 --- --- --- 0.042 0.063

3 60 17 --- --- --- 0.044 0.043

472
III. 4. 5. Yttria-Zirconia Powder

Lab lEA Method Al Si Ca Ti

# Vial # Code % % % %

1 /l 1ibo i u . U Jj U . Ui4 A

U

AO/,

. Uz4

1 /l /i n7 1 u . U J (3 A

U . Um-U Au

not;

. Uz J

1 ft 1 O i u . U-JZ A

U . UiZ

1 ft io O JM- i u no . UZD A

U

18 0R012 1

_ _ _ 0 .033 0 .014 _ _ _ 19 31 1 0 .070 0 ,010 0 .010 0 .060

1 Q ft 0 i U . u / u U , UiU A

u . U lU AU . UbU

1 Q / Z'+ 1 nu . u / u

riU ,, UiU Au

,

. U±U AU ,. U jU

19 297 1 0 .080 0,,010 0,.010 0,,050

19 396 1 0 .070 0,,010 0,.010 0,,050

19 428 1 0,.070 0,,010 0,.010 0,,040

19 582 1 0,.070 0,,010 0,.010 0,,060

U(_<U L -J X nu ,. U / U nu

,

, U lU nu

,

. U LU Au

.

, UM-U

1 629 2 0,,040 0,.006 0.,026

1 659 2 0,.050 0.,007 0,.028

u i!4.n3 z.9 n u . n

D

^; o oz u

.

