NIST Special Publication 260-161

Certification of SRM 114q: Part I

Chiara F. Ferraris

William Guthrie

Ana Ivelisse Avilés

Robin Haupt

Bruce S. MacDonald

NIST Special Publication 260-161

Certification of SRM 114q: Part I

Chiara F. Ferraris

Materials and Construction Research Division

Building and Fire Research Laboratory

William Guthrie

Ana Ivelisse Avilés

Statistical Engineering Division

Information Technology Laboratory

Robin Haupt

Materials and Construction Research Division

Construction Materials Reference Laboratory

Bruce S. MacDonald

Measurement Services Division

Technology Services

National Institute of Standards and Technology

Gaithersburg, MD 28099

July 2005

U.S. DEPARTMENT OF COMMERCE

Carlos M. Gutierrez, Secretary

TECHNOLOGY ADMINISTRATION

Michelle O’Neill, Acting Under Secretary of Commerce for Technology

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY

Hratch G. Semerjian, Acting Director
Certain commercial entities, equipment, or materials may be identified in this

document in order to describe an experimental procedure or concept adequately. Such

identification is not intended to imply recommendation or endorsement by the

National Institute of Standards and Technology, nor is it intended to imply that the

entities, materials, or equipment are necessarily the best available for the purpose.

National Institute of Standards and Technology Special Publication 260-161

Natl. Inst. Stand. Technol. Spec. Publ. 260-161, 36 pages (July 2005)

CODEN: NSPUE2

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 2005

_________________________________________

For sale by the Superintendent of Documents, U.S. Government Printing Office

Internet: bookstore.gpo.gov — Phone: (202) 512-1800 — Fax: (202) 512-2250

Mail: Stop SSOP, Washington, DC 20402-0001
Abstract

The standard reference material (SRM) for fineness of cement, SRM 114, is an integral 

part of the calibration material routinely used in the cement industry to qualify cements. 

Being a powder, the main physical properties of cement, prior to hydration, are its surface 

area and particle size distribution (PSD). Since 1934, NIST has provided SRM 114 for 

cement fineness and it will continue to do so as long as the industry requires it. Different 

lots of SRM 114 are designated by a unique letter suffix to the SRM number, e.g., 114a, 

114b, .... ,114q. A certificate that gives the values obtained using ASTM C204 (Blaine), 

C115 (Wagner) and C430 (45 μm sieve residue) is included with each lot of the material. 

The supply of SRM 114p, which was released in 1994, was depleted in 2004. 

Therefore, a new batch of SRM 114 needed to be developed. This process included 

selection of the cement, packaging the cement in small vials, and determination of the 

values for the ASTM tests reported. In this case, the Blaine, Wagner and 45 μm sieve 

residue were the tests used. Later the particle size distribution (PSD) will be added. 

The purpose of this report is to provide a detailed description of the process used to 

package and certify SRM 114q. All measurements used for the certifications are provided 

along with descriptions of the statistical analyses. 

iii
Acknowledgements

The authors would like to thank all participants of the round-robin (listed below in 

alphabetical order by institution) for providing time and staff to perform the Blaine, 

Wagner, and particle size distribution (PSD)1

 tests used for certification of this material. 

Also, we would like to thank Stephen Small and the staff of the Cement and Concrete 

Reference Laboratory (CCRL), who were instrumental in providing the samples to the 

round-robin participants and making sieve residue measurements. 

The authors would also like to thank some NIST key persons without whom this 

certification could not have being completed: Max Peltz for the PSD measurements; John 

Winpigler for the homogeneity measurements using loss of ignition; Mark Cronise and 

Curtis Fales for packaging all the materials; and Vince Hackley of the Materials Science 

and Engineering Laboratory for the numerous discussions during the planning stage. 

Round-Robin Participants (Alphabetical)

American Engineering Testing, Inc., St. Paul, MN: Ken Prom

Armstrong Cement, Cabot, PA: Eugene Szymborski 

Ash Grove Cement Co., Chanute, KS: Marc Melton 

Ash Grove Cement Co., Louisville, NE: Doug Jaquier 

Ash Grove Technical Center, Overland Park, KS: Kristen Freeman 

Buzzi Unicem USA Greencastle, IN: John Wachal 

Buzzi Unicem USA (formerly Lone Star), Greencastle, IN: W.D. Henry Robinson 

Buzzi Unicem USA, Inc. Independence KS Plant, Independence, KS: Jan J Benson 

Buzzi Unicem USA, New Orleans Slag Facility, New Orleans, LA: Ronald J. Rajki 

California Portland Cement Co., Mojave, CA: Rebecca Lara 

Cementa Research AB, Slite: Roger Lehrberg 

Cemento De El Salvador S.A., EL Espino Antiguo Cuscatlan: Guillermo Osorio 

Cementos Andino-Planta Betania, Bogota, Colombia: Maria M. Penaloza 

Cementos Andino-Planta San Gil, Bogota, Colombia: Joost E. Oostra 

Cementos del Norte,S.A.,Cortes: Jorge A. De J. Bueso 

Cementos Progreso, S.A. Planta San Miguel, La Pedrera Lic.: Luis Velasquez 

Cemex Inc. Fairborn, Xenia, OH: Rusty Strader 

CEMEX-Central Plans LLC, Dixon, IL: Guido Tenaglia 

CEREC-Cementos Progreso, S.A., La Pedrera: Emilio Beltranena 

Ciment Quebec Inc., St-Basile (Quebec): Serge Vallerand 

Concrete Technology-CECON-INTI, Buenos-Aires: Alejandra Benitez 

Connecticut DOT Research & Materials Testing, Rocky Hill, CT: John R. Giannini 

Construction Technology Laboratories, Skokie, IL: Ella Shkolnik 

Delaware DOT, Dover, DE: Karl Zipf 

ESSROC, Logansport, IN: Kevin Jensen 

 

