NISTIR 6931 

Analysis of the ASTM Round-Robin 

Test on Particle Size Distribution of 

Portland Cement: Phase I1 

Chiara F. Ferraris 

Vincent A. Hackley 

Ana Ivelisse Ad& 

Charles E. Buchanan, Jr. 

National Institute of Standards and Technology 

Technology Administration, U.S. Department of Commerce 

NISTIR 6931 

Analysis of the ASTM Round-Robin 

Test on Particle Size Distribution of 

Portland Cement: Phase I1 

Chiara F. Ferraris 

Building and Fire Research Laboratory 

National Institute of Standards and Technology 

Vincent A. Hackley 

Materials Science and Engineering Laboratory 

National Institute of Standards and Technology 

Ana Ivelisse Avilks 

Information Technology Laboratory 

National Institute of Standards and Technology 

Charles E. Buchanan, Jr. 

Roan Industries, Inc. 

Bakersville, NC, (USA) 

December 2002 

U.S. Department of Commerce 

Donuld L. Evuns, Secretary 

Technology Administration 

Phillip J. Bond, Under Sccretui-y for Technology 

National Institute of Standards and Technology 

Arden L. Bemcnt, Jr., Director 

Abstract 

A distribution of sizes or particle size distribution (PSD) is an essential property of cement 

powder. The only standard method to measure the PSD of cement, namely ASTM C115 [ 11 is 

limited in scope; this standard only describes a method for determining “fineness” with a lower 

size detection limit of 7.5 pm. As there is no standard procedure covering the whole range of 

cement PSD, the implementation of different measurement methods varies widely within the 

industry. A first report [2] was prepared to examine the methods used in the cement industry. 

The high variability of the data led to the necessity for further research. 

ASTM committee C01.25.01 sponsored a second round-robin test to measure the PSD of cement. 

The aim of the current report is to analyze the data generated during that test and to summarize 

the various approaches available to measure the PSD of cement. The analysis of the data is 

conducted in two parts. In the first part, an attempt is made to establish a reference distribution 

using a standard cement powder (SRM 114p), improving the results already obtained from the 

first round-robin. This is followed by examination of the parameters and methodology used by 

the participants in order to initiate discussion on developing a standard test method for cement 

PSD to be submitted for ASTM consideration. The report provides all raw data collected during 

the round-robin tests, and the results of a statistical analysis of the collected data. 
Acknowledgements 

The authors would like to thank the ASTM Task Group CO1.25.01 for providing the opportunity 

for this round-robin. We would like to thank all participants of the round-robin (listed below by 

alphabetical order of the institution) for providing time and staff to perform the tests. 

Also, we would like to thank Robin Haupt and the staff of the Cement and Concrete Reference 

Laboratory (CCRL), who were instrumental in providing the samples to the round-robin 

participants. 

Participants to the Round-Robin: 

William Phillips, Arizona Portland Cement 

Kristen Freeman, Ash Grove Cement Technical Center 

Ren Xu, Beckman Coulter 

Rebecca Lara, CA. Portland Cement Co. 

Luis Velasquez, Cementos Progreso, S.A. 

Karen Ornelas, Cemex 

Ella Shkolnik, Construction Technology Labs 

Charlotte Lehmann, Dragon Products Co 

Claus- Jochen Hacker, Dyckerhoff Zement 

Thuy Ai Nguyen, Essroc Technology Center 

Bjarne Osbaeck, F.L. Smidth A/S 

Linda Lore, Florida Rock Industries 

Muller-Pfeiffer, Forschumgsinstitut der Zementindustrie 

Rita J. McKinley, Halliburton Energy Services 

Dick Roush, Holcim 

Michael Pohl, Horiba Instruments 

Robin Cowdrey, Inland Cement Limited 

Tom Griffiths, Lafarge 

Lisa McEvoy, Harvi Sodhi and Daniel Decary, Lafarge Canada 

Richard McCorkle, Lafarge North America 

Jim Davis, Lehigh Cement 

Jeffrey Hook, Lehigh Portland Cement 

Tony Nutter and Ron Rajki, Lone Star Industries 

Mike Bollinger and Henry Robinson, Lone Star Industries 

Tom Gepford, Mitsubishi Cement Corp. 

Boyd Clark, RJ Lee Group 

Tanya Cable, ROAN Laboratories Inc. 

Walter Pearce, St Marys Cement 

John Falletta, St. Lawrence Cement, Inc. 

Jesse Uribe, TXI Riverside Cement 

Miquel Latorre, Uniland Cementera, S. A. 

Vijay Gupta, W.R. Grace 

Paolo Forni, W.R. Grace Italiana 
TABLE OF CONTENTS 

1 Introduction ........................................................................................................................... 1 

2 

3 

Description of methods used in the cement industry ......................................................... 2 

Scanning Electron Microscopy (SEM) ........................................................................... 2 

Analysis of data from the round.robin ................................................................................ 4 

Reference distribution using SRM 1 14p ......................................................................... 5 

Determination of the reference distribution for laser diflraction (Approach 2) ..... 6 

2.1 

3.1 

3.1. I Methodology ............................................................................................................ 5 

3.1.2 ................................................................................................................................... 6 

................................................................................................................................... 7 

3.1.3 Determination of reference distribution using Approach I: all-inclusive .............. 9 

3.1.4 Correction procedure ............................................................................................ 10 

3.1.5 Summary ................................................................................................................ 11 

Analysis of methodologies ............................................................................................ 16 

3.2. I Laser digraction with the specimen dispersed in a liquid (US- W) ..................... 16 

3.2.1.1 Summary of the participant's procedures for sample preparation ... ......... 16 

3.2.1.2 Summary of the analysis methods ................................................... ......... 20 

3.2.2 Laser difSraction with the specimen dispersed in air (US-D) ............................. 23 

3.2.3 Electrical zone sensing ( EM .......................................................... 25 

3.2.3.1 . SEM sample preparation ............ ................. 26 

3.2.4 Summary ................................................................................................................ 27 

Recommendations and conclusions ................................................................................... 28 

4.1 Reference material ......................................................................................................... 28 

4.2 Standard method ............................................................................................................ 28 

5 References ............................................................................................................................ 29 

3.2 

4 

APPENDICES ........................................................................................... A-31 

.. .. _I_- . __ ...... -~___-___ 
LIST OF FIGURES 

Figure 1 : Graphical comparison of the Bootstrap mean curves obtained in Table 1 to Table 3 . For 

clarity. the standard deviations are not shown here. but can be found in the corresponding 

tables ........................................................................................................................................ 7 

Figure 2: Graphical comparison of the Bootstrap mean curves obtained in Table 4 to Table 6 . For 

clarity, the standard deviations are not shown here, but can be found in the corresponding 

tables ........................................................................................................................................ 9 

Figure 3: Comparison of the mean LAS and the ESZ and SEM results ....................................... 10 

Figure 4: Graphical comparison between the distributions calculated from the one calculated 

from only the LAS-W (Table 3) or LAS-D data (Table 6) . For clarity, the standard 

deviations are not shown here, but can be found in the corresponding tables ...................... 11 

Figure 5: Concentration of the dispersion in the cell for each participant . The values on top of the 

bars represent values that are off the scale selected .............................................................. 18 

Figure 6: Distribution of the ultrasonication duration for all applicable participants ................... 19 

Figure 7: Distribution of the durations of the measurement ......................................................... 20 

Figure 8: Effectiveness of the duration of the sonication as shown by the dispersion of the 

Figure 9: Distribution of the optical model used with LAS-W ..................................................... 23 

Figure 10: Distribution of measurement durations by participant ................................................ 24 

Figure 1 1 : Relationship between the D 10 and the pressure used during the measurement in LASD ............................................................................................................................................ 25 

Figure 12: Distribution of the reported optical models used with LAS-D .................................... 25 

smaller particles ..................................................................................................................... 21 
LIST OF TABLES 

Table 1 : Bootstrap data for the LAS-W by YM (without the outliers) ........................................... 6 

Table 2: Bootstrap data for the LAS-W by SPEC (without the outliers) ........................................ 7 

Table 3: Bootstrap data for the LAS-W by SPEC and YM (without the outliers) .......................... 7 

Table 4: Bootstrap data for the LAS-D for YM (without the outliers) ........................................... 8 

Table 5: Bootstrap data for the LAS-D for SPEC. No outliers were found .................................... 8 

Table 6: Bootstrap data for the LAS-D by SPEC and YM (without the outliers) ........................... 8 

Table 7: Data from EZS (A15, 1773) and SEM (Al). .................................................................... 9 

Table 8: Data from LAS-W by “your method” (YM) (see text). The results from the Bootstrap 

calculation are also shown. Data that are outside the 95 % confidence limits are shown in 

bold and data that are more than 5 % (absolute value) outside the 95 % confidence limits are 

shown in gray highlight. ........................................................................................................ 12 

Table 9: Data from LAS-W by specification (SPEC) (see text). The results from the Bootstrap 

calculation are also shown. Data that are outside the 95 % confidence limits are shown in 

bold and data that are more than 5 % (absolute value) outside the 95 % confidence limits are 

shown in gray highlight. ........................................................................................................ 13 

Table 10: Data from LAS-D for YM (see text). The results from the Bootstrap calculation are 

also shown. Data that are outside the 95 9% confidence limits are shown in bold and data that 

are more than 5 % (absolute value) outside the 95 9% confidence limits are shown in gray 

highlight. ............................................................................................................................... 14 

also shown. Data that are outside the 95 % confidence limits are shown in bold and data 

that are more than 5 % (absolute value) outside the 95 5% confidence limits are shown in 

gray highlight. ....................................................................................................................... 15 

Table 12: Medium used for dispersing the cement. Total number of participants 26 ................... 17 

Table 13: Control of solids concentration in the measurement cell. The total number of 

participants is 26 .................................................................................................................... 18 

Table 14: The ultrasonication characteristics ................................................................................ 19 

Table 15: Refractive indices used by the participants in LAS-W. If no value is shown, it signifies 

that no value was provided (not known) or used by that participant. The latter would include 

those using the Fraunhofer optical model. ............................................................................ 22 

.. 