. Uo

D

u

,

15 314 2 0,.052 0..011 0,.024

17 5924 2 0..260 0,,010 0..020

8 117 5 0.,017 0.,002

8 372 5 0.,003 0.,002

8 395 5 0.,050 0.,007

2 73 6 0.,046 0. 027 0. 026

24 AF017 12 0. 042 0. 023 0. 025

24 0F018 12 0. 042 0. 023 0. 026

24 0V018 12 0. 042 0. 022 0. 025

14 559 17 0. 048 0. 025

17 5925 17 0. 250 0. 010 0. 020

Fe

%

0.150

0.120

0.130

0.010

0.010

0.010

0.010

0.010

0.010

0.010

0.010

0.003

0.004

0.002

0.005

0.020

0.100

0.060

0.100

0.014

0.015

0.014

0.003

0.030

473
Table III. 5 Data Tables for Minor Nonmetallic and Metallic Impurities

III. 5.1. Silicon Nitride Reference Powder

Lab

#

14

14

16

16

16

16

16

16

24

24

24

lEA

Vial //

103

593

717

717

1667

1667

1747

1747

244

1182

9005

Method

Code

1

1

1

1

1

1

1

1

1

1

1

S

%

CI

%

Na

%

0.0021

0.0024

0.0040

0.0070

0.0010

0.0020

0.0010

0.0020

Mg

%

0.0080

0.0082

0.0070

0.0070

0.0060

0.0060

0.0060

0.0070

0.0360

0.0240

0.0200

1

1

5

6

6

7

7

7

7

7

7

13

13

13

13

13

13

13

13

13

13

13

15

20

22

22

22

22

1358

1358

1309

1640

1677

683

683

1235

1235

1235

1235

56

253

375

400

624

1016

1113

1281

1315

1880

9012

965

1394

898

898

898

898

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

2

0.0040

0.0323 0.0047

0.0600

0.0300

0.0012

0.0002

0.0060

0.0060

0.0063

nd

0.0065

0.0080

0.0080

0.0073

0.0075

0.0075

0.0075

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0200

0.0100

0.0100

0.0100

0.0071

0.0002

0.0030

0.0030

0.0030

0.0040

474
Silicon Nitride Reference Powder

Lab lEA Method S CI Na Mg

# Vial # Code % % % %

6 1640 3 --- 0.0004

6 1677 3 --- 0.0065

7 1681 7 --- --- 0.0008 0.0080

22 898 7 --- 0.0063

22 898 7 --- 0.0046

23 1744 7 --- --- --- 0.0100

17 875 8 0.0110

14 593 17 --- --- 0.0031 0.0074

17 643 17 --- --- --- 0.0070

17 875 17 --- --- --- 0.0070

25 1869 17 --- --- --- 0.0075

24 25 20 --- --- 0.0100

24 638 20 --- 0.0100

475
Silicon Nitride Reference Powder

Lab lEA Method K Ti Cr Mn

# Vial # Code % % % %

14 103 1 --- 0.0015

16 717 1 --- --- --- 0.0005

16 717 1 --- --- --- 0.0008

16 1667 1 --- --- 0.0005

16 1667 1 --- --- --- 0.0006

16 1747 1 --- --- --- 0.0007

16 1747 1 --- --- --- 0.0007

6 1640 2 --- nd nd nd

6 1677 2 --- --- --- nd

7 683 2 --- 0.0030

7 683 2 --- 0.0030 --- ---

7 1235 2 --- 0.0029

7 1235 2 --- 0.0029

7 1235 2 --- 0.0029

7 1235 2 --- 0.0028

15 965 2 --- 0.0030 0.0003 0.0007

18 885 2 --- 0.0500

19 1171 2 --- --- --- 0.0006

7 1681 7 --- 0.0030 --- 0.0020

25 188 17 --- 0.0030

24 25 20 0.0100

476
Silicon Nitride Reference Powder

Lab lEA Method Ni W B

# Vial # Code % % %

23 1744 1 --- --- 0.0020

24 244 1 0.0100

24 1182 1 nd

1 1358 2 --- --- 0.0100

1 1358 2 --- --- 0.0200

6 1677 2 nd

15 965 2 --- --- 0.0004

19 1171 2 0.0003

20 1394 2 0.0005

7 1681 7 --- --- 0.0010

17 643 17 --- 0.0050

477
III. 5. 2. Silicon Nitride Test Powder

Lab lEA

Vial //

Method

Code

CI Na

%

Mg

14

14

24

24

6

15

17

20

1108

1380

598

598

1426

381

304

252

1

1

1

1

2

2

2

2

0.0080

0.0080

0.0119

0.0002

0.0010

0.0010

0.0130

0.0090

0.0002

0.0083

0.0014

25

25

25

25

25

25

1060

1060

1060

1060

1060

1060

3

3

3

3

3

3

0.0094

0.0088

0.0082

0.0082

0.0094

0.0082

8

8

171

1360

5

5

0.0005

0.0001 0.0003