1

 PSD data will be discussed in another report under preparation

iv
ESSROC San Juan, San Juan: Fernando Silvagnoli 

ESSROC Bessemer Laboratory, Bessemer, PA: Patricia Dubchak 

ESSROC Cement Corporation (Plant 1& Plant 3), Nazareth, PA: Bill Fink 

ESSROC Italcementi Group, Picton Ontario: Melissa Eaton 

F.L. Smidth A/S, LaboratoryCopenhagen: Bjarne Osbaeck 

GCC Dacotah, Rapid City, SD: Larry Paulsen 

Glens Falls Lehigh Cement, Glens Falls, NY: Donna Malone 

Hanson Permanante Cement, Cupertino, CA: John Lacy 

Hawaii DOT Materials Testing and Research Branch, Honolulu, HI: Jonathan Yee 

Hawaiian Cement-Cement Division, Kapolei, HI: Len B. Lagunoy 

Hellenic Cement Research Center (EKET) Attikis: Vassilis Kaloidas 

Hercules Cement Company, Stockertown, PA: Charles R. Ogle 

Holcim Group Support Ltd., Holderbank: Werner Flueckiger 

Holcim US Inc. Theodore Plant, Theodore, AL: Alissa Collins 

Kansas DOT Central Laboratory, Topeka, KS: Rodney Montney 

Lafarge - St. Constant, St. Constant, Quebec: Julie Arsenault 

Lafarge North America, Ravena, NY: Randy Bitely 

Lafarge North America, Calera, AL: Liz Higgins 

Lafarge North America Alpena Plant, Alpena, MI: William Ulrich 

Lafarge North America Exshaw Plant, Exshaw, Alberta: Carol Zaleski 

Lafarge North America Joppa Plant, Grand Chain, IL: Eric Bowman 

Lafarge North America Paulding Plant, Paulding, OH Tim Rawlsky 

Lafarge North America Sugar Creek Plant, Sugar Creek, MO: Nick Ewing 

Lehigh Cement Company, Leeds, AL: Michael Reylander 

Lehigh Cement Company, Waco, TX: J.W.Davis 

Lehigh Cement Company Union Bridge, Union Bridge, MD: Jeff Hook 

Lehigh Southwest Cement Co., Tehachapi, CA: Garry Bell 

Lone Star Industries- Buzzi Unicem USA, Pryor, OK: Mike Trimble 

Master Builders, Inc., Cleveland, OH: Brad Hulvey 

MD State Hwy Administration, Lutherville, MD: Vicki R. Stewart 

Minnesota DOT, Maplewood, MN: Rod Patrin 

Mississippi DOT, Jackson, MS: Richard Sheffield 

Mitsubishi Cement Corp., Lucerne Valley, CA: Tom Gepford 

Montana DOT.-Mat.Bureau ,Helena, MO: R. Scott Barnes 

National Cement Co., Ragland, AL: Frank Holcomb 

ND DOT, Bismarck, ND: Dennis Blasl 

Nebraska Dept. of Roads-Mat.& Res. Div., Lincoln, NE: George Woolstrum

NORCEM AS, Brevik Brevik: David Verdu 

Ohio DOT, Office of Materials Mgmt. Columbus, OH: Bryan Struble 

Penn DOT Materials & Testing Lab,Harrisburg, PA: Roy Trout 

RMC Pacific Materials Inc., Davenport, CA: Chow Yip 

St. Lawrence Cement, Inc., Mississauga, Ontario: John Falletta 

St. Marys Cement, Detroit, MI: Linda Harris 

St. Marys Cement, St.Marys : Walter Pearce 

Texas Lehigh Cement Co., Buda, TX: Jim Jarl 

Texas Midlothian Cement Plant, Midlothian, TX: Jeff Wendel 

v
The Euclid Chemical Co., Cleveland, OH: Bob Bucheral 

TPI Polene Standard Laboratory, Saraburi: Zaw Zaw Hlaing 

Texas DOT, Austin, TX: Lisa Lukefahr 

TXI Hunter Cement, New Braunfels, TX: Herman Borchers 

TXI Riverside Cement Co., Riverside, CA: Syed A. Rasheed 

TXI Riverside Cement Co., Oro Grande Plant , Oro Grande, CA: Bob Sylvia 

vi
Table of Contents 

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

2 Description of methods used....................................................................................... 2

2.1 Blaine ASTM C 204 ........................................................................................... 2 

2.2 Wagner ASTM C 115 ......................................................................................... 2 

2.3 Sieve Residue ASTM C 430............................................................................... 3 

3 Materials ..................................................................................................................... 4

3.1 Characteristics of the cement.............................................................................. 4 

3.2 Packaging............................................................................................................ 5

3.3 Homogeneity determination................................................................................ 5

4 Experiment Design and Data Analysis....................................................................... 7 

4.1 Blaine ASTM C 204 ........................................................................................... 7 

4.2 Wagner ASTM C 115 ......................................................................................... 8 

4.3 Sieve Residue ASTM C 430............................................................................... 9 

4.3.1 Cross check of the residue ........................................................................ 14 

5 Summary of Certified Values ................................................................................... 15 

6 Process Improvement................................................................................................ 16

6.1 Packaging.......................................................................................................... 16

6.2 Testing............................................................................................................... 16

7 Acknowledgments..................................................................................................... 16

8 References................................................................................................................. 17

9 Appendices................................................................................................................ 18

10 Certificate of SRM 114q....................................................................................... 23 

vii
List of Tables 

Table 1: Chemical composition .......................................................................................... 4 

Table 2: Cement compounds according to ASTM C150.................................................... 5 

Table 3: Results from the LOI tests.................................................................................... 6 

Table 4: ANOVA Output from the Fit of a Nested, Random-Effects Model with Factors 

Box, Lab, and Vial to the Blaine Data ........................................................................ 7 

Table 5: Summary of the Specific Surface Area Results for SRM 114q using the Blaine 

Procedure .................................................................................................................... 8 

Table 6: ANOVA Output from the Fit of a Nested, Random-Effects Model with Factors 

Box, Lab, and Vial to the Wagner Data...................................................................... 9 

Table 7: Summary of the Specific Surface Area Results for SRM 114q: Wagner 

Procedure .................................................................................................................... 9 

Table 8: ANOVA Output from the Fit of a Nested, Random-Effects Model with Factors 

Box and Vial to the Sieve Residue Data for the 38 μm Sieve .................................. 11 

Table 9: ANOVA Output from the Fit of a Nested, Random-Effects Model with Factors 

Box and Vial to the Sieve Residue Data for the 47 μm Sieve .................................. 11 

Table 10: ANOVA Output from the Fit of a Nested, Random-Effects Model with Factors 

Box and Vial to the Sieve Residue Data for the 56 μm Sieve .................................. 12 

Table 11: Residue Verification Using SRM’s 114p and 114q ......................................... 15 

List of Figures 

Figure 1: Plot of sieve residue data showing two outliers (square plotting symbols) from a 

vial that had been noted as containing cement of a different color than the other 

vials........................................................................................................................... 10 

Figure 2: Plot of sieve residue data for the 47 μm sieve (with the outlier omitted) that

shows evidence of day-to-day variation in the measurement process. ..................... 10 

Figure 3: A Brooks-Gelman-Rubin plot [12] showing the ratio (upper trace) of the 

variation between and within (lower pair of traces) four parallel Markov chains that 

were simulated for this model. The fact that the ratio approaches 1 and the variation 

within and between chains levels off by 50 000th iteration indicates convergence. 13 

 Figure 4: The posterior probability distribution of the sieve residue for a 45 μm sieve. 14 

viii
1 Introduction 

A standard reference material (SRM) is a material that has been well characterized with 

regard to its chemical composition, physical properties, or both. National Institute of 

Standards and Technology (NIST) provides over 1300 different SRMs to industry and 

academia. These materials are used in quality assurance programs, for calibration, and to 

verify the accuracy of experimental procedures. Every NIST SRM is provided with a 

certificate of analysis that gives the official characterization of the material’s properties. 

In addition, supplementary documentation, such as this report, that describes the 

development, analysis and use of SRMs is also often published by NIST to provide the 

context necessary for effective use of these materials. 

There are several SRMs related to cement (http://ts.nist.gov/ts/htdocs/230/232/232.htm). 

SRM 114 is related to the fineness of cement, as measured by various indirect methods 

giving its surface area and by passing the material through a fine sieve. This SRM is an 

integral part of the calibration material routinely used in the cement industry to qualify a 

cement. Being a powder, the main physical properties of cement are its surface area and 

particle size distribution (PSD). Since 1934, NIST has provided SRM 114 for cement 

fineness and it will continue to do so as long as the industry requires it. Different lots of 

SRM 114 are designated by a unique letter suffix to the SRM number. A certificate that 

gives the values obtained using ASTM C 204 (Blaine) [1], C 115 (Wagner) [2] and C 430 

(45-μm residue) [3] is included with each lot of the material. 

In 1934, only the Wagner test and the 45 μm residue were listed. In 1944, the Blaine 

measurement was added to the certificate of the SRM 114. In 2003, the PSD measured by 

laser diffraction was added as an information value, i.e., not certified. The PSD was 

obtained under the sponsorship of ASTM Task Group C01.25.01 [4, 5, 6]. 

The supply of SRM 114p, which was released in 1994, was depleted in 2004. Therefore, 

a new batch of SRM 114 needed to be developed. The development process included the 

selection of a cement, packaging of the cement in small vials, and determination of the 

values for the ASTM tests reported. In this case, the Blaine, Wagner and 45 μm sieve 

residue were the tests used. Later the particle size distribution (PSD) will be added. 

The values given in this report were obtained through a round-robin inter-laboratory 

study by volunteer participants from companies participating in the CCRL certification 

program. The particle size distribution by laser diffraction was also collected in the same

round-robin study but will be discussed in a separate report. 

The purpose of this report is to provide the description of the development of SRM 114q. 