Table 1 1 : Data from LAS-D for SPEC (see text). The results from the Bootstrap calculation are 

.. 

1 Introduction 

This report summarizes the data obtained from the second cement particle size distribution 

(PSD) round-robin tests sponsored by ASTM committee C01.25.01. The first round-robin [2] 

involved 2 1 participants, while the second round-robin (reported here) involved 4 1 participants. 

Some participants took part in both round-robins. In both tests, there were two primary themes: 

Attempt to establish a reference cement particle size distribution using a standard cement 

Identify potential methods that could be used to draft a standard method 

0 

0 

(NIST-SRM 114~) 

How to accurately measure the PSD of a cement powder is an important issue, because currently 

no standard or universally accepted method exists [3]. The cement PSD is essential for the 

complete characterization of a cement powder, as it is linked to its performance. The 

measurement of the cement PSD is rendered difficult by two main questions: 1) how to properly 

disperse the cement in a continuous medium, i.e., liquid or air; and 2) how to determine if the 

method yields the “correct” distribution (defining what is meant by “correct” is yet an additional 

issue in the context of method development and validation). Therefore, a reference material 

needs to be established, but also a methodology to disperse the cement in the medium needs to be 

drafted. 

The aim of these two ASTM-sponsored round-robins is to address these questions. The reference 

material selected was SRM 114p, currently used primarily for Blaine measurements. A correct 

PSD of this cement needed to be established, and the approach taken was to establish a 

consensus curve. This pragmatic solution was required because establishing an analytically 

“correct” PSD, with our current understanding of how cement powders are structured and with 

currently available characterization techniques, was impractical and fundamentally unsound. The 

question of how to properly disperse the cement was addressed by conducting some detailed 

experiments at NIST, and by examining common industry practices as represented by 

participants in the second round-robin. 

The two round-robins had some similarities and some differences. The same cement, SRM 114p, 

was used as a potential reference material, and various cements provided by CCRL were also 

included in the tests as was done in the first round-robin. However, the second round-robin 

requested that participants provide details describing their methodology and perform one set of 

measurements according to specified criteria with the goal of reducing user bias. 

General information and the approach to data interpretation were described in the first report [2] 

and will not be repeated here unless necessary for the understanding of the present results. It is 

the intent of the authors to prepare a peer reviewed publication that would summarize the salient 

issues and combined results derived from the two round-robin tests. 
2 Description of methods used in the cement industry’ 

During the first round-robin the following methods were determined as being used for 

characterization of cement PSD: 

1. Laser Diffraction 

a. with the specimen dispersed in liquid (suspension-based) 

b. with the specimen dispersed in air (aerosol-based) 

2. Electrical Zone Sensing (Coulter Principle) (EZS) 

3. Sedimentation 

4. Sieving 

5. Scanning Electron Microscopy (SEM) 

The second round-robin included more participants (almost doubling, from 21 to 41), but the 

number of methods was reduced because sieving and sedimentation were not used by any other 

participants. The EZS method was used by only two participants; one participant was an 

instrument manufacturer, leading to the conclusion that EZS is not widely employed in the 

cement industry. SEM, considered a research-oriented method, was used by only one participant, 

also an instrument manufacturer. 

Techniques listed above were detailed in the report prepared for the first round-robin [2], 

therefore, they will not be describe here. The only exception being the SEM method, which was 

significantly modified from the previous round-robin. 

2.1 Scanning Electron Microscopy (SEM) 

The SEM is an analytical tool that uses a focused beam of electrons to form magnified images. 

Under ideal conditions, the SEM is capable of producing images with a feature resolution at the 

nanometer m) level. In addition to image capabilities, a properly equipped SEM can 

provide information on the elemental composition of microscopic features. Information on the 

image and elemental characteristics of a sample are obtained through the interaction of the 

electron beam with the sample material, which produces various effects that can be monitored 

with suitable detectors. The resulting signals, which include secondary and backscattered 

electrons along with characteristic photoelectron X-rays, can be collected in synchronization 

with the position of the electron beam to provide detailed spatial and compositional information. 

Simply stated, secondary and backscattered electron signals provide image information, while Xrays are used to determine elemental composition (except for light elements such as C). 

The computer controlled SEM (CCSEM) can provide simultaneous measurement of individual 

particle size, shape (aspect ratio), and elemental composition by combining a scanning electron 

microscope (SEM), an X-ray analyzer (EDS), and a digital scan generator under computer 

Commercial equipment, instruments, and materials mentioned in this report are identified to foster understanding. 

Such identification does not imply recommendation or endorsement by the National Institute of Standards and 

Technology (NIST), nor does it imply that the materials or equipment identified are necessarily the best available for 

the purpose. 

I 

2 
control. Use of the computer to control the analysis permits relatively large numbers of 

individual particles to be analyzed in a time efficient manner. During the CCSEM analysis, 

fields on the samples were analyzed “in order”, Le., the particles were detected on the support 

(see section 3.2.3.1 for details on the preparation) by moving the electron beam in discrete 

increments (“x, y” pattern) across the sample and monitoring the resultant backscattered signal to 

determine when the electron beam was on a particle. The average, maximum, and minimum 

diameters were recorded during the analysis. Approximately 10 000 to 11 000 particles were 

analyzed from each sample. This included scanning the sample area at a magnification of lOOX 

for 2 500 particles greater than 10 pm. Then, 6 000 particles from 1 pm to 10 pm in average 

diameter were analyzed at a magnification of 800X and finally 2 500 particles were analyzed 

from 0.04 to 1 pm in average diameter. Details on the method can be found in several 

publications [4, 5, 61. Upon measurement of the particle size, the elemental composition of the 

particle was determined through collection of characteristic X-rays that were generated when the 

electron beam was on the particle. The elemental composition was neither requested nor is 

analyzed in this report, which is strictly related to the PSD. 
3 Analysis of data from the round-robin 

ASTM committee C01.25.01 sponsored the second phase round-robin test to measure the PSD of 

cement. The participants were asked to use the PSD technique that they routinely employ. If their 

technique was based on laser diffraction (either wet/liquid dispersion or dry /aerosol), they were 

also asked to make measurements on SRM 114p using a preset method provided by NIST. The 

data requested from the participants included the cumulative PSD of three runs on each cement. 

Also, a detailed analysis report was to be returned with the data. All data were collected 

electronically. Forty-one organizations participated with the following methods represented: 

0 Laser diffraction wet (LAS-W) 25 participants 

0 Laser diffraction dry (LAS-D) 13 participants 

EZS 2 participants 

0 SEM 1 participant 

As one organization provided two sets of data measured by LAS-W at different ultrasonication 

conditions, we really have 42 sets total including 26 sets in laser diffraction wet. The identity of 

each participant's organization remains confidential; therefore an alphanumeric code is used to 

represent participants in the data analysis. Each participant knows their individual code, but is 

unaware of the codes for the other participants. 

Two portland cements provided by CCRL were included in the tests: 143 and 144 (the numbers 

were assigned by CCRL). The characteristics of these cements, as measured in the CCRL 

proficiency program, are given in Appendix A. The standard cement, SRM 114p, was also used 

to establish a reference PSD for cement. SRM 114p is routinely used to calibrate Blaine as well 

as other surface area measurements. 

Appendix B summarizes in a tabular format all averaged PSD data received from the participants 

for CCRL cements 143 and 144. The data received for SRM 114p are shown in Table 8 to Table 

11. In the remainder of this section, the data are analyzed first to establish the reference 

distribution using SRM 114p and then to provide a detailed examination of the methods used by 

each participant. Appendices C and D provide a copy of the type of information requested. 

Three runs of the same powder sample were reported for each test material. An average curve 

was calculated using a simple arithmetic mean. Since participants may report different numbers 

of points or different size increments for the measured PSD, depending on the specific 

instrument and test parameters used, each data set was reduced to 15 sizes given in pm: 1, 1.5, 

2, 3, 4, 6, 8, 12, 16, 24, 32, 48, 64, 96, and 128. This provides a more convenient basis for 

analysis and comparison. The reduction was made by simply combining the cumulative results 

reported by the participants. For instance, if data were reported for 0.1 pm, 0.5 pm and 1 pm, the 

sum of the cumulative percentage was reported for 1 pm. 

4 
3.1 Reference distribution using SRM 1 14p 

3.1 .I Methodology 

As was done in the first round-robin analysis, results for SRM 114p were analyzed separately 

from the other cements with the objective of producing a reference material that instrument 

operators could use to "calibrate" their systems or at least to validate their methodology. In other 

words, the reference distribution of SRM 114p could be used to check that the PSD results 

obtained by a particular instrument fall within a defined margin of error, or it could be used to 

offset the measured values by a size-range-dependent factor in order to bring them within the 

acceptable margin of error. To achieve this goal, two approaches were considered: 

1. Establish a single calibration curve that represents an average distribution for all methods 

inclusive (i.e., all-inclusive approach) 

2. Establish a single calibration curve for each method, e.g., LAS-W or EZS (i.e., methodspecific approach) 

Both approaches have advantages and disadvantages. In the first approach (all-inclusive), the 

calibration curve would be less precise (greater margin of error) due to propagation of 

uncertainties as a result of variations in the precision of different methods. On the other hand, the 

first approach is simpler and more convenient because all customers would use the same 

calibration curve. In the second approach (method-specific), the calibration should be more 

precise, because variations resulting from differences in measurement principle or precision 

between different techniques would be eliminated. As a disadvantage, several calibration curves 

would have to be established independently: one curve for each method. 

There were 39 participants (93 9% of all participants) using the laser diffraction method. Of these, 

26 (62 9% of all participants) dispersed the specimen in a liquid (LAS-W) and 13 used a dry 

powder method (LAS-D). On the other hand, we had only one participant using SEM and two 

using EZS. Therefore, following the method-specific approach (Approach 2), we can determine 

only the calibration curve for LAS-W and LAS-D. Obviously, all 42 sets could be used if the allinclusive method (Approach 1) is followed, but the resulting curve would be heavily weighted by 

diffraction results. 