0.0001

0.0001

428 0.0080

22

22

22

786

1154

1154

7

7

7

0.0075

0.0056

0.0074

5

5

5

5

21

21

441

441

1235

1235

1385

1385

13

13

13

13

13

13

0.0076

0.0072

0.0069

0.0072

0.0102

0.0100

14 1108 17 0.0004

24

24

742

742

20

20

nd

nd

478
Silicon Nitride Test Powder

Lab lEA Method K Ti Cr Mn

# Vial # Code % % % %

14 1108 1 0.0022

14 1380 1 0.0020

16 994 1 --- --- --- 0.0003

15 381 2 --- --- 0.0005 0.0000

17 304 2 --- 0.0149

18 1480 2 --- 0.0300

19 101 2 --- --- --- 0.0001

19 217 2 --- --- --- 0.0000

19 621 2 --- --- --- 0.0001

19 959 2 --- --- --- 0.0000

19 1061 2 --- --- --- 0.0000

19 1324 2 --- --- --- 0.0000

19 1470 2 --- --- --- 0.0001

8 171 5 0.0002 --- 0.0003

8 1328 5 0.0002 --- 0.0002

8 1360 5 0.0002 0.0001 0.0003

2 428 6 --- --- 0.0006 0.0000

479
Silicon Nitride Test Powder

Lab lEA Method Ni W B

# Vial # Code % % %

24 598 1 0.0280

24 598 1 nd

15 381 2 0.0004 --- 0.0002

19 101 2 0.0006

19 217 2 0.0006

19 621 2 0.0006

19 959 2 0.0005

19 1061 2 0.0005

19 1324 2 0.0005 --- ---

19 1470 2 0.0006

20 252 2 0.0005

8 171 5 0.0001

8 1328 5 0.0001

8 1360 5 0.0004

7 433 7 0.0005

480
III. 5. 3. Silicon Carbide Powder

Lab lEA Method S CI Na Mg

# Vial # Code % % % %

10 46 1 --- --- --- 0.0016

16 79 1 --- --- --- 0.0002

16 80 1 --- --- --- 0.0002

16 87 1 --- --- 0.0008

6 102 2 0.0044 --- 0.0011

15 65 2 --- --- 0.0024 0.0003

20 88 2 --- --- 0.6000 0.0170

20 89 2 --- --- 0.3000 0.0110

6 102 3 --- 0.0241

8 262 5 --- --- --- 0.0010

21 1011 13 --- 0.0055

21 1011 13 --- 0.0049

21 1011 13 --- 0.0050

25 55 14

25 54 17 --- --- --- 0.0003

25 54 17 --- --- --- 0.0003

25 54 17 --- --- --- 0.0004

25 54 17 --- --- --- 0.0001

481
Silicon Carbide Powder

Lab lEA Method K Ti Cr Mn

# Vial if Code % % % %

16 87 1 0.0003

6 102 2 --- 0.0047

15 65 2 --- 0.0043 0.0023 0.0001

20 88 2 --- 0.0010

20 89 2 --- 0.0010

10 1025 12 --- 0.0060

25 54 17 --- 0.0035

25 54 17 --- 0.0037

25 54 17 --- 0.0042

25 54 17 --- 0.0044 -- - . 25 54 17 --- 0.0038

25 54 17 --- 0.0032

482
Silicon Carbide Powder

Lab lEA Method

# Vial # Code

15 65 2

20 88 2

20 89 2

21 2 2

21 2 2

21 2 2

Ni W B

% % %

0.0005 --- 0.0005

0.0050

0.0050

0.0005

0.0006

0.0006

483
III. 5. 4. Silicon Powder

Lab lEA

Vial #

Method

Code

S

%

F

%

CI

%

Na

%

1

16

167

28

1

1

0.0010

0.0012

6

15

20

20

80

11

33

34

2

2

2

2

0.0005

0.0012

0.0008

0.0013

80 0.0210

80 0.004

5

5

5

5

52

52

53

53

13

13

13

13

0.002

0.002

0.002

0.002

0.0037

0.0046

0.0043

0.0033

484
Silicon Powder

Lab lEA

Vial #

Method

Code

Mg K

%

Ti Cr

%

1

16

16

19

19

19

19

19

19

19

19

19

167

28

31

227

228

229

230

231

232

233

234

1005

1

1

1

1

1

1

1

1

1

1

1

1

0.0020

0.0030

0.0030

0.0032

0.0027

0.0022

0.0028

0.0020

0.0027

0.0031

0.0025

0.0024

0.0100

0.0007

0.0005

0.0007

0.0007

0.0007

0.0008

0.0007

0.0007

0.0006

0.0006

0.0007

0.0002

0.0001

0.0001

0.0003

0.0003

0.0001

0.0001

0.0001

0.0002

6

7

7

15

20

20

80

162

164

11

33

34

2

2

2

2

2

2

0.0042

0.0037

0.0029

0.0074

0.0010

0.0010

0.0007

0.0007

0.0008

0.0004

8

3

3

3

3

204

6

7

19

60

5

17

17

17

17

0.0030

0.0050

0.0050

0.0050

0.0050

485
Silicon Powder

Lab lEA Method Mn Ni W B

# Vial # Code % % % %

1