It includes a detailed description of the process used to package and certify the cement. 

Also a brief description of the ASTM tests in the certificate is given. All measurements 

used for the certifications are provided along with the statistical analysis. 

1
2 Description of methods used 

2.1 Blaine ASTM C 204 

The Blaine measurement described in ASTM C 204 was adopted by ASTM in 1946. 

R.L. Blaine published the test in 1943 [7]. The principle of operation is that the 

permeability of a bed of fine particles is proportional to the fineness of the particles. 

Therefore, the test is a measurement of the flow rate of air through a bed of cement 

particles. From the beginning, it was stated that this is a relative test as it depends on the 

shape of the particles, and the compaction level or porosity of the bed. For this reason, 

ASTM C 204 section 4.1 states that the calibration of the instrument needs to be done by 

using a reference material, such as SRM 114 [8]. 

In brief, the test is carried out by packing the cement to be measured in a cell of known 

volume and placing it on top of a U-tube manometer that contains a non-hygroscopic 

liquid of low viscosity and density, e.g., dibutyl phthalate or a light grade of mineral oil. 

The cell is placed on the U-tube in such a way that a tight seal is created and a vacuum is 

created under the cement cell so that the liquid in the manometer is higher toward the 

cell. Then, the air is allowed to flow back only through the cement sample. The time for 

the liquid in the manometer to descend a set distance is measured. This time is used to 

calculate the fineness quantified by the surface area S of the cement defined using the 

following formula: 

s

s

T

S T S = (1)

where Ss is the surface area of the reference material, i.e., SRM 114 

 Ts is the time of flow using the reference material, i.e., SRM 114 

T is the time of flow of the material under test 

S is the surface area of the material under test 

Therefore, the surface area of the material tested can be calculated from the reference

material. 

The results requested from the participants in the round-robin study to determine the 

value of SRM 114q were calculated using SRM 114p as the reference material. All 

participants were requested to measure the SRM 114p material immediately before 

measuring the SRM 114q material and to report both results. 

2.2 Wagner ASTM C 115 

The Wagner test method described in ASTM C115 was adopted by ASTM in 1934 after a 

paper published by L.A. Wagner in 1933 [9]. This test is also referred as the turbidimeter 

fineness test because it measures the turbidity of a cement suspension in kerosene. 

2
A source of light shines through the cement suspension and is detected by a photoelectric 

cell. The intensity of the current generated by the cell is recorded. The calibration is done 

by calculation of a calibration factor, K, which depends on the cell used. To determine 

this factor a reference material, such as SRM 114, must be used. 

Using a reference with known surface area, this test can be used to obtain the surface area 

of materials similar to the reference, (i.e. Portland cements), by comparing the two 

relative levels of turbidity. This method could also determine the particle size 

distribution, but is limited to particles larger than 7.5 μm. Due to this bound on particle 

size and various other sources of error, it is rarely used for PSD determinations. 

The results requested from the participants in the round-robin study for SRM 114q used 

SRM 114p as the calibrant. 

2.3 Sieve Residue ASTM C 430 

The principle of this test is to measure the residue or retained amount of cement on a 

calibrated sieve. The sieve was selected as having a 45 μm opening (No. 3252

). Since a 

direct certification of sieve openings is impractical and expensive for production-scale 

work, sieves are calibrated by using a reference material, such as SRM 114. A sieve 

correction factor is calculated by measuring SRM 114 on the selected sieve and 

correcting the result with the certified value of the SRM 114. 

To avoid the need to propagate the SRM 114p uncertainty in the certification of the sieve 

residue for the SRM 114q material, however, three sieves with nominal openings of 38 

μm, 47 μm, and 56 μm were directly calibrated for use in reference material certification. 

Interpolation was then used to obtain the value at 45 μm. 

Although direct sieve calibration was also used for previous generations of this material, 

The procedure used for the 114q material was different in several respects from the 

certification of the two preceding lots of SRM 114: 

• For SRM 114n sieves with openings of 42 μm to 43.9 μm were used. The average 

results were plotted against the average sieve opening. The certified value was 

calculated by extrapolation to 45 μm. 

• For SRM 114p sieves with openings of 42 μm to 46 μm were used and all data 

points (rather than the averages) were plotted against the minimum sieve opening. 

The certified value was calculated by interpolation to 45 μm. 

 

2

 Sieve number follow the USA definition given in ASTM E11 

3
3 Materials 

3.1 Characteristics of the cement 

Based on the properties of past lots of SRM 114, CCRL and NIST identified a plant with 

a suitable cement for SRM 114q from Lehigh Cement Company3

, Union Bridge, 

Maryland, who donated 1300 kg of the cement for this SRM. The material selected was 

Type I according to the ASTM C 150 Standard Classification, and had a mass fraction of 

less than 8 % tricalcium aluminate (C3A) as defined by ASTM C 150. This requirement

was the same as for SRM 114p. Material was collected for shipment to NIST directly 

from the finish mill process stream into bags. 

The approximate chemical composition has been determined by ASTM Standard Test 

Method C 114-02 to provide additional information on this cement. The analyses of this 

cement (CCRL Portland Cement Proficiency Sample No. 150) were performed by 70 to 

170 laboratories. The composition, which is not certified but is provided for information 

only, is shown on Table 1. 

Calculation of cement compounds from this chemistry, according to ASTM C 150-02, are 

shown in Table 2, again for information only. 

The density of the cement was also measured using a modified ASTM C 188 method. 

The modification was to use isopropanol (IPA) as the medium instead of kerosene, 

otherwise a calibrated Le Chatelier flask was used as described in the ASTM test. Two 

measurements were done: 3.255 g/cm3

 and 3.248 g/cm3. This leads to an average of 

3.25 g/cm3 ± 0.005 g/cm3

. 

Table 1: Chemical composition 

CaO SiO2 A12O3 Fe2O3 SO3 K2O TiO2 P2O5 Na2O MgO

loss on 

ignition 

Percent 

by mass

fraction 64 20.7 4.7 3.2 2.4 0.7 0.3 0.12 0.07 2.2 1.67

 

3

 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. 

4
Table 2: Cement compounds according to ASTM C150 

Compound Percent by mass

fraction 

C3S (tricalcium silicate) 60 

C2S (dicalcium silicate) 14 

C3A (tricalcium aluminate) 7 

C4AF (tetracalcium alumino-ferrite) 10 

3.2 Packaging 

Upon its arrival at NIST, the cement was blended in a V-blender (1.7 m3 or 60 ft3) and 

then transferred to 0.2 m3 (55 gal) drums lined with 0.15 mm (6 mil) polyethylene liners 

to minimize hydration of the cement in storage prior to preparation and packaging. Over 

the next two days, the cement from each drum was sealed in foil bags, each containing

about 16 kg of cement. The foil bags were stored, and subsequently packaged as 

described below into vials, in a climate-controlled area. 

Each foil bag was packaged into vials and capped and boxed. Each box contained 

approximately 500 sealed vials and the boxes were sequentially labeled from 1 to 118. 

Usually about five boxes were filled per day. The more than 60 000 glass vials produced, 

each containing approximately 5 g of cement, were subsequently sealed into smaller 

individual foil bags. The vials were randomly selected (see section 4) and shipped to the 

participating laboratories for measurements. After the analysis of the results was 

completed the vials were packaged in boxes containing 20 vials each. 

 

3.3 Homogeneity determination 

After the material was packaged, it was necessary to determine whether the material in

different vials was the same. A special concern was any absorption of moisture during 

packaging from original delivery to placement in the vials. Therefore, the first test that 

was performed was loss of ignition (LOI). Cement taken from random vials was 

submitted to the following procedure: 

• The content of each sampled vial was divided among 3 crucibles (about 2 g of 

cement per crucible) and the mass was recorded 

• The crucible was placed in an oven at 105 °C for 12 h, and then allowed to cool 

down in a dessicator containing a desiccant. 