To determine the curve that best represents the results, outliers should not be considered in the 

calculation of the mean curve. Therefore, a key issue is elimination of outliers from the 

calculation of the reference distribution. The method that was adopted here is based on the 

calculation of the mean and the two-sided 95 9% confidence limits using the bootstrap method 

(details on the bootstrap method are given in Appendix C of ref. 123). The bootstrap method does 

not inherently provide the criteria needed to determine the outlier. Therefore, we selected the 

following criteria for elimination of outliers: if more than 27 % of the points in a data set (four 

data points) are greater than 5 % absolute value outside the confidence limits based on analysis 

of all data sets, then this data set is considered an outlier. The absolute value 5 % is defined as 

the absolute difference between the measured value and the confidence limits. Once the outliers 

are determined, the mean and 95 ?6 confidence limits are recalculated excluding the outliers. 

This mean curve would be defined as the reference curve representing SRM 1 14p. 

5 
Therefore, in the following sections, various mean curves will be calculated depending on the 

two scenarios: 

0 All data 

Data from one method 

Size 

rw1 

Mean 

High 

LOW 

3.1.2 Determination of the reference distribution for laser diffraction (Approach 

2) 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

5.0 7.9 11.1 16.3 20.5 27.9 34.1 45.8 54.7 69.7 80.4 92.6 97.1 99.4 99.9 

6.3 9.5 12.5 17.8 22.1 29.4 35.5 47.8 56.6 71.6 82.1 93.7 97.9 99.7 100.0 

3.5 6.4 9.6 14.8 19.0 26.5 32.8 43.9 52.7 68.0 78.8 91.5 96.4 99.0 99.7 

For the laser diffraction measurements, both wet and dry, two types of results were collected: 

Your method (YM): the participants were requested to use the method that they normally 

use and to describe it in detail 

Specifications (SPEC): the participants were requested to repeat the measurements using 

parameters specified by NIST (Appendix D). 

Therefore, we will examine the two sets of data separately and then in combination after 

excluding the outliers. As a result of this process, three mean bootstrap curves with 95 % 

confidence limits will be provided each for LAS-W and LAS-D. The issue is to decide which of 

these three distributions should be used as a reference for LAS-W and LAS-D. As shown in 

Figure 1 and Figure 2, the differences between the three distributions are not very large, and the 

combined distribution uses the largest number of data sets. Therefore, it could be argued that the 

combined PSD should be used as the reference curve. In this report, the combined distribution 

will be used to calculate the correction factors for the CCRL cements. 

3.1.2.1 US-W 

The calculated bootstrap mean and 95 % confidence limits are shown in Table 8 for YM and in 

Table 9 for SPEC. Using the same criteria described in Section 3.1.1, the outliers are identified 

as 

0 

A1 1 S, A20 206,450,605 and 125 1 W for YM. 

A1 lS, A20, V6,206,450, 1483, and 2021 for SPEC 

The bootstrap mean is then calculated without using the outliers. These results are shown in 

Table 1 for YM and Table 2 for SPEC. If all results obtained with LAS-W (i.e., both YM and 

SPEC) but excluding the outliers, are included, then the distribution is as shown in Table 3. A 

graphical comparison of the three distributions is given in Figure 1. 
Size 

[Pml 

Mean 

High 

LOW 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

6.0 9.5 13.7 19.0 23.4 30.7 37.3 49.0 58.0 72.5 83.4 94.3 98.3 99.7 100.0 

8.3 12.1 15.9 21.3 25.7 33.3 39.7 52.1 61.2 75.1 85.3 95.5 98.9 99.9 100.0 

3.9 7.2 11.6 16.7 21.1 28.3 34.9 45.7 55.0 69.8 81.3 93.0 97.5 99.5 99.9 

100 

90 

80 

70 

$ 60 

% 50 

40 

=I 30 

0 

20 

10 

0 

CI 

.- 

- 

- 

Size 

[CLmI 

Mean 

High 

LOW 

1 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

5.4 8.7 12.2 17.5 21.8 29.1 35.5 47.2 56.2 71.0 81.7 93.4 97.6 99.6 99.9 

6.7 10.0 13.5 19.0 23.2 30.6 37.0 49.1 57.9 72.6 83.1 94.2 98.1 99.8 100.0 

4.2 7.2 10.9 16.2 20.4 27.7 34.1 45.4 54.2 69.5 80.3 92.5 97.1 99.3 99.8 

10 100 

Size bm] 

Figure 1: Graphical comparison of the Bootstrap mean curves obtained in Table 1 to Table 

3. For clarity, the standard deviations are not shown here, but can be found in the 

corresponding tables. 

3.1.2.2 U S - D 

The calculated bootstrap mean and 95 % confidence limits are shown in Table 4 for YM and in 

Table 5 for SPEC. Using the same criteria described in Section 3.1.1, the outliers are identified 

as 

0 

0 no outliers for SPEC 

A1 ID and A7 for YM. 
The bootstrap mean is then calculated without using the outliers. This is shown in Table 4 for 

YM and in Table 5 for SPEC. If all results obtained with LAS-D (Le., both YM and SPEC) 

excluding the outliers, are included, the distribution is as shown in Table 6. A graphical 

comparison of the three distributions is given in Figure 2. 

Size 

[WI 

Mean 

High 

LOW 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

5.0 7.9 12.3 18.1 23.0 30.9 37.1 47.3 55.3 68.9 78.8 90.7 95.9 98.7 99.1 

7.3 10.9 14.5 20.6 26.0 34.4 40.5 50.7 58.4 71.6 81.2 92.6 97.5 99.7 99.9 

2.7 4.5 10.2 15.5 20.2 27.6 33.9 44.0 52.2 65.9 76.4 88.7 94.2 97.5 97.9 

Size 

[Wl 

Mean 

High 

LOW 

Table 6: Bootstrap data for the LAS-D by SPEC and YM (without the outliers) 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

4.4 6.7 11.9 17.2 21.5 28.7 34.7 45.3 53.7 67.9 78.6 91.5 96.7 99.5 99.9 

6.2 9.2 13.3 19.3 23.6 30.8 36.7 47.3 55.4 69.3 79.7 92.7 97.7 99.8 100.0 

2.6 3.9 10.3 15.4 19.3 26.0 32.1 43.2 52.0 66.7 77.6 90.4 95.9 99.2 99.8 

Size 

[WI 

Mean 

High 

LOW 

8 

1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 

4.7 7.3 12.1 17.7 22.3 29.9 35.9 46.4 54.6 68.4 78.7 91.1 96.3 99.1 99.5 

6.1 9.5 13.4 19.3 24.2 32.0 38.1 48.4 56.7 70.1 80.2 92.2 97.3 99.6 100.0 

3.3 5.4 10.6 16.1 20.3 27.8 33.9 44.4 52.8 66.9 77.3 89.9 95.3 98.3 98.8 
100 

90 

80 

E 70 

g 60 

- %50 

40 

3 30 

0 

20 

10 

0 

- 

.- 

I 

~ 

+YM 

+SPEC P 

A15 

1773 

A1 

0.4 5.1 13.7 21.1 34.5 47.8 74.3 100 100 100 100 100 

0 0.3 0.6 1.5 2.9 6.2 10.1 18.8 28.4 48 63 82.6 90.3 100 100 

1.4 3.7 6.9 13.8 19.9 34.5 45.9 64.2 75.4 89.6 96.9 100 100 100 100 

1 10 100 

Size [mm] 

Figure 2: Graphical comparison of the Bootstrap mean curves obtained in Table 4 to Table 

6. For clarity, the standard deviations are not shown here, but can be found in the 

corresponding tables 

3.1.3 Determination of reference distribution using Approach 1 : all-inclusive 

Two other methods were used in this round-robin: EZS and SEM. As the data from LAS-W and 

LAS-D are already shown in previous tables and Sections, Table 7 will show only the data from 

the three participants using EZS and SEM. No mean could be calculated from these few tests. 

Also, if an overall mean using all methods (including LAS-W and LAS-D) was calculated, it 

could be argued that it is skewed toward the results obtained by the laser diffraction methods. As 

we cannot claim that the real PSD is the mean obtained using the laser diffraction methods, it is 

not statistically valid to calculate an overall mean PSD for all techniques. For information 

purpose only Figure 3 shows the data from ESZ and SEM compared with the mean value 

obtained by laser diffraction. 

Table 7: Data from EZS (A15,1773) and SEM (Al). 

Size1 1 1.5 2 3 4 6 8 12 16 24 32 48 64 96 128 3 
100 

90 

80 

70 8 

9) 60 

- %50 

- E’ 40 

0 30 

20 

10 

0 

- 

Y 

.- > 

=I 

1 10 

Size [pm] 

100 

Figure 3: Comparison of the mean LAS and the ESZ and SEM results 

3.1.4 Correction procedure 

The purpose of a reference PSD based on an easily accessible reference material is twofold: 1) to 

verify the efficacy of the instrument or method being used, and 2) to correct measurement results 

by applying a set of correction factors. A methodology using the mean PSD curve to correct 

measured data obtained using various instruments would work in the following manner: 

0 Calculate the correction factor for each size, defined as the ratio between the measured value 

and the mean value as shown in Table 3 or Table 6. The selection of the table depends on the 

method used. 

0 Multiply all measured data for unknown samples by this correction factor. 

This procedure was applied to the two cements (CCRL #143 and 144) used in this study, for all 

available data sets. In Appendix E, the corrected data and the correction factors are shown using 

the method-specific reference curve (Approach 2). 