16

16

19

19

19

19

19

19

19

19

19

167

28

31

227

228

229

230

231

232

233

234

1005

1

1

1

1

1

1

1

1

1

1

1

1

0.0010

0.0007

0.0007

0.0007

0.0007

0.0007

0.0007

0.0007

0.0008

0.0007

0.0007

0.0008

0.0010

0.0005

0.0003

0.0003

0.0002

0.0003

0.0005

0.0003

0.0002

0.0003

0.0010

7

7

15

20

20

162

164

11

33

34

2

2

2

2

2

0.0010

0.0010

0.0006

0.0010

0.0004

0.0005

0.0005

0.0014

486
III. 5.

5

Yttria-Zirconia Powder

Lab lEA Method Hf Sn Nd Ho

# Vial # Code % % % %

18 549 1 1.840

18 654 1 1.790

18 OR012 1 1.950

1 629 2 1.720

1 659 2 1.720

6 403 2 0.080 0.059 --- 0.025

6 630 2 --- 0.014 0.028

17 5924 2 1.770

8 117 5 0.600

8 372 5 0.600

8 395 5 0.600

22 3 12 1.840

22 3 12 1.830

22 3 12 1.830

22 75 12 1.820

22 75 12 1.820

22 75 12 1.830

17 5925 17 1.760

487
Yttria-Zirconia Powder

Lab

#

lEA

Vial //

Method

Code

Na

%

Mg K

%

Ga

%

Ba

%

14

14

19

19

19

19

19

19

19

19 0C013

24 AF017

24 0F018

24 OVOIB

166

407

31

82

224

297

396

428

582

1

1

1

1

1

1

1

1

1

1

1

1

1

0.0036

0.0039

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0080

0.0070

0.0070

0.0009

0.0011

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0100

0.0050

0.0050

0.0050

0.0050

0.0050

0.0050

1

1

6

15

17

629

659

403

314

5924

2

2

2

2

2

0.0022

0.0010

0.0010

0.0093

0.0060

0.0030

0.0058 0.0330

8

8

8

117

372

395

5

5

5

0.0100

0.0500

0.0100

14

17

73

559

5925

17

17

0.0077

0.0070

0.0020

0.0006

488
APPENDIX IV - Phase Composition

The codes identifying the quantitative analysis method are explained

in Table IV. 1.

Table IV. 1 X-ray Diffraction Codes

CODE PROCEDURE

1 Peak scan, qualitative

2 Peak scan, quantitative, single phase

3 Ratio of peak heights

4 Ratio of integrated intensities

a. Zr02: Method of Garvie and Nicholson^

5 Modified ratio equation, either peak heights or integrated

intensities

a. a,B-Si3N/,: Method of Mencik, Short and Peters^

b. a,Ji-Si3N4: calibration curve

c. a,Il-Si3N4: Method of Gazzara and Messier^

d. Zr02: Modified Garvie -Nicholson method

(1) Method of Toraya et al .

(2) Method of Schmid''

6 Least squares, matrix of intensities

a. SiC: Peak areas, Lorentzian shape assumed, 8x4 system of

coefficients equated to 8 peak areas^

7 Whole pattern methods, e.g., Rietveld refinement

489
4I

I Table IV. 2. Phase Composition Data Organized by Powders !

IV. 2.1. Silicon Nitride Reference Powder

Lab lEA Method Alpha Beta SizON

Vial # Code ( %

20 637 2 95 000 5 000

20 1394 2 95 000 5 000

22 660 2 95 000 5 000

22 667 2 95 402 4 598

22 667 2 95 434 4 566

16 505 3 92 800 7 200

16 505 3 92 900 7 100

16 505 3 92 100 7 900

16 718 3 92 000 8 000

16 718 3 92 900 7 100

16 718 3 92 500 7 500

21 9007 3 97 000 3 000

24 1669 3 93 000 7 000

2 1482 4 94 500 5 100 0.40

4 1344 4 92 000 5 000

5 230 4 93 700 6 300

5 1309 4 93 800 6 200

6 422 4 95 000 5 000

13 56 4 94 000 6 000

13 253 4 94 000 6 000

13 375 4 93 000 7 000 0.50

13 400 4 93 000 7 000

13 624 4 94 000 6 000 0.50

13 1016 4 94 000 6 000

13 1113 4 94 000 6 000

13 1281 4 94 000 6 000

13 1315 4 94 000 6 000

13 1880 4 94 000 6 000

13 9012 4 94 000 6 000 0.50

15 9013 4 94 000 6 000

25 281 4 95 700 4 300

25 289 4 95 300 4 700

25 1214 4 95 400 4 600

I

r

!