• The mass was recorded, and the crucible was placed in a furnace at 950 °C for 

3 h. 

• The sample was allowed to cool down in a dessicator and the mass was recorded. 

• The LOI was calculated as the water loss during the residence in the furnace per 

mass of the sample (after the oven drying). 

The LOI value is an indication of the amount of water loss during the drying procedure. 

A high value would be an indication of improper handling of the cement. 

5
The LOI values are shown in Table 3. The Box # identifies a randomly sampled vial from

that box. The LOI averages are very small (less than 0.15 %). Therefore, we conclude 

that there was no significant intake of moisture during packaging. 

Nevertheless, further checks were performed during the analysis of the round-robin data 

by determining whether a box-to-box or vial-to-vial variation was detected (see Section 

4). 

Table 3: Results from the LOI tests 

Box 

# 

LOI 

[%]

Average 

[%]

St. Dev 

[%]

0.224 

0.045 

9 

0.050 

0.11 0.10

0.097 

0.224 

27 

0.137 

0.15 0.07

0.100 

0.243 

35 

0.048 

0.13 0.10

0.047 

0.179 

47 

0.000 

0.08 0.09

0.000 

0.000 

53 

0.046 

0.02 0.03

0.049 

0.000 

56 

0.290 

0.11 0.16

0.048 

0.135 

72 

0.141 

0.11 0.05

0.139 

0.189 

76 

0.049 

0.13 0.07

0.091 

0.000 

98 

0.000 

0.03 0.05

0.089 

0.046 

118 

0.100 

0.08 0.03

6
4 Experiment Design and Data Analysis 

4.1 Blaine ASTM C 204 

The data for the Blaine test, ASTM C 204, were collected using a nested experiment

design with three factors, laboratory, box, and vial. In this design, two randomly selected 

laboratories who use the Blaine test were each supplied two randomly drawn vials of 

cement from a randomly assigned box of vials. The laboratory was then asked to measure 

duplicate samples from each vial. Use of this design allows assessment of lab-to-lab

variability, box-to-box heterogeneity of the cement, and vial-to-vial heterogeneity of the

cement. 

For the analysis of the Blaine data, the first step was to screen the data for non-statistical 

problems. Based on this screening, results from three labs, 209, 247, and 932, were 

eliminated from the data set. In each case, the data from these laboratories were omitted

from the analysis because Blaine measurements were made on one vial from the box 

designated for the Blaine measurements and one vial from the box designated for the 

Wagner measurements. Due to the nature of the experiment design, including these 

results would have made it more difficult to distinguish between the different potential 

sources of variation. 

Next, a nested, random-effects, analysis of variance (ANOVA) model [10] was fit to the

remaining data to check for box-to-box, lab-to-lab, and vial-to-vial variability. Residual 

plots to verify that the model fit the data showed that two labs each had two extreme 

outlying measurements. Since there were a large number of labs (66) for this analysis and 

only two had unusual data, the data from these two labs (123 and 886) was also omitted 

from the analysis. After refitting the model, residual plots indicate that the model fits the 

data well. The output from the analysis of variance is shown in Table 4. The low p values 

(<0.05) corresponding to the F tests for the significance of lab-to-lab and vial-to-vial 

variability provide strong evidence that there is significant lab-to-lab variation and vialto-vial heterogeneity. The high p value for the F test for box-to-box variability (0.365) 

indicates that there is not strong evidence of significant box-to-box heterogeneity in this 

data. 

Table 4: ANOVA Output from the Fit of a Nested, Random-Effects Model with 

Factors Box, Lab, and Vial to the Blaine Data 

Source 

Degrees of 

Freedom 

Sums of 

Squares 

Mean 

Squares F Statistic p value 

Box-to-Box 37 18703.91 505.511 1.143 0.365

Lab-to-Lab (in Box) 26 11494.21 442.085 29.328 0.000 

Vial-to-Vial (in Box/Lab) 64 964.72 15.074 2.960 0.000 

Residuals 128 651.83 5.092

7
Because there is significant vial-to-vial heterogeneity, a prediction interval should be

used for certification. Based on the ANOVA results above, a summary of the material's

properties as measured with the Blaine procedure is given in Table 5. 

Table 5: Summary of the Specific Surface Area Results for SRM 114q using the 

Blaine Procedure 

Mean Blaine Result: 381.81 m2

/kg 

Standard Uncertainty of Mean: 1.31 m

2

/kg 

Effective Degrees of Freedom: 26.00 

Standard Uncertainty of Heterogeneity: 2.23 m

2

/kg 

Effective Degrees of Freedom: 26.55 

Standard Uncertainty of 114p 2.93 m

2

/kg 

Effective Degrees of Freedom: 60.00 

Combined Standard Uncertainty: 3.91 m

2

/kg 

Effective Degrees of Freedom: 102.66 

Coverage Factor (95 % coverage): 1.98 

Expanded Uncertainty: 7.76 m

2

/kg 

4.2 Wagner ASTM C 115 

The experiment design and analysis used for the Wagner [2] data are analogous to the 

design and analysis used for the Blaine data. As the first step in the analysis, the Wagner 

data were also screened for non-statistical problems. Based on this screening, data from

one lab, 247, were eliminated from the data set because Wagner measurements were 

made on one vial from the box designated for the Wagner measurements and one vial 

from the box designated for the Blaine measurements. 

Next we fit a nested, random effects, analysis of variance model to the remaining data to 

check for box-to-box, lab-to-lab, and vial-to-vial variability. Residual plots indicate that 

the model fits the data well, although there is only one degree of freedom for estimating 

the lab-to-lab variability. The analysis of variance results are shown in Table 6. The high 

p values for the tests for significant box-to-box and vial-to-vial variability do not provide 

strong evidence that the material is heterogeneous as measured by the Wagner method. 

Even with one degree of freedom, however, significant lab-to-lab variation is evident as 

indicated by the low p value for the F test for the significance of lab-to-lab variability. 

8
Table 6: ANOVA Output from the Fit of a Nested, Random-Effects Model with 

Factors Box, Lab, and Vial to the Wagner Data 

Source 

Degrees of 

Freedom 

Sums of 

Squares 

Mean 

Squares F Statistic p value

Box-to-Box 4 250579.600 62644.900 0.335 0.841

Lab-to-Lab (in Box) 1 186966.100 186966.100 295.696 0.000 

Vial-to-Vial (in Box/Lab) 6 3793.800 632.300 0.907 0.522 

Residuals 12 8367.500 697.300

Since there is no evidence of vial-to-vial or box-to-box variability, it was decided to base 

the certified value and uncertainty for the Wagner method on the mean and standard 

deviation of the laboratory means. Based on this decision, a summary of the certification 

results is given in Table 7. The final uncertainty is large because so few labs are using the 

Wagner method and could provide results using this method in the inter-laboratory study. 

Table 7: Summary of the Specific Surface Area Results for SRM 114q: Wagner 

Procedure 

Mean Wagner Result: 218.33 m2

/kg 

Standard Uncertainty of Mean: 6.04 m2

/kg 

Effective Degrees of Freedom: 5.00 

Standard Uncertainty of 114p: 2.35 m

2

/kg 

Effective Degrees of Freedom: 60.00 

Combined Standard Uncertainty: 6.48 m2

/kg 

Effective Degrees of Freedom: 6.62 

Coverage Factor (95 % coverage): 2.44 

Expanded Uncertainty: 15.86 m2

/kg 

4.3 Sieve Residue ASTM C 430 

A nested design with three factors, day, box and vial was used to collect the sieve 

residue data. The same design values were used to make measurements on each of the 

three sieves with one measurement per sieve made from each vial tested. This design

allows for the estimation of day-to-day, box-to-box, and vial-to-vial variation. In 

addition, since the three sieves are each of different sizes spanning the sieve value of 

interest, 45 μm, the data from this experiment can also be used to fit a model relating 

sieve residue to the sieve opening size.