The ASTM committee was hoping that a single method and reference PSD could be used to 

correct all measurements. Unfortunately, in practice this proved more complicated. If the target 

measurement results themselves (not the calibration curve) contain outliers, (Le., data points that 

are more than 5 96 absolute value outside the confidence limits obtained with the bootstrap 

method), the correction is not sufficient to bring the entire curve within the confidence limits of 

the calibration curve. This can be seen in Appendix E. On the other hand, if the data set lies 

completely within the confidence limits defined by the reference curve, the correction factor will 

reduce the spread of the data. Therefore, the reference SRM 114p could be used in two ways: 

To check that measurements are within the confidence limit range of the reference. This will 

allow the operator to determine if sample preparation problems or a malfunctioning 

instrument should be considered (Le., as a validation method). 

10 
To calibrate the instrument by correcting the results obtained using the reference cement, 

after the method has been validated. 

3.1.5 Summary 

Two approaches to determine the reference distribution for cement were examined. In Approach 

1 all available data, without consideration of the measurement method, were included. In 

Approach 2, only the data generated with the LAS-W or LAS-D method were used. Only in 

Approach 2 could mean PSDs be generated using either LAS-W or LAS-D, and these mean 

distributions are shown in Figure 4. Though both curves appear to follow the same general form, 

there is some significant scatter apparent. The decision that needs to be made is which curve 

should be considered for assignment to a reference material. A discussion at the ASTM 

committee level could yield a consensus answer, but the authors propose that all available data 

(excluding outliers), from both Phase I and Phase II round-robins, should be included in the 

assignment of a reference curve for 114P. Two curves should be provided: 1) LAS-W, 2) LASD. An all inclusive curve (covering all techniques) would not be statistically correct due to the 

lack of data on methods not based on laser diffraction. 

100 

90 

80 

70 

60 

50 

40 

30 

20 

10 

0 

1 10 100 

Size [Fm] 

Figure 4: Graphical comparison between the distributions calculated from the one 

calculated from only the LAS-W (Table 3) or LAS-D data (Table 6). For clarity, the 

standard deviations are not shown here, but can be found in the corresponding tables. 

11 
rd 

m 

W 

03 

m 


s 

m 

W 

W 

2 

00 

f 

3 

2 
3.2 Analysis of methodologies 

The scope of this round robin was also to compare the specimen preparation and measurement 

parameters used by industry for each method. To facilitate this comparison, participants were 

asked to provide specific detailed information about their in-house methods. A list of the 

requested information can be found in Appendix C. In this section we will examine the methods 

used and see if it is possible to determine a “best practice” that could eventually be presented to 

ASTM for approval as part of a standard test method. Since measurement parameters and sample 

preparation can be method-specific, each method will be examined separately. 

3.2.1 Laser diffraction with the specimen dispersed in a liquid (LAS-W) 

Participant-provided information concerning in-house methodology is divided into two areas: 

sample preparation and analysis. It is important to examine the responses with two goals in mind: 

1) can a consensus procedure or procedures be established; 2) can we identify key parameters 

that affect the results? Towards the first goal, an examination of the procedures used to obtain 

the outliers or the “best” distribution (defined as the closest to the mean bootstrap value; see 

Section 3.1) will provide a clue as to the best or consensus procedure. In the second case, a 

statistical analysis of the response information for specific procedures or parameters should help 

identify important aspects that need to be controlled or investigated more closely. 

3.2.1.1 Summary of the participant’s procedures for sample preparation 

In the area of sample preparation, the following key information was requested where 

appropriate: 

0 Dispersion medium 

0 

0 Surfactant 

0 

Concentration used and how dilution was achieved 

Type and duration of ultrasonic treatment 

Each of these issues should be clearly defined when a standard test is proposed to ASTM. 

Table 12 shows a comparison of the reported medium used for dispersion of the cement powder 

in a liquid prior to and during analysis. Over 50 % of the participants used isopropyl alcohol 

(PA). There were only two participants who used a non-alcoholic medium (Le., water-based). 

One of the participants (#206) used water with no added surfactant and no ultrasonication. 

Participant #450 used water, with no added surfactant, but ultrasonication of 20 W for 60 s. 

Previously (see Section 3.1.2), results #206 and #450 were both identified as outliers by the 

statistical analysis. Given the propensity for reaction of cement powder with water, this is not a 

unexpected result. It is possible that the PSD could change during the course of the measurement 

due to the hydration of cement, or that the reactive cement particles cling to the optical cell walls 

and thereby influence the precision and accuracy of the results. 

16 
Medium Number of Percentage of 

Ethanol a 31 

IPA 14 54 

Methanol 2 8 

Water 2 8 

participants total [%I 

Examination of the correlation between the type of medium used and whether the data set is an 

outlier shows that: 

0 

0 

Data sets which used water are outliers. 

On the outlier list, there are three tests performed using IPA and one using ethanol. 

From these observations, it could be inferred that water is not a suitable medium as those sets 

underestimate the finest fraction. Between ethanol and PA the number of outliers is proportional 

to the number of participants using those mediums. Therefore, no conclusions could be drawn on 

whether one of the alcohols was better than the another. 

The second issue concerns the concentration of cement in the measuring cell and the dispersion 

method. This information is paramount because it can affect the capability to correctly disperse 

the cement and, therefore, could lead to a bias or increased variability in the measurements. It is 

clear from Table 13 that the vast majority of participants prepared their cement powder 

suspensions in one step (Le., without dilution from a stock concentrate). In some cases a known 

amount of cement was added, while in other cases the addition amount was varied to achieve a 

certain optical obscuration level in the cell. The optimal percentage obscuration range was 

predetermined by the manufacturer of the device. As can be seen in Figure 5, the concentration 

varies widely and is reported explicitly by only 12 participants out of 26 who used liquid 

dispersion. It could be concluded from these results that the most common practice is to adjust 

concentration based on obscuration. It might therefore be difficult to prescribe a fixed solids 

concentration for a standard test method, since different instruments may require different 

obscuration levels. An alternative route would be to specify the solids content for a stock 

concentrate, which would be used to control sample dispersion properties. The stock could then 

be diluted as needed to obtain the optimal obscuration level for a particular instrument. Existing 

standards outside the U.S. should also be closely examined to determine the best method. 

Only one participant (#736) used a surfactant during sample preparation. The medium used in 

this case was ethanol and the surfactant was SrC12 at a dose of O.O6g/L. No conclusions can be 

drawn from this lone test. 
Table 13: Control of solids concentration in the measurement cell. The total number of 

participants is 26. 

I Dilution from I Number of Percentage 3 

I Stock I participants of total [%I I Y/N 

c 

v) 

0 0.0020 

.- 

L 

8 0.0015 

v) 

m 

.I 

- 

3 0.0010 

0.0005 

'E 5g Y 

E 

0 0.0000 

c, 

c 

E 

0 

0 

0.087 0.02 0.78 

Participant code 

Figure 5: Concentration of the dispersion in the cell for each participant. The values on top 

of the bars represent values that are off the scale selected. 

Another factor is how the dispersion was further prepared by using ultrasonication. Analysis 

results show that 69 9% employed ultrasonic treatment to disperse cement suspensions prior to 

measurement. Of these, 63 ?6 used the on-line ultrasonication provided by the instrument, while 

the remainder used an externally applied ultrasonic treatment prior to the introduction of the 

sample to the device. One participant (V2) reported using both external and in-line 

ultrasonication. 

The power and the duration of the ultrasonication should be compared to determine the best 

procedure for an ASTM standard. Unfortunately, the power cannot be clearly compared because 

values are not always reported in fundamental units (Le. Watts versus a relative ?6 scale) nor is 

output power always clearly defined with respect to the ultrasonic geometry and sample volume. 

In some cases the frequency is reported and in others it is not. Table 14 summarizes the available 

information. On the other hand, the duration is always reported and this is shown in Figure 6. 

The values range from 10 s to 300 s, with a median value of 60 s. It does not seem that there is a 

correlation between the duration and whether the distribution contains outliers. Further studies to 
determine the impact of ultrasonic treatment duration and power output on dispersion of cement 

in alcoholic media are ongoing at NIST. Preliminary results indicate that after an initial treatment 

duration (4 20 s), further ultrasonic treatment provides no additional particle dispersion in 

alcoholic media. 

Table 14: The ultr sasonication characteristics 

E 0 350 

(P 300 0 

250 E 

200 ! 

3 ,! 150 

0 100 

E 

.- 0 50 

.- 

CI 

.- 

8 

- CI- 

.c 

w 

! 0 

n 

S 

I I 

Participant code 

Figure 6: Distribution of the ultrasonication duration for all applicable participants. 

19 
3.2.1.2 Summary of the analysis methods 

There were three specifications requested from the participants with respect to the analysis step: 

0 Duration of the measurements 

0 

Model used to interpret the results: Mie, Fraunhofer or both 

If Mie, complex refractive index used (real and imaginary) for the cement and the medium 

The duration of the measurements varied from 4 s to 120 s. This is a wide range that seems to 

depend on the particular commercial device used. Figure 7 shows the distribution of 

measurement durations obtained. It is clear that the majority of measurements last 60 s or less. 

Figure 8 shows the relationship between the sizes of the lower 10 96 (Dlo) of the particles as a 

function of the duration of the sonication. If the sonication was effective, the sizes should be 

smaller with the higher sonication. It is clear that there is no correlation. This seems to imply that 

other factors influence the dispersion of the particles. 

20 40 60 80 loo 120 

Duration of experiment [SI 

Figure 7: Distribution of the durations of the measurement. 

20 
4.0 

8 3.0 n 

Y 

0 

p’ 2.0 

1.0 

0 .o 

0 100 200 300 400 

Duration of Sonication [SI 

+ 

+ 

-*- =cL. I 1 I 

Figure 8: Effectiveness of the duration of the sonication as shown by the dispersion of the 

smaller particles. 

The refractive index is critical if the Mie optical model is used to interpret the data and obtain the 

PSD of the cement. Table 15 shows the indices used by the participants reporting Mie results. 