! 490

III
Silicon Nitride Reference Powder

Lab lEA

Vial #

Method

Code

Alpha

%

Beta SizON

%

23

23

499

1189

5

5

90.800

92.000

6.700

6.900

23

23

23

23

107

291

1160

1354

6

6

6

6

95.200

94.790

95.180

94.960

4.800

5.210

4.820

5.040

9

9

9

9

9

9

9

9

76

76

606

606

973

973

1475

1475

7

7

7

7

7

7

7

7

94.200

94.300

93.900

94.100

94.000

94.200

93.900

94.500

800

700

100

900

000

800

100

5.600

491
IV. 2. 2. Silicon Nitride Test Powder

Lab lEA

Vial #

Method

Code

Alpha

%

Beta SiaON

%

20

22

22

22

22

252

60

60

237

237

2

2

2

2

2

97.000

97.434

97.462

97.550

97.170

3.000

2.566

2.538

2.450

2.830

14

16

16

16

16

16

16

21

24

24

723

382

382

382

916

916

916

LSM05

1093

1321

3

3

3

3

3

3

3

3

3

3

96 . 900

94.600

95.100

94. 500

95.100

95.200

95.100

97.000

95.000

95.000

3.100

5

4

5

4

4,

4

3

5,

5,

400

900

500

900

800

900

000

000

000

2

4

4

5

5

6

15

25

80

169

675

821

1090

444

LSM09

919

4

4

4

4

4

4

4

4

97.000

95 .000

95 .000

96.700

96.400

96.000

96.000

97.500

3,

2,

2,

3,

3,

4,

,000

,000

,000

, 300

,600

,000

4.000

2.500

23

23

1351

1364

5

5

97.100

96.800

000

200

23

23

23

23

80

502

993

1813

6

6

6

6

90.510

90. 200

90.340

90.450

9

9

9

9

490

800

660

550

492
IV . 2 . 3 . Silicon Carbide Powder

Lab lEA

Vial #

Method

Code

6H

%

15R 4H 3C

4

4

6

74

75

98

5

5

5

77.3

76.5

85.0

16.4

13.8

9.0

4.0

5.5

6.0

2.3

4.2

14 53.0 35.0 11.0 1.0

1

493
IV. 2.4. Silicon

Lab lEA Method Cubic -8F

Vial # Code %

2 9 1 100.00

18 39 1 100.00

4 72 2 100.00

4 73 2 100.00

5 180 2 100.00

6 1003 2 100.00

20 33 2 100.00

20 34 2 100.00

22 97 2 100.00

22 97 2 100.00

22 98 2 100.00

22 98 2 100.00

494
IV. 2. 5. Yttria- Stabilized Zirconia Powder

Lab lEA

Vial #

Method

Code

Cubic

%

Tetra.

%

Monoc

,

%

9

9

9

22

72

289

580

43

2

2

2

2

84.40

84.40

84,90

87.92

15.60

15.60

15.10

12.08

2

14

24

24

24

599

528

AF017

0F018

OV018

3

3

3

3

3

82.00

80.00

81.00

78.00

79.00

18.00

20.00

19.00

22.00

21.00

6

15

18

18

18

18

18

18

191

OE014

259

549

OR012

OR012

OR012

OR012

4

4

4

4

4

4

4

4

90.60

83.00

79.70

80.00

79.30

80.00

77.00

75.90

9.40

17.00

20.30

20.00

20.70

20.00

23.00

24.10

495

oL'.S. GOVERNMENT PRINTING OFFICE: 1995-386-627/37929

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