For the analysis of the sieve residue data, the data were first plotted to graphically 

identify potential factor effects and to look for any unusual observations. The plot in 

Figure 1 identifies two outliers, from measurements on a vial that had been noted to 

contain a different color of cement than the others. Since these points were obtained from

a suspect sample and were very different from all of the other data, they were eliminated 

from the analysis. Measurements of other samples from this vial, which did not appear to 

9
have unusual values, were still used, however. After removal of the outliers, some

evidence of day-to-day variation between the samples is also evident in Figure 2. 

Sieve Opening Size, mm

Sieve Residue, %

40 45 50 55

0.5 1.0 1.5 2.0

Figure 1: Plot of sieve residue data showing two outliers (square plotting symbols) from 

a vial that had been noted as containing cement of a different color than the other vials.

Day

Sieve Residue, %

1 2 3 4 5

0.50 0.55 0.60 0.65 0.70 0.75

Figure 2: Plot of sieve residue data for the 47 μm sieve (with the outlier omitted) that

shows evidence of day-to-day variation in the measurement process.

10
Next, a nested, random effects analysis of variance model was fit to the data from each 

sieve to check for day-to-day, box-to-box, and vial-to-vial variability. To maintain the

balance of the design for the two sieves for which 1 of the 40 measurements was omitted, 

the means of the remaining data from the same box as the omitted vial were substituted 

for the missing data points. Residual plots from each fit verify that the models fit the data 

from each sieve reasonably well. The ANOVA results, showing the output from the fit of

the model to the data from each sieve, are given in Table 8 to Table 10. The relatively

high p values in Table 8 (p > 0.05) indicate that there is not strong evidence for day-today, box-to-box, or vial-to-vial in these data collected using the 38 μm sieve. The low p

value for the F test for significant day-to-day variation (0.025) does indicate that there is 

significant day-to-day variation in the data collected using the 47 μm sieve. There is no 

evidence of significant variability from the other two factors, however. Finally, the high 

p values for day-to-day and box-to-box variability for the 56 μm sieve indicate that those 

factors are not significant, but the low p value for the F test for vial-to-vial variability

indicates that there is significant vial-to-vial variation in the measurements made with the

56 μm sieve 

Table 8: ANOVA Output from the Fit of a Nested, Random-Effects Model with 

Factors Box and Vial to the Sieve Residue Data for the 38 μm Sieve

Source 

Degrees of 

Freedom 

Sums of 

Squares 

Mean 

Squares F Statistic p value 

Day-to-Day 4 0.124 0.031 1.126 0.439

Box-to-Box (in Day) 5 0.138 0.028 2.085 0.095 

Vial-to-Vial (in Day/Box) 10 0.178 0.018 1.614 0.174 

Residuals 20 0.220 0.011

Table 9: ANOVA Output from the Fit of a Nested, Random-Effects Model with 

Factors Box and Vial to the Sieve Residue Data for the 47 μm Sieve

Source 

Degrees of 

Freedom 

Sums of 

Squares 

Mean 

Squares F Statistic p value 

Day-to-Day 4 0.047 0.012 7.406 0.025

Box-to-Box (in Day) 5 0.008 0.002 0.722 0.612 

Vial-to-Vial (in Day/Box) 10 0.017 0.002 0.679 0.731 

Residuals 20 0.049 0.002

11
Table 10: ANOVA Output from the Fit of a Nested, Random-Effects Model with 

Factors Box and Vial to the Sieve Residue Data for the 56 μm Sieve

Source 

Degrees of 

Freedom 

Sums of 

Squares 

Mean 

Squares F Statistic p value 

Day-to-Day 4 0.010 0.003 0.965 0.500

Box-to-Box (in Day) 5 0.013 0.003 1.066 0.399 

Vial-to-Vial (in Day/Box) 10 0.4690 0.005 3.261 0.012 

Residuals 20 0.029 0.001

For the certification analysis, a Bayesian model relating the sieve residue of the 114q 

material from each sieve to the measured sieve size was developed. A Bayesian model 

was used in order to be able to account for the uncertainty in both the sieve calibrations 

and the measurements of the reference material made using those sieves. Because of the 

apparent day-to-day and vial-to-vial variation, and to allow for the fact that those effects 

were not consistently visible for all sieves, the Bayesian model accounts for all four 

possible sources of random variation that were included in the design, day-to-day, box-tobox, vial-to-vial, and measurement uncertainty. Although it might not be necessary to 

treat all of the sieves in the same way, since only one exhibited significant apparent dayto-day variability and one exhibited significant apparent vial-to-vial variability, it was

decided to treat them consistently in case those effects (or box-to-box effects) were 

simply not detected for the other two sieves. 

In order to specify inter-relationships among the data, the model specifies the 

hypothesized relationships between the unknown true values underlying the data (called 

parameters in statistical jargon), which are to be estimated. In this case, the model 

specifies a quadratic relationship between the true sieve residues and true sieve sizes. The 

data gives us the quantitative information needed to estimate the parameter values. Then 

the model is used to interpolate the result that would be obtained from a sieve with

openings of exactly 45 μm. 

In order to use the Bayesian model, initial assessments of the values of each parameter in

the model must be provided. The initial assessment for each parameter is specified as a 

probability distribution for the parameter’s unknown value. Because these probability

distributions are specified independently of the data (i.e. before the data are observed or

used), these distributions are commonly called prior distributions. For this analysis, noninformative prior distributions were used. These distributions are essentially very flat and 

have very large variances so that they will not provide any quantitative information about 

the values of the parameters as part of the model. 

A probability distribution for each measurement, given with respect to the parameters in

the model, is also specified. This distribution is called the likelihood of the data. For this 

analysis, based on typical assumptions for the statistical analysis of metrological data, 

normal distributions with means specified by the quadratic relationship between residue 

and sieve size and standard deviations based on sieve size were used for the likelihood. 

Then, based on the hypothesized relationships between the parameters, the likelihood, 

and the observed data, the prior distributions for each parameter are updated using Bayes’ 

12
Theorem to obtain new distributions for each parameter given the information in the data. 

Finally, these new distributions, called posterior distributions, are used to obtain 

uncertainty intervals about each quantity of interest. 

The Bayesian model was fit using Markov Chain Monte Carlo simulation [11]. Figure 3 

shows a plot comparing the within and between chain variation [12] that indicates that the

Markov Chains had converged by the 50 000th iteration of the simulation. Then 10 000 

additional iterations were run for each of 4 parallel Markov chains to estimate the 

parameter values. Based on these results, the posterior probability distribution describing 

the sieve residue for a 45 μm sieve is shown in Figure 4. A 95 % probability interval for 

the value of the sieve residue obtained from this posterior distribution is 

0.79 % ± 0.19 %. 

r45p chains 1:4

0 20000 40000 60000

Iteration

 0.9

 1.0

 1.1

Brooks-Gelman-Rubin Statistics 

Figure 3: A Brooks-Gelman-Rubin plot [12] showing the ratio (upper trace) of the

variation between and within (lower pair of traces) four parallel Markov chains that were 

simulated for this model. The fact that the ratio approaches 1 and the variation within and 

between chains levels off by 50 000th iteration indicates convergence. 

13
r45p chains 1:4 sample: 40000

 -0.5 0.0 0.5 1.0 1.5

 0.0

 2.0

 4.0

 6.0

Sieve Residue, % 

Probabilit

y Densit

y

 Figure 4: The posterior probability distribution of the sieve residue for a 45 μm sieve.

4.3.1 Cross check of the residue 

Because the 114q material has such a different residue than previous generations of this 

material, it is important to verify that the correct results will be obtained when the

certified value is used to calibrate a sieve as described in ASTM C430. The standard 

implies that the SRM 114q is sieved using a sieve with an unknown opening (although it 

should nominally be about 45 μm). The result is used with the certified value to calibrate 

the sieve and correct results of unknown cements. 