The selection of the real refractive index of the powder varies from 1.23 to 1.88. But if we 

exclude the single value at 1.23 (participant #A1 9), the minimum value is 1.6 and the range is 

significantly narrowed. The median value is 1.725, if 1.23 is excluded. Most participants (64 9%) 

used 0.1 for the complex refractive index of cement. Other values reported were 0.01 (27 9’0 of 

the participants) and 1.5 by a single participant (#A19). A consensus value for the real and 

complex indices would yield 1.73 and 0.1, respectively. It should be noted that participant #A19, 

while using refractive index values far from the mean, nevertheless was not determined to be an 

outlier in the statistical analysis presented in Section 3.1.2. Sources for the refractive indices 

reported by the participants were not requested and were not revealed. Since these values can 

vary with powder composition, it is an interesting observation that each participant apparently 

selected a single set of values and applied them to all cements irregardless of composition. If 

some consideration was given to the compositional variations during the selection process, it was 

not possible to determine this from the present study. The influence of variations in the real and 

imaginary components on the apparent PSD for cement is the subject of an on-going NIST 

investigation. 
Table 15: Refractive indices used by the participants in LAS-W. If no value is shown, it 

signifies that no value was provided (not known) or used by that participant. The latter 

would include those using the Fraunhofer optical model. 

Participanl 

Code 

A3 

A6 

A8 

A1 1 

A13 

A19 

A20 

v3 

v5 

V6 

98 

206 

450 

605 

61 1 

202 1 

tefractive index of powder 

Real 

1.729 

1.729 

1.729 

1.700 

1.700 

1.230 

1.725 

1.680 

1.680 

1.700 

1.810 

1.680 

1.880 

1.800 

1.729 

1.600 

Imaginary 

0.0 1 

0.0 1 

0.10 

0.10 

0.10 

1 SO 

0.01 

0.10 

0.10 

0.10 

0.10 

There are generally two optical models for interpreting angle-dependent scattering by particles: 

Fraunhofer and Mie. Only the second one requires the refractive indices to be specified. 

According to IS0 13320-1 [7], the Fraunhofer model works well for particle sizes > 50 pm. For 

particle sizes e 50pm, the Mie model is preferred if a reasonable estimate of the refractive 

indices are available. In the intermediate range from about 1 ym to 50 pm, the appropriateness of 

the choice of optical model will depend on whether the relative refractive indices (ratio of 

particle to medium) are high or low, and thus the decision is more complicated. In the 

submicrometer range, the Fraunhofer model is not applicable. The availability of different 

optical methods on a particular commercial instrument may also be a limiting factor for some 

users. Figure 9 shows the distribution of the methods as reported by the participants. It is clear 

that 80 9% of the participants use either Fraunhofer, Mie or both. It is surprising that as many as 

16 9% of the participants seem unaware of which optical model they are using to analyze their 

data. 

A standardized test method would have to account for the possibility that either the Fraunhofer 

or the Mie model might not be available to every instrument user. An ASTM standard should 

also recommend refractive indices to be used for certain types of cement, or, alternatively, a 

method for estimating these values based on the known composition of the powder. Further 

studies to establish the influence of the model choice and model parameters are underway at 

NIST. 
Figure 9: Distribution of the optical model used with LAS-W. 

3.2.2 Laser diffraction with the specimen dispersed in air (LAS-D) 

The sample preparation issue is greatly simplified in the case of LAS-D, since powders are 

introduced to the measurement device in dry form with dispersion provided internally by the 

instrument. Available aerosol dispersion methods for commercial LAS-D instruments are based 

on the use of compressed air, vacuum, or both in combination. In addition, each instrument 

company incorporates its own proprietary sample delivery and dispersion system, which might 

include, for instance, use of vibration, a venturi, or other mechanical devices. There were 13 

participants who used LAS-D: 85 96 of those used systems based on compressed air, one used a 

vacuum based system (#A14), and one used a system incorporating both compressed air and 

vacuum (#441). One should keep in mind that this information was reported by the participant, 

and is not necessarily an accurate and complete assessment of the instrument's actual 

specifications or capabilities. Reporting bias or user ignorance may therefore impact these 

numbers somewhat. Another potentially significant measurement parameter, the duration of the 

measurements as reported, varied from 4 s to 130 s. The median value was 15 s (Figure IO). 

The pressure used during the measurement when compressed air was used varied from 1 bar to 4 

bar. This is generally the maximum pressure that is available by a LAS-D. As shown in Figure 

11 there is no correlation between the diameter of the smaller fraction of the particles and 

pressure used. 
120 

100 

80 

60 

40 

20 

0 

Laboratory code 

Figure 10: Distribution of measurement durations by participant 

Like LAS-W, LAS-D requires the use of an appropriate optical model and, where appropriate, 

the selection of appropriate optical constants. Figure 12 shows the frequency in the reported 

optical model used for PSD analysis. The majority reported using the Fraunhofer model 

(=45 9%). The category “other” includes those not reporting a specific model or providing 

information that could not be clearly identified with either Fraunhofer or Mie. The variation in 

the refractive indices reported is very small for LAS-D, with only 8 participants reporting values. 

This is not surprising, as most participants employed the Fraunhofer model, which does not 

require knowledge of the optical constants for the calculations. This also is reflected that in Table 

10, where data in the lower sizes are often considered outside the 95 % confidence limits. 

In LAS-D, since the dispersing medium is air, refractive indices are needed only for the particle 

phase. All participants who reported a complex refractive index used 0.1 for the imaginary 

component. This value has also been commonly reported in the literature, but neither the exact 

origin nor its appropriateness are clearly established. Most of the reported values for the real 

component were near 1.7: 1.68 (3 participants) and 1.70 (4 participants). One participant 

reported a value of 1.0, which is clearly too low for a cement powder. Based on the typical 

composition of portland cements and the known refractive index values for the individual 

components [8], a value near 1.7 appears appropriate. Again, a procedure for selecting or 

estimating the refractive indices should be established for any standard method using laser 

diffraction. 
: 3.0 

2.5 

0 i& --- 1.5 I 

0.0 8 

0 1 2 3 4 

Pressure [bar] 

Figure 11: Relationship between the D10 and the pressure used during the measurement in 

LAS-D. 

0' 

Y 

2 40 

n 

:E 30 

n 

am 20 

C 

Q 

5 

5 10 

0 

E 

a 

=o 

I MIE Fraunhofer Both Others 

Figure 12: Distribution of the reported optical models used with LAS-D. 

3.2.3 Electrical zone sensing (EZS) and SEM 

The other two measurement methods, EZS and SEM, were used by only three participants in 

total: 

SEM: 1 participant (Al) 

EZS: 2 participants (#A15, #1773) 

Therefore, the examination of the method used for dispersing the cement will be based on the 

details provided by each participant. 

Participant #A15 reported that 1.1 g of sample was wetted with a few drops of IPA in a small 

container. Once the sample was completely wet, IPA was added to a total volume of 20 mL and 

25 
the cuvette was capped. The cuvette was then rocked by hand before being placed in an 

ultrasonic bath (125 W for 15 s). Two drops of the dispersion were added to 100 mL of 

electrolyte (2 % mSCN in PA added as an electrical conductor) with a transfer pipette. The 

concentration of the dispersion was 0.055 g/mL. The dispersion was stirred during the 

measurement using a magnetic stir bar to avoid sedimentation. A single orifice of size 0.140 mm 

was used during measurements. The measurement was completed in 60 s. 

The following information is available from participant #1773. The concentration of the 

dispersion was 0.0001 g/mL and it was prepared by dilution from a more concentrated stock 

(5.0g/mL). The medium used was PA with no additives. The stock dispersion was 

ultrasonicated, prior to dilution and introduction to the measuring device, for 5 s at an 

undetermined output power in a bath sonicator. The orifice used was smaller than 400 pm and 

the measurement lasted 120 s. 

The SEM method was used only by participant #Al. The general description of the method is 

given in Section 2.1. The sample preparation is summarized below. The type of medium used 

for dispersion was ethanol and the duration of the measurement varies depending on knowledge 

of the sample to be analyzed. It appears that it could take anywhere from 11 min to about 9 h to 

analyze the distribution by SEM. The preparation of the specimen prior to the analysis requires 

less than 10 min according to the participant #AI. 

3.2.3.1 SEA4 sample preparation 

This procedure was reported by participant #A1. The goal in preparing cement samples by the 

method described here is to obtain a representative portion of an as-received bulk powder 

sample, redeposit that portion onto a polycarbonate filter, and mount the filter onto a SEM stub 

for analysis. The procedure is divided in five steps: 

1. Preparation of the sample dispersion 

2. Redeposition of the solution onto the SEM stub 

3. Checking the particle loading on the filter 

4. Mounting the filter onto the SEM stub 

5. Carbon coating of the sample 

The sample dispersion is prepared by taking a representative portion of the as-received bulk 

sample and mixing it in a beaker with a sufficient amount of acetone. The beaker is sonicated for 

1 min to 3 min (or longer) to disperse all particles. To deposit the cement onto the SEM stub the 

following procedure is used. A polycarbonate filter, shiny side up, is placed onto the filtration 

apparatus, with a funnel placed on top of the filter to secure it. The dispersion prepared above is 

poured onto the filter apparatus and rinsed with acetone. Immediately the vacuum pump is turned 

on and the sides of the funnel are rinsed with acetone before the solution has completely filtered. 

The vacuum pump is left on to partially dry the filter. 

To determine that the particles are properly deposited, the filter is examined under a light 

microscope at lOOOX magnification. The criteria used is that there should be an even loading 

distribution, Le., particles are not touching each other, approximately 15 to 20 particles per field. 

26 
Once the filter is dry, a 20 mm (0.75 in) square piece is cut from the filter, and glued onto the 

SEM stub using colloidal graphite “dag”. After the dag is completely dry, a thin coat of carbon is 

applied by evaporative deposition. 

3.2.4 Summary 

From the analysis of the methodology reported by the participants, it is clear that most of the 

participants used a laser diffraction method, either wet or dry. Although there is a wide range of 

methods used to prepare and analyze the specimen, some tendencies could be found for each 

method. This could be used for the basis of a draft standard method, at least for one based on 

laser diffraction. 

In LAS-W, the following parameters could be established based on the results of this roundrobin: 

Medium:IPA 

0 Concentration of the dispersion determined from the obscuration value and not a fixed 

concentration, or a fixed stock concentration followed by obscuration-based dilution. 

On the other hand, a better understanding of the influence of the following parameters on the 

results should be investigated further: 

0 

0 

Refractive indices (especially the real value) 

The duration and intensity of ultrasonication 

Since there were fewer parameters to select for the LAS-D method, the standardization should be 

less complicated. It is clear that the compressed air method is the most widely used, but this 

could not be a parameter to be fixed in the ASTM procedure because it depends on the 

manufacturer and not on the user. The pressure varies somewhat but the median value could be 

selected or more studies could be made to determine the influence of the pressure on the 

dispersion of the cement particles. The results are interpreted using the same methods as for 

LAS-W, i.e., Mie or Fraunhofer or both. As the size of the smallest particles could not be 

correctly determined using Fraunhofer, the authors suggest that both models be included. As it is 

not known how the participants selected the refractive index, further research to determine 

appropriate refractive indices should be conducted. 

No clear conclusions could be drawn for the other methods due to the small number of 

participants using them. 

27 
4 Recommendations and conclusions 

This report had two goals and therefore there should be two sets of recommendations: 

A reference material 

Standard method to measure PSD of cement 

4. I Reference material 

As SRM 114p is widely used in the cement industry for calibration of the Blaine measurement, it 

is an appropriate choice to be used as a reference material for PSD determination. In this report 

and in the previous one [2], various PSDs were obtained by statistically analyzing the data 

obtained from round-robins sponsored by ASTM. To obtain a larger data set and to improve the 

statistical reliability of the results, one could conceivable combine the data from both roundrobins to establish the PSD for SRM 114p. Nevertheless, it should be kept in mind that more 

than one PSD could be established from the data. The following two PSDs could be made 

available: 1) LAS-W; 2) LAS-D. 

NIST is prepared to combine the data from the two round-robins and to incorporate the results 

into the certification for SFW 114p as informational data. This could be accomplished in early 

2003. 

The supplies of SRM 114p available at NIST will cover industry needs for about 18 months. 

Therefore, NIST is initiating the procedure for securing and characterizing the next SRM 114. 

The certificate for the new SRM 114 should also include the PSD of the cement. 

4.2 Standard method 

There are several methods used to measure the PSD of cements. From this report and from the 

previous report [2], it is clear that the majority of the cement industry uses either LAS-W or 

LAS-D. Other methods are used by a small percentage of industry only. 

In the EZS case, it should be noted that only one participant (out of 2) belonged to the cement 

industry; the other was an instrument manufacturer. This infers that the cement industry by and 

large does not use EZS in standard practice. Therefore, a standard method for EZS would not be 

widely used and would therefore be unsupportable. The third method used in this round-robin, 

SEM, is in our opinion at the research and development stage, and is also not widely used in 

industry. Development of a SEM standard method would therefore not be warranted based on 

current industry use. It would seem that the duration of the measurements and the lengthy 

preparation procedure would limit SEM use primarily to research or special projects. The 

designers of this test argue that it could also give the composition of the cement simultaneously 

with PSD, and this may be the single most important benefit of SEM in this respect. If 

compositional data were necessary, SEM might prove extremely useful. The authors believe that 

this information is not necessary for quality control at a cement plant on a daily basis. 

Therefore, there is a strong argument for ASTM committee CO1.25.01 and NIST to make an 

investment in time and effort to design a standard test method to measure the PSD of cement 

28 
powder using laser diffraction (both wet and dry). From this report, several parameters could 

already be narrowed or fixed. A small task group could conceivably help define the next set of 

specifications to be recommended for a future round-robin as part of the standards development 

process. 

I References 

“Standard Test Method for Fineness of Portland Cement by the Turbidimeter” ASTM C 

1 15-96, Annual Book of ASTM Standards, Vol. 04.01. 

Ferraris, C.F, Hackley V.A., Aviles A.I., Buchanan C.E., “Analysis of the ASTM RoundRobin Test on Particle Size Distribution of Portland Cement: Phase I” NISTIR 6883, 

May 2002. 

Jillavenkatesa A., Dapkunas S. J., Lum L.-S. H., “Particle Size Characterization,” NIST 

Special Publication 960- 1,200 1. 

A.J. Schwoeble, A.M. Dalley, B.C. Henderson, G.S. Casuccio, “Computer-Controlled 

SEM and Microimaging of Fine Particles,” J. Metals, pp. I 1 - 14, 1988. 

G.S. Casuccio, P.B. Janocko, R.J. Lee, J.F. Kelly, S.L. Dattner, J.S. Mgebroff, “The Use 

of Computer Controlled Scanning Electron Microscopy in Environmental Studies,” 

APCA Journal, 33 [IO], pp. 937-943, 1983. 

S.K. Kennedy, W. Walker, and B. Forslund, “Speciation and Characterization of Heavy 

Metal-Contaminated Soils Using Computer-Controlled Scanning Electron Microscopy,” 

in Press 2002. 

IS0 13320- 1 : 1999(E), “Particle size analysis - Laser diffraction methods -Part 1 : 

General principles”. 

Cyr, M. and Tagnit-Hamou, A., “Particle size distribution of fine powders by Laser 

diffraction spectrometry. Case of cementitious materials,” Muter Struct, 34, pp. 342-350, 

2001. 

29 

APPENDICES 

A-3 1 
A-32 
TABLE OF CONTENT 

APPENDIX A: CEMENT CHARACTERISTICS .................................................................. 35 

APPENDIX B: PSD DATA RECEIVED FOR THE CEMENTS CCRL 143 AND 144 ....... 42 

APPENDIX C: FORM RETURNED BY PARTICIPANTS ................................................... 49 

APPENDIX D: SPECIFICATION FOR THE TO TESTS SRM114P ................................... 56 

APPENDIX E-1: PARTICLE SIZE DISTRIBUTION USING ONLY DATA FROM LASER 

WET .............................................................................................................................................. 58 

APPENDIX E-2: PARTICLE SIZE DISTRIBUTION USING ONLY DATA FROM LASER 

DRY .............................................................................................................................................. 59 

A-33 

I -_ _ - 
A-34 
Appendix A: Cement characteristics’ 

CCRL PROFICIENCY SAMPLE PROGRAM 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Heat of Hydration Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average - S.D. C.V. 

Heat Solution Dry caVg 19 604.3 20.3 3.35 597.2 10.4 1.74 

Heat Solution Dry caYg * 18 599.7 3.9 0.645 599.3 5.3 0.882 

Heat Sol 7-day caVg 19 528.8 24.3 4.59 521.8 7.4 1.41 

Heat Sol 7-day caVg * 18 523.3 5.5 1.06 523.0 5.4 1.03 

Heat Sol 28-day caVg 11 502.9 40.6 8.08 499.3 45.6 9.14 

Heat Sol28-day caVg * 10 515.0 6.0 1.165 513.0 4.2 0.825 

Heat Hyd 7-day caVg 19 75.7 5.9 7.76 75.6 6.9 9.12 

Heat Hyd 28-day caVg 11 86.2 6.5 7.55 86.9 5.6 6.40 

* ELIMINATED LABS: Data over three S.D. from the mean 

Heat Solution Dry 1916 

Heat Solution 7-day 1916 

Heat Solution 28-day 557 

The policy of the National Institute of Standards and Technology is to use the International System of Units (metric units) 

on all its publications. In this appendix however, all the tables are reproduced, with permission, and as published by CCRL 

which describes measurements in certain non-SI units. 

I 

A-35 
CCRL PROFICIENCY SAMPLE PROGRAM 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Chemical Rapid Method Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S.D. C.V. 

Silicon Dioxide prcnt 1.16 20.366 0.24 1.17 

Silicon Dioxide prcnt 

Aluminum Oxide prcnt 

Aluminum Oxide prcnt 

Ferric Oxide prcnt 

Ferric Oxide prcnt 

Calcium Oxide prcnt 

Calcium Oxide prcnt 

Magnesium Oxide prcnt 

Magnesium Oxide prcnt 

Sulfur Trioxide prcnt 

Sulfur Trioxide prcnt 

176 

* 172 

184 

* 179 

183 

* 178 

177 

* 172 

185 

* 172 

172 

* 165 

21.216 

21.213 

4.472 

4.465 

3.521 

3.527 

63.78 1 

63.765 

1.689 

1.678 

2.728 

2.728 

0.25 

0.22 

0.18 

0.15 

0.07 1 

0.057 

0.65 

0.39 

0.18 

0.055 

0.13 

0.084 

1.06 

3.96 

3.35 

2.02 

1.62 

1.02 

0.6 16 

10.4 

3.28 

4.65 

3.07 

20.359 

5.306 

5.31 1 

2.354 

2.346 

64.55 1 

64.607 

0.980 

0.960 

2.998 

3.020 

0.20 

0.18 

0.12 

0.130 

0.060 

0.66 

0.45 

0.18 

0.060 

0.26 

0.104 

1 .oo 

3.35 

2.33 

5.52 

2.56 

1.02 

0.693 

18.6 

6.20 

8.66 

3.43 

CONTINUED ON REVERSE SIDE 

* ELIMINATED LABS: Data over three S.D. from the mean 

Silicon Dioxide 93 501 547 690 

Aluminum Oxide 132 142 501 504 547 

Ferric Oxide 142 360 493 501 787 

Calcium Oxide 23 56 360 547 1715 

Magnesium Oxide 

Sulfur Trioxide 56 687 121 142 692 918 1053 

36 56 116 142 360 501 134 416 557 687 1373 1715 2144 
CCRL PROFICIENCY SAMPLE PROGRAM 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Chemical Rapid Method Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S.D. C.V. 