To verify the performance of the 114q material, we did a double verification as shown in 

Table 11. The verification consisted of calculating the correction factor using one of the 

SRMs and testing the other SRM using this correction factor. For example in column 1 

(Table 11) SRM 114p is used to calculate the correction factor that is then used to correct 

a measurement of SRM 114q. If everything it working as expected, the residue found for

SRM 114q should match the value found in the certificate, which it does. Similarly, the 

results obtained for SRM 114p, when 114q is used to calibrate the sieve, do not disagree 

with the value from the 114p certificate, although the uncertainty in the corrected result 

for 114p is rather large. 

14
Table 11: Residue Verification Using SRM’s 114p and 114q 

Sieve Correction Factor Calculation SRM 114p SRM 114q 

Certified residue on 45 μm sieve [%] 8.24 ± 0.37 0.79 ± 0.19 

Residue for 1 g sample [g] 0.0824 ± 0.0037 0.0079 ± 0.0019 

Residue on sieve being calibrated [g] 0.0683 ± 0.0068 0.0060 ± 0.0006 

Difference [g] 0.0141 ± 0.0077 0.0019 ± 0.0020 

Correction factor [%] 20.6442 ± 13.22 31.6667 ± 34.2949 

Cement Tested SRM 114q SRM 114p 

Residue from sample being tested [g] 0.0060 ± 0.0006 0.0683 ± 0.0068 

Corrected residue [%] 0.7239 ± 0.1074 8.9928 ± 2.5090 

Certified residue on 45 μm sieve [%] 0.79 ± 0.19 8.24 ± 0.37 

Note: Uncertainties shown for each value are expanded uncertainties at the 95 % 

confidence level. A coverage factor of k = 2 was used in all cases. 

5 Summary of Certified Values 

The certified values for the SRM 114q certificate are: 

 

Measurement and ASTM Method Result

Specific Surface Area C 204-96a 

(Blaine)

3818 cm2/g ± 78 cm2/g 

(381.8 m2/kg ± 7.8 m2/kg) 

 

Specific Surface Area C 115-96a 

(Wagner) 

 

2183 cm2/g ± 160 cm2/g 

(218 m2

/kg ± 16 m2/kg) 

Sieve Residue C 430-96

(45 μm sieve) 

0.79 % ± 0.19 % 

15
6 Process Improvement 

6.1 Packaging 

As stated above, the cement received from the manufacturer was sealed in foil bags after 

being blended. It was the original intention that each foil bag would be open, divided in 

the vials and any left over would be discarded. This would ensure that the cements left in 

the foil bags overnight (or longer due to scheduling) would not hydrate in between vial 

filling. If hydration occurs the cement properties will change. As a further quality 

assurance, the temperature, relative humidity should be recorded. If a log is kept of the 

temperature, relative humidity, vials filled, it would results in a better correlation between 

homogeneity problems and specific vials. 

 

During the filling of this batch of 600 000 vials, the procedure outlined above was 

followed but no log was kept of the temperature and relative humidity. Therefore, when it 

was discovered that vials, checked for homogeneity using other methods such as PSD, 

were found not satisfactory [13], it was not possible to rule out that the packaging 

conditions were one of the effects. 

This situation did not affect the data presented here probably because none of the tests

used are sensitive to complete dispersion, as it is the case for PSD measurements. 

6.2 Testing 

As shown in Table 3, one vial per box was used for the LOI testing. With this design, 

box-to-box and vial-to-vial differences in the LOI results cannot be differentiated. One 

minor improvement to the design for LOI testing in the future would be to sample two 

vials per box so that potential vial-to-vial variability could be separated from box-to-box 

variability in the LOI results. If necessary, half as many boxes could be sampled in order 

to keep the total number of measurements the same. Reducing the number of boxes 

sampled would reduce our ability to identify box-to-box differences, since some of the 

degrees of freedom would be used to check for vial-to-vial variability, but the added 

ability to separate vial-to-vial variability from box-to-box variability would give us the 

potential for additional insight into the process that would offset that loss. 

Because of the small sieve residue for this cement, some digitization was evident in the 

sieve residue data. For future sieve residue assessments on cements with residues in this 

low range, use of a balance with a finer resolution would be advantageous. 

7 Acknowledgments

The authors would like to thank Max Peltz for helping with the sample preparations, and 

Romayne Hines for helping in distribution of the samples for the round-robin. Special 

thanks are extended also to Vince Hackley for his numerous suggestions and fruitful 

16
discussions, and Edward Garboczi (NIST), Kenneth Snyder (NIST) and Charles 

Hagwood (NIST) for their valuable comments. 

8 References 

1. “Standard Test Method for Fineness of Hydraulic Cement by Air Permeability 

Apparatus”, ASTM C204-00 Volume: 04.01 

2. “Standard Test Method for Fineness of Portland Cement by the Turbidimeter”, 

ASTM C115-96a (2003) Volume: 04.01 

3. “Standard Test Method for Fineness of Hydraulic Cement by the 45-μm (No. 325) 

Sieve”, ASTM C430-96 (2003) Volume: 04.01 

4. Ferraris, C.F, Hackley V.A., Aviles A.I., Buchanan C.E., "Analysis of the ASTM 

Round-Robin Test on Particle Size Distribution of Portland Cement: Phase I" NISTIR

6883, May 2002 (http://ciks.cbt.nist.gov/~garbocz/nist6883/nistir6883.htm)

5. Ferraris, C.F, Hackley V.A., Aviles A.I., Buchanan C.E., "Analysis of the ASTM 

Round-Robin Test on Particle Size Distribution of Portland Cement: Phase II" 

NISTIR 6931, December 2002 

6. Ferraris C.F., Hackley V.A., Avilés A.I., “Measurement of Particle Size Distribution 

in Portland Cement Powder: Analysis of ASTM Round-Robin Studies”, Cement, 

Concrete and Aggregate Journal, Dec. 2004, vol. 26 #2, pp 71-81 

7. Blaine R.L., “A Simplified Air Permeability Fineness Apparatus” , ASTM Bulletin, 

No.123, 1943, pp 51-55 

8. Bean L. B., Dise J.R., “Causes of Variation in Chemical Analyses and Physical Tests 

of Portland Cement”, NBS, Building Series #17, 1969 

9. Wagner, L. A., “A Rapid Method for the Determination of the Specific Surface of 

Portland Cement,” Proceedings, ASTM, ASTEA, Vol 33, Part II, 1933, p. 553 

10. Montgomery, Douglas C., Design and Analysis of Experiments, 2nd Edition, John 

Wiley and Sons, New York, 1984 

11. Gelman, A., Carlin, J.B., Stern, H.S., Rubin, D.B., Bayesian Data Analysis, Chapman 

and Hall, London, 1995 

12. Brooks S.P. and Gelman A. “Alternative methods for monitoring convergence of 

iterative simulations,” Journal of Computational and Graphical Statistics, 7, 1998, pp 

434-455 

13. Ferraris, C.,F. Avilés A.I., Guthrie W., Haupt, R., MacDonald, B. S., Peltz, M. 

“Certification of SRM 114q: Part II”, to be published in 2005 

17
9 Appendices 

Appendix A: Data received from the round robin for Blaine 

Raw data as received: Grey [m2/ kg]; white [s] Calculated Blaine (SRM 114

SRM 114p Vial #1 Vial #2 Vial #1 

CCRL 

Lab 

Code Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box 

6 85.1 19 89.9 89.46 19 89.01 88.35 19 3878 3869 1

10 104 45 90.7 89.8 45 88.56 89.3 45 3525 3507 411 74 89 80 78 89 79 79 89 3924 3875 818 85 87.5 30 71 66.5 30 64.5 67.5 30 3424 3314 319 118 70 129.2 129.4 70 129.6 128.8 70 3949 3952 720 85.3 114 91.6 90.01 114 91.29 92.6 114 3912 3877 1127 152 149 107 157 157 107 158 157 107 3855 3855 1028 3800 81 3910 3910 81 3880 3900 81 3910 3910 840 109.6 108.7 109 121.1 119.9 109 115.5 117.9 109 3975 3956 1041 75.7 9 76.9 76.7 9 75.9 76 9 3804 3799 9 43 91.4 55 95.2 95.1 55 95.7 95.8 55 3852 3850 554 3772 3770 89 3814 3748 89 3878 3882 89 3814 3748 856 3820 3840 50 3810 3770 50 3810 3790 50 3810 3770 560 114 114 80 121 120 80 119 120 80 3888 3872 869 77.4 76.8 40 78.8 79.1 40 78.6 78.2 40 3815 3823 473 80 58 83 82 58 80 81 58 3844 3821 575 3810 3800 77 3695 3715 77 3697 3708 77 3695 3715 784 115.4 120 116.555 115.7 120 122.1 121.4 120 3793 3779 1292 68.8 66.56 118 71.35 68.0 118 70.17 69.5 118 3876 3784 1195 77.5 77 80 85.5 85 80 85 85.5 80 3970 3959 8

105 85.4 85.9 11 86.7 86.9 11 85.7 86 11 3797 3801 1121 81.4 47 83.20 84.6 47 84.3 84.1 47 3816 3847 4123 84 88 105 80 88 83 83.5 88 4219 3683 8

18
Raw data as received: Grey [m2/ kg]; white [s] Calculated Blaine (SRM 114

SRM 114p Vial #1 Vial #2 Vial #1 

CCRL 

Lab 

Code Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box 

124 70 70.5 13 75 75.5 13 75.5 75.5 13 3900 3912 1125 3752 11 3861 3861 11 3796 3752 11 3861 3861 1148 83.9 82.8 75 81.0 79.3 75 82.8 82.2 75 3720 3680 7151 89.1 86.6 116 87.3 86.0 116 90.8 88.7 116 3762 3734 11157 93 58 95 94 58 94 93 58 3814 3794 5162 3745 3756 14 3796 3806 14 3777 3788 14 3796 3806 1166 81 81 86 90 90 86 90 90 86 3978 3978 8167 3750 3730 98 3800 3800 98 3860 3850 98 3800 3800 9175 106 110 30 110 111 30 109 111 30 3809 3827 3178 77.5 77.4 3 67.4 69.5 3 73.6 70.3 3 3521 3575 3 205 90 89.8 50 91.9 90.9 50 90.9 91.5 50 3816 3795 5209 85.3 84 66 90.7 89.9 113 88.4 91.0 66 3907 3889 11222 87.7 28 87.8 86.5 28 87.6 87.3 28 3776 3748 2225 105 106 40 110 111 40 109 110 40 3854 3871 4245 80 19 73 72.5 19 73 74 19 3605 3593 1246 71.5 21 81 80.3 21 79.8 79.1 21 4017 4000 2247 88 43 93 109 92 43 3880 0 10254 3765 3788 97 3854 3846 97 3807 3815 97 3854 3846 9255 3730 77 3800 3720 77 3800 3839 77 3800 3720 7284 97.0 97.5 86 104.0 104.0 86 104.0 103.5 86 3903 3903 8303 92.9 92.2 32 94.5 93.9 32 95.5 92.4 32 3814 3801 3309 88 88 116 90 90 116 90 90 116 3817 3817 11354 77.7 76.5 31 80.95 80.65 31 79.82 78.75 31 3867 3860 3360 100 100 3 100 98 3 99 97 3 3774 3736 3 413 Too variable to report441 3760 3760 114 3740 3650 114 3710 3690 114 3740 3650 11493 83 84 32 87 90 32 90 88 32 3852 3918 3494 97 98 66 100 100 66 98 98 66 3822 3822 6

19
Raw data as received: Grey [m2/ kg]; white [s] Calculated Blaine (SRM 114

SRM 114p Vial #1 Vial #2 Vial #1 

CCRL 

Lab 

Code Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box # Meas#1 Meas.#2 Box 

551 3751 3769 112 3892 3887 112 3926 3930 112 3892 3887 11557 100 100 18 101 100 18 100 101 18 3793 3774 1605 3816 28 3879 3879 28 3859 3816 28 3879 3879 2690 3774 88 3801 3801 88 3828 3828 88 3801 3801 8736 99.6 97.8 71 108.2 105.3 71 107.6 106.5 71 3951 3898 7886 3705 3735 119 3832 3784 119 3624 3851 119 3832 3784 11932 115.4 19 121.4 122.9 75 123.2 123.8 19 3871 3895 7

1042 111.6 111.1 21 114.4 114.3 21 110.9 112.6 21 3824 3823 21054 83 85 14 93 93 14 90 90 14 3971 3971 11251 3765 3757 107 3891 3874 107 3883 3883 107 3891 3874 101715 72.9 72.3 13 74.8 75.1 13 75.6 75.5 13 3829 3837 11773 101.1 101.4 47 91.3 91.6 47 90.4 90.7 47 3584 3590 41819 82.59 83.00 9 86.4 87.1 9 86.1 86.5 9 3855 3870 9 1916 88.9 88.7 31 94.1 95.2 31 95.6 94.2 31 3884 3908 31940 3716 3753 18 3870 3901 18 3825 3922 18 3870 3901 12116 47.5 48.0 118 50.5 50.0 118 50.5 49.5 118 3881 3862 112190 85.3 86.0 111 86.3 85.8 111 87.5 86.3 111 3789 3778 112191 75.4 74.3 111 73.6 77.4 111 79.7 81.4 111 3744 3837 11

NA 65.2 64.8 70 66.7 67.0 70 66.5 66.5 70 3824 3832 7

20
Appendix B: Data received from the round robin for Wagner 

CCRL 114p Box A Box B 

code Meas. #1 Meas. #2 Box # Meas. #1 Meas. #2 Box # Meas. #1 Meas. #2 

73 2049 9 1984 1986 9 1997 2040

125 2130 9 2330 2290 9 2310 2300205 2070 119 2380 2380 119 2380 2350247 43 2280 2240 109 2260 2280254 2060 2085 43 2046 2020 43 2117 2043494 2088 2078 66 2113 2126 66 2135 2079551 2045 2067 113 2227 2262 113 2272 2232