Loss on Ignition prcnt * 126 1.522 0.103 6.79 2.151 0.093 4.33 

Loss on Ignition prcnt 13 1 1.525 0.16 10.21 2.153 0.14 6.39 

Sodium Oxide prcnt 176 0.132 0.1 1 82.0 0.131 0.16 125.4 

Sodium Oxide prcnt * 171 0.122 0.024 19.8 0.1 14 0.027 23.9 

Potassium Oxide prcnt 184 0.71 1 0.068 9.6 1 0.750 0.058 7.72 

Potassium Oxide prcnt * 175 0.722 0.021 2.95 0.760 0.026 3.37 

Manganic Oxide prcnt 8 1 0.06 1 0.19 309 0.060 0.1 1 184 

ManganicOxide prcnt * 80 0.040 0.013 32.1 0.048 0.0 14 28.5 

Phosphorus Pent prcnt 1 13 0.055 0.027 48.9 0.101 0.026 25.4 

Phosphorus Pent prcnt * 107 0.050 0.01 10 21.8 0.095 0.0096 10.0 

Titanium Dioxide prcnt 127 0.215 0.040 18.5 0.309 0.044 14.5 

Titanium Dioxide prcnt * 122 0.217 0.018 8.27 0.3 10 0.027 8.70 

* ELIMINATED LABS: Data over three S.D. from the mean 

Loss on Ignition 56 181 438 450 996 

Sodium Oxide 56 36 547 698 1373 

Potassium Oxide 56 78 106 132 116 181 360 542 2190 

Manganic Oxide 619 

Phosphorus Pentoxide 

Titanium Dioxide 124 166 181 438 502 

127 142 181 492 502 1 196 

A-37 

.. 
CCFX PROFICIENCY SAMPLE PROGRAM 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Physical Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S .D. C.V. 

N.C. Water prcnt 236 25 .OS 1.5 6.12 24.66 1.6 6.29 

N.C. Water prcnt * 234 25.18 0.42 1.67 24.77 0.42 1.68 

Vicat TS Initial min 224 121 15.3 12.6 92 18.2 19.8 

Vicat TS Initial min * 21 8 120 13.6 11.3 90 12.9 14.3 

Vicat TS Final min 220 216 33.7 15.6 173 32.2 18.6 

Vicat TS Final min "216 217 30.7 14.2 173 31.5 18.3 

Gillmore TS Initial min 176 151 22.7 15.0 122 23.8 19.4 

Gillmore TS Initial min * 173 151 21.8 14.5 121 18.7 15.5 

Gillmore TS Final min 174 245 36.7 15.0 200 34.6 17.3 

Gillmore TS Final min * 172 245 34.1 13.9 200 33.8 16.9 

False Set prcnt 193 82.1 8.1 9.85 73.0 11.3 15.5 1 

Autoclave Expan prcnt 2 19 -0.009 0.040 -446.22 0.03 1 0.063 202.90 

Autoclave Expan prcnt * 2 16 -0.007 0.022 -3 12.68 0.032 0.027 84.48 

Air Content prcnt * 217 8.49 1.1 12.5 10.83 1.2 11.4 

AC Mix Water prcnt 21 8 67.87 7.0 10.4 66.79 7.1 10.6 

AC Mix Water prcnt * 212 68.29 2.3 3.39 67.20 2.8 4.18 

AC Flow prcnt 2 17 88.0 3.6 4.04 89.3 3.3 3.70 

AC Flow prcnt * 216 88.1 3.5 3.97 89.4 3.3 3.7 1 

Air Content prcnt 2 19 8.46 1.1 13.3 10.79 1.3 12.1 

CONTINUED ON REVERSE SIDE 

* ELIMINATED LABS: Data over three S.D. from the mean 

Normal Consistency 

Vicat TS Initial 

Vicat TS Final 

Gillmore TS Initial 

Gillmore TS Final 

Autoclave Expansion 

Air Content 

Air Content Mix Water 

Air Content Flow 

201 221 

36 49 819 1190 1483 1644 

11 124 156 1190 

124 252 996 

124 270 

15 1526 1819 

360 2144 

354 127 360 1523 1956 2144 

886 
CCRL PROFICIENCY SAMPLE PROGRAM 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Physical Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S .D. C.V. 

Comp Str 3-day psi 242 3862 284.2 7.36 3608 283.7 7.86 

Comp Str 3-day psi * 238 3871 266.8 6.89 361 1 234.8 6.50 

Comp Str 7-day psi 241 4693 301.6 6.42 4456 294.7 6.61 

Comp Str 7-day psi * 239 4689 296.6 6.32 4445 27 1.9 6.12 

Comp Str 28-day psi 201 5933 391.6 6.60 55 10 360.3 6.54 

Comp Str 28-day psi * 197 5932 375.8 6.33 5499 323.6 5.88 

CS Flow prcnt 20 1 121.4 11.5 9.49 115.0 10.7 9.28 

Fineness AP cm’lg 239 3979 150.1 3.77 4122 123.7 3 .OO 

Fineness WT cm’lg 33 2237 113.5 5.08 2128 110.7 5.20 

45ym sieve prcnt 2 16 96.586 0.81 0.840 91.161 1.20 1.315 

45ym sieve prcnt * 211 96.683 0.46 0.472 91.153 0.93 1.024 

Fineness AP cm’lg * 229 3982 79.9 2.01 4123 83.5 2.02 

Fineness WT cm’lg * 32 2249 92.6 4.12 2136 101.3 4.74 

* ELIMINATED LABS: Data over three S.D. from the mean 

Comp Strength 3-day 

Comp Strength 7-day 30 1657 

Comp Strrengh 28-day 30 38 1251 1657 

Fineness Air Perm 22 23 46 49 283 431 1025 1053 1916 2144 

Fineness Wagner Turb 787 

45 pm Sieve 

14 30 152 1053 

80 207 265 886 2144 
CCRL Proficiency Sample Program 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Chemical Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S.D. C.V. 

Silicon Dioxide prcnt 156 21.137 0.25 

Silicon Dioxide prcnt * 152 

Aluminum Oxide prcnt 137 

Aluminum Oxide prcnt * 132 

'(P205 & Ti02 not included) 

Femc Oxide prcnt 149 

Ferric Oxide prcnt * 145 

Calcium Oxide prcnt 153 

Free Lime prcnt 146 

Magnesium Oxide prcnt 152 

Magnesium Oxide prcnt * 146 

Sulfur Trioxide prcnt 158 

Sulfur Trioxide prcnt * 154 

21.143 

4.5 16 

4.500 

3.533 

3.531 

63.730 

0.520 

1.690 

1.680 

2.73 1 

2.735 

0.2 1 

0.22 

0.20 

0.08 1 

0.069 

0.48 

0.17 

0.15 

0.10 

0.09 1 

0.077 

1.16 

0.995 

4.84 

4.36 

2.30 

1.96 

0.750 

32.8 

9.06 

6.1 1 

3.32 

2.82 

20.337 

20.327 

5.322 

5.324 

2.370 

2.354 

64.5 13 

1.189 

0.997 

0.966 

3.032 

3.037 

0.25 

0.22 

0.19 

0.15 

0.134 

0.050 

0.47 

0.23 

0.2 1 

0.10 

0.1 17 

0.098 

1.23 

1.077 

3.65 

2.88 

5.66 

2.13 

0.735 

19.5 

21.13 

10.73 

3.87 

3.22 

CONTINUED ON &VERSE SIDE 

* ELIMINATED LABS: Data over three S.D. from the mean 

Silicon Dioxide 116 178 492 1526 

Aluminum Oxide 98 142 413 501 1526 

Ferric Oxide 142 501 1025 1526 

Magnesium Oxide 

Sulfur Trioxide 116 121 142 918 

25 36 78 142 413 501 
CCFU Proficiency Sample Program 

Portland Cement Proficiency Samples No. 143 and No. 144 

Final Report - Chemical Results 

March 22,2002 

SUMMARY OF RESULTS 

Sample No. 143 Sample No. 144 

Test #Labs Average S.D. C.V. Average S.D. C.V. 

Loss on Ignition prcnt 186 1 SO8 0.1 1 7.15 2.142 0.1 1 5 .oo 

Loss on Ignition prcnt * 179 1.51 1 0.090 5.94 2.152 0.086 3.99 

Insoluble Residue prcnt 174 0.323 0.220 68.3 0.392 0.096 24.5 

Insoluble Residue prcnt * 168 0.294 0.076 25.9 0.389 0.088 22.8 

Sodium Oxide prcnt 129 0.123 0.038 30.5 0.1 12 0.034 30.4 

Sodium Oxide prcnt * 124 0.121 0.024 19.7 0.1 11 0.026 23.4 

Potassium Oxide prcnt 133 0.7 18 0.032 4.4 1 0.755 0.044 5.90 

Potassium Oxide prcnt * 128 0.719 0.028 3.86 0.757 0.032 4.24 

Phosphorus Pent prcnt 69 0.060 0.061 102.5 0.1 10 0.107 97.1 

Phosphorus Pent prcnt * 67 0.050 0.014 28.6 0.097 0.019 19.5 

Titanium Dioxide prcnt 79 0.2 17 0.03 1 14.5 0.345 0.326 94.6 

Titanium Dioxide prcnt * 76 0.2 18 0.0 15 7.04 0.312 0.02 1 6.61 

* ELIMINATED LABS: Data over three S.D. from the mean 

Loss on Ignition 

Insoluble Residue 36 60 93 154 694 1379 

Sodium Oxide 134 413 975 1251 1373 

Potassium Oxide 3 542 1251 78 2190 

Phosphorus Pentoxide 96 502 

Titanium Dioxide 96 166 502 

206 221 450 694 996 1936 2191 

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Appendix C: Form returned by participants 

Form to be returned with your results 

Identification: (the information in this section will be kept confidential) 

Laboratory name: 

Address: 

Contact person: Phone: 

E-mail: 

Operator: 

Date of the tests: 

METHOD USED (select one and then go to the section indicated) 

o Laser Diffraction (wet): specimen dispersed in a liquid Section A 

o Laser Diffraction (dry): specimen dispersed in air Section B 

o SEM Section C 

R Particle Counting Technique (EZS, SPOS) Section D 

o Sieve and Sedimentation Section E 

Please use the appropriate section(s) corresponding to your method. 

Return all relevant sections by March 10,2002 to: 

Clarissa Ferraris (e-mail: clarissa@nist.gov; Fax: 301-990 6891) 

AND 

Charles Buchanan (e-mail: charlesjr@roanind.corn; Fax: 828-688 5855) 

Note: The MS EXCEL spreadsheet containing all the PSD data should be e-mailed back, 

the forms can be faxed or e-mailed. 

(Assigned code: I 

A-49 
SECTION A: Laser Diffraction (wet): specimen dispersed in a liquid 

Device brand and model: 

Reference material used (if any): 

Sample preparation : 

> Medium used (circle one): Methanol Ethanol Isopropanol (IPA) 

other (specify): 

> Concentration of the dispersion: [g/mL] Diluted from more concentrated 

stock? yes no 

0 

If yes, give stock concentration [&I: 

Note: use particle density of 3.2 g/mL for calculation of solids concentration. Also 

indicate density used for medium [g/mL]: 

> Was a surfactant used? (circle one) Yes No 

if yes, please specify name and dosage: 

> Ultrasonication of sample suspension (circle one): Yes No 

If yes, please specify intensity and duration: 

> Was ultrasonic treatment performed (circle one): 

(a) inside PSD device; (b) prior to introduction into device; 

If (b) or (c), please identify type of external ultrasonicator used (circle one) 

(c) both 

bath submersible horn 

If (b) or (c), was the external ultrasonication performed on a (circle one) 

concentrate or dilute dispersion* 

*refers to a suspension at or near the solids concentration used in the actual measurement 

Test and results: 

> Complex refractive index used for powder: Real: Imaginary : 

P Refractive index (real) used for medium: 

> Model used to interpret the results: (circle one): Mie Fraunhofer Both 

> Duration of the measurement in the PSD device [sec]: 

Notes: (add any information that could be useful to better describe the procedure used): 
SECTION B: Laser Diffraction (Dry): specimen dispersed in air 

Device brand and model: 

Reference material used (if anv): 

Particle dispersion : 

k Dispersion procedure: (circle one) compressed air vacuum 

If compressed air, pressure setting used [bar] 

P Duration of the measurement in the PSD device [SI: 

Test and results: 

k Give the Refractive index used: Real: Imaginary : 

> Model used to interpret the results: (circle one): Mie Frau n hofer 

Notes: (add any information that could be useful to better describe the procedure used): 
SECTION C: Scanning Electron Microscopy (SEM) 

Device brand and model: 

Reference material used (if any): 

Sample areaaration: 

> Concentration of the dispersion: [g/mL] 

> Medium used (circle one): Methanol Ethanol Isopropanol (IPA) 

Other (specify): 

0 Note: use particle density of 3.2 g/mL for calculation of solids concentration. Also 

indicate density used for medium [g/mL]: 

> Was a surfactant used? (circle one) Yes No 

if yes, please specify name and dosage: 

> Ultrasonication of sample suspension (circle one): Yes No 

If yes, please specify intensity and duration: 

If yes, please identify type of ultrasonicator used (circle one) 

bath submersible horn 

Test and results: 

> Number of fields analyzed: 

> Number of particles measured per field: 

> Magnification used and range of related PSD: 

> Duration of the measurement in the PSD device [SI: 

> Describe the method used to interpret the results: 

Notes: (add any information that could be useful to better describe the procedure used): 
SECTION D: Particle Counting [Electrical Zone Sensing (EZS) or Single 

Particle Optical Sensing (SPOS)] 

Device brand and model: 

Reference material used (if any): 

Samule ureuaration: 

> Concentration of the dispersion [g/mL]: Diluted from more concentrated 

stock? yes no If yes, give stock concentration [gL]: 

> Medium used (circle one): Methanol Ethanol Isopropanol (IPA) 

Other (specify): 

0 Note: use particle density of 3.2 g/mL for calculation of solids concentration. Also 

indicate density used for medium [g/mL]: 

> Was a surfactant used? (circle one) Yes No 

if yes, please specify name and dosage: 

> Ultrasonication of sample suspension (circle one): Yes No 

If yes, please specify intensity and duration: 

> Was ultrasonic treatment performed (circle one): 

(a) inside PSD device; (b) prior to introduction into device; (c) both 

If (b) or (c), please identify type of external ultrasonicator used (circle one) 

bath submersible horn 

If (b) or (c), was the external ultrasonication performed on a (circle one) 

concentrate or dilute dispersion" 

"refers to a suspension at or near the concentration used in the actual measurement 

Test and results: 

> Size of the orifice(s) [mm]: 

> Duration of the measurement in the PSD device [SI: 

> Describe the method used to interpret the results: 

Notes: (add any information that could be useful to better describe the procedure used): 
SECTION E: Sieving and Sedimentation 

k Was sieving done before sedimentation? Yes No 

If yes, please, also answer questions in the section Sieving, if not proceed directly to the 

section Sedimentation 

Sieving 

Device brand and model: 

Reference material used (if any): 

> How was the cement measured (circle one): dry wet 

If wet, proceed to Part I; if dry, proceed to Part II 

PART I: Sieving of liquid-dispersed powders (wet sieving) 

Sample preparation 

> Medium used (Circle one) Methanol Ethanol Isopropanol 

(specify): 

> Concentration of the dispersion: [g/mL] 

Other 

0 Note: use particle density of 3.2 g/mL for calculation of solids concentration. Also 

indicate density used for medium [g/mL]: 

if yes please specify name and dosage 

If yes, please specify intensity and duration: 

(a) during sieving; (b) prior to sieving; (c) both 

> Was a surfactant used? Yes No, 

k Ultrasonication of sample suspension (circle one): Yes No 

> Was ultrasonic treatment performed (circle one): 

If (b) or (c), please identify type of external ultrasonicator used (circle one) 

bath submersible horn 

Test and results: 

> Type of sieving procedure used (circle one): manual 

k Number of sieves used: 

automated 

Size of the sieves used (use the ASTM El 1 designations): 

Describe the method used to interpret the results: 

PART II: Sieving of dry powders (dry sieving) 

> If applicable, describe how powder was dispersed prior to sieving: 

A-54 
> Type of sieving method used (circle one): manual automated 

> Duration of the test [sec]: 

> Number of sieves used: 

Size of the sieves used (use the ASTM El 1 designations): 

> Describe the method used to interpret the results: 

Sedimentation 

Was the Sedimentation method (circle one): gravitational or centrifugal ? 

Device brand and model: 

Reference material used (if any): 

Sample preparation: 

> Medium used (Circle one) Methanol Ethanol Isopropanol Other 

(specify): 

> Concentration of the dispersion: [g/mL] 

0 Note: use particle density of 3.2 g/mL for calculation of solids concentration. Also 

indicate density used for medium [g/mL]: 

if yes please specify name and dosage 

If yes, please specify intensity and duration: 

If yes, please identify type of ultrasonicator used (circle one) 

> Was a surfactant used? Yes No, 

> Ultrasonication of sample suspension (circle one): Yes No 

bath submersible horn 

Test and results: 

P Particle density used (g/mL): measured? yes no 

if yes, by what method? 

P Detection method used: (circle one) 

optic a1 x-ray cumulative mass 

> Duration of the measurement [sec]: 

Notes: (add any information that could be useful to better describe the procedure used): (use the 

back of the page if needed) 
APPENDIX D: Specification for the to tests SRM114p. 

SECTION A: Laser Diffraction (wet) - specimen dispersed in a liquid 

Sample preparation procedure: 

> Dispersion medium: Isopropanol (IPA) (density: 0.7855 g/mL at 20 "C) 

> & surfactants should be used for dispersion of the cement powder. 

> Use a standard Pyrex glass beaker to prepare stock suspension 

> Prepare stock concentrate at solids concentration [g/L]: 85 

Add 10 g cement powder to 90 g (1 15 mL) of IPA 

P Ultrasonicate stock concentrate prior to measurement: 

If available, use an external, submersible-horn-twe ultrasonic disruptor 

Ultrasonicate on a medium setting for 1 min duration 

Indicate make & model of ultrasonicator device: 

Indicate output power setting used [watts]: 

Place beaker with sample in bath and use the highest setting available for 5 min 

duration: 

Indicate make & model of ultrasonicator device: 

If submersible-type is not available, use an ultrasonic bath 

Test and results: 

> Run measurements at or near 20 "C. If measurement temperature deviates by more than f 2 

"C from 20 "C, then indicate temperature here: 

> Refractive index values for powder: Real: 1.70 Imaginary: 0.1 

> Refractive index value for medium: 1.378 (indicate if instrument requires that you use a 

different value for RI): 

> For measurements, use drop-wise additions of concentrate to particle-free IPA circulating 

within the measurement device until the appropriate obscuration level (Le., particle 

concentration) is obtained according to the instrument manufacturer's recommendations. 

> Indicate duration of the measurement in the PSD device [SI: 

> Use model to interpret the results (circle one): Mie Fraunhofer Both 

Note: if available, analyze data using both models separately, and provide separate sets of 

results for each. 

Notes: (add any information that could be useful to better describe the procedure used, use 

additional blank sheets if necessary): 

A-56 

_- 
SECTION B: Laser Diffraction (Dry): specimen dispersed in air 

Particle diwersion: 

> Dispersion procedure: (circle one) compressed air vacuum 

If compressed air, use manufacturer’s recommended pressure setting, and indicate here [bar] - 

Test and results: 

> Refractive index values for powder: Real: 1.70 Imaginary: 0.1 

> Use manufacturer’s recommendations for amount of powder to introduce into device, and 

use recommended values for parameters not specifically indicated here. 

> Duration of the measurement in the PSD device [SI: 

> Use model to interpret the results (circle one): Mie Fraunhofer Both 

Note: if available, analyze data using both models separately, and provide separate sets of 

results for each. 

Notes: (add any information that could be useful to better describe the procedure used): 

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