21
Appendix C: Data obtained for Residue 

Day Box Vial Residue 

Sieve 1 Sieve 2 Sieve 3 

1 118 1 0.0010 g 0.0035 g 0.0015 g 

1 35 1 0.0150 g 0.0060 g 0.0030 g 

1 118 1 0.0160 g 0.0050 g 0.0010 g 

1 35 2 0.0160 g 0.0050 g 0.0020 g 

1 35 2 0.0155 g 0.0060 g 0.0010 g 

1 35 1 0.0150 g 0.0055 g 0.0030 g 

1 118 2 0.0170 g 0.0050 g 0.0025 g 

1 118 2 0.0150 g 0.0060 g 0.0025 g 

2 47 2 0.0160 g 0.0060 g 0.0025 g 

2 27 1 0.0180 g 0.0065 g 0.0010 g 

2 27 1 0.0180 g 0.0060 g 0.0020 g 

2 47 2 0.0160 g 0.0060 g 0.0025 g 

2 27 2 0.0185 g 0.0060 g 0.0020 g 

2 47 1 0.0175 g 0.0060 g 0.0030 g 

2 27 2 0.0160 g 0.0055 g 0.0025 g 

2 47 1 0.0170 g 0.0065 g 0.0020 g 

3 53 2 0.0150 g 0.0020 g 

3 98 1 0.0165 g 0.0065 g 0.0025 g 

3 53 2 0.0160 g 0.0065 g 0.0025 g 

3 98 2 0.0170 g 0.0075 g 0.0025 g 

3 98 2 0.0155 g 0.0060 g 0.0020 g 

3 98 1 0.0150 g 0.0060 g 0.0025 g 

3 53 1 0.0170 g 0.0070 g 0.0025 g 

3 53 1 0.0150 g 0.0060 g 0.0015 g 

4 76 2 0.0135 g 0.0055 g 0.0025 g 

4 72 2 0.0165 g 0.0060 g 0.0025 g 

4 76 1 0.0170 g 0.0065 g 0.0025 g 

4 76 2 0.0150 g 0.0065 g 0.0025 g 

4 76 1 0.0135 g 0.0060 g 0.0020 g 

4 72 1 0.0195 g 0.0070 g 0.0025 g 

4 72 1 0.0175 g 0.0065 g 0.0025 g 

4 72 2 0.0145 g 0.0065 g 0.0025 g 

5 56 2 0.0160 g 0.0055 g 0.0025 g 

5 56 2 0.0160 g 0.0060 g 0.0020 g 

5 9 1 0.0180 g 0.0065 g 0.0030 g 

5 56 1 0.0170 g 0.0070 g 0.0025 g 

5 9 2 0.0155 g 0.0065 g 0.0025 g 

5 56 1 0.0165 g 0.0060 g 0.0025 g 

5 9 1 0.0180 g 0.0065 g 0.0025 g 

5 9 2 0.0165 g 0.0065 g 0.0025 g 

0.0060 g 

Note: Box 118 vial 1 - slightly different color than that of box 118 vial 2 and both vials 1 and 2 

from box 35 

22
10 Certificate of SRM 114q 

Below the certificate of SRM 114q is provided for information only. As, the certificate will be 

updated later in 2005 to add the particle size distribution of the cement [13], the official version 

is the available online at: https://srmors.nist.gov/certificates/view_cert2gif.cfm?certificate=114q

Or by selecting “Standard Reference Materials” from the website www.NIST.GOV and typing in 

114q 

23
National Institute of Standards & Technology 

Certificate of Analysis 

Standard Reference Material 114q 

Portland Cement Fineness Standard 

This Standard Reference Material (SRM) is intended for use in calibrating fineness testing equipment according to 

ASTM Standard Methods. The SRM unit consists of 20 glass vials with plastic caps containing powdered cement 

(each vial is contained in a sealed foil bag). Each vial contains approximately 5 g of cement. 

Certified Values and Uncertainties: A NIST certified value is a value for which NIST has the highest confidence

in its accuracy and that all known or suspected sources of bias have been investigated or accounted for by NIST. 

The certified values for specific surface area and sieve residue are given in Table 1. The certified values for the

surface area are the mean of results from analyses performed by cooperating laboratories. The certified value for 

sieve residue was calculated from a quadratic fit of NIST data using three sieves having openings ranging from

38 μm to 56 μm.

The expanded uncertainties of the certified values for specific surface area were calculated according to the NIST

uncertainty policy described in the NIST Technical Note 1297 [1], and are at the 95 % confidence level. The 

uncertainties include measurement variability within and between laboratories. The surface area uncertainties also 

include material variability and the uncertainty of the surface area values for the superseded SRM 114p Portland

Cement Fineness Standard, which was used as the calibrant for this material. The expanded uncertainty for the

sieve residue was computed using a Bayesian analysis and is also at the 95 % probability level. The expanded

uncertainty accounts for the variability of random measurement effects, sieve calibrations, and material

inhomogeneity.

Table l. Certified Values 

Measurand ASTM Method Certified Value and Expanded 

 Uncertainty 

Specific Surface Area C 204-96a(a) 

(Blaine) 

 3818 cm2

/g ± 78 cm2/g

 (381.8 m2

/kg ± 7.8 m2/kg) 

Specific Surface Area C 115-96a(b) 

(Wagner)

 2183 cm2

/g ± 160 cm2/g

 (218 m2

/kg ± 16 m2/kg) 

Sieve Residue (45 μm residue) C 430-96(c) 0.79 % ± 0.19 % 

(a) Standard Test Method for Fineness of Portland Cement by Air Permeability Apparatus [Blaine]. 

(b) Standard Test Method for Fineness of Portland Cement by the Turbidimeter [Wagner]. 

(c) Standard Test Method for Fineness of Hydraulic Cement by the 45 μm (No. 325) Sieve.

Expiration of Certification: The certification of SRM 114q is valid, within the measurement uncertainties 

specified, until 31 December 2016, provided the SRM is handled in accordance with the instructions given in this

certificate (see “Instructions for Use”). This certification is nullified if the SRM is contaminated or otherwise 

modified. 

Maintenance of Certification: NIST will monitor representative samples from this SRM lot over the period of its 

certification. If substantive changes occur that affect the certification before the expiration date, NIST will notify

the purchaser. Registration (see attached sheet) will facilitate notification.

 James St. Pierre, Chief 

 Materials and Construction Research Division 

Gaithersburg, MD 20899 Robert L. Watters, Jr., Chief 

Certificate Issue Date: 24 March 2005 Measurement Services Division

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See Certificate Revision History on Last Page

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The preparation of the material and the coordination of the technical measurements leading to certification were 

performed by C. Ferraris of the NIST Materials and Construction Research Division. 

Statistical consultation on measurement design and analysis of the certification data was performed by W.F. Guthrie

and A.I. Avilés of the NIST Statistical Engineering Division. 

The support aspects involved in the issuance of this SRM were coordinated through the NIST Standard Reference 

Materials Program by B.S. MacDonald of the NIST Measurement Services Division. 

INSTRUCTIONS FOR USE 

Stability and Use: This material is considered to be extremely hygroscopic. Based on measurements in 1993 of

several earlier renewals of SRM 114, the properties certified are stable as long as the foil bag remains sealed. The

specific surface area of cement changes on exposure to the moisture in air. Therefore, this cement should be used

immediately after opening the outer foil bag.

Allow the sealed foil bag to equilibrate to testing temperature before opening. To open the pouch, cut off the end

with scissors. Fluff the cement in accordance with ASTM Standard C204, Section 3.4, allow the cement to settle for 

2 minutes, and then perform the measurement.

Material Selection and Packaging: The desired properties were determined to be generally the same as those

selected for the previous issues of SRM 114; however, in order to better represent current cements, the material

selected for SRM 114q consists of a finer particle size distribution than previously issued. The Cement and 

Concrete Reference Laboratory (CCRL) and NIST identified a plant with suitable cement: Lehigh Cement Company 

(Union Bridge, Maryland)

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 donated 1300 kg of appropriate cement for this SRM. The material selected was Type I 

according to the ASTM C 150 Standard Classification and had a mass fraction of less than 8 % tricalcium aluminate 

(C3A). The material was collected for shipment to NIST directly from the finish mill process stream into bags. 

Upon arrival at NIST, the cement was blended in a V-blender (1.68 m3) and then transferred to 208 L (55 gallon)

drums lined with 0.015 cm (6 mil) polyethylene liners to minimize hydration of the cement in storage prior to

preparation and packaging. Over the next two days, the cement from each drum was sealed in foil bags, each 

containing about 16 kg of cement. The foil bags were stored in a climate-controlled area. The contents of each bag 

were subsequently packaged into vials. The vials were then capped and packaged in boxes of about 500 vials per

box. The boxes were sequentially labeled from 1 to 118. About 5 boxes were filled per day. Nearly 59 000 glass 

vials, each containing approximately 5 g of cement, were produced. Each vial was then individually sealed in a foil

bag. Vials were selected from the lot by stratified random sampling [2] for both homogeneity and certification

analyses. Selected vials were shipped to the participating laboratories for measurements. The remaining vials were

packaged into SRM unit boxes of 20 vials each. 

Homogeneity Assessment and Certification Analyses: Homogeneity testing of the material was performed on

48 random-selected samples. Measurements of the loss of ignition (LoI) showed no reversible moisture take-up by

the cement during packaging. The data received from the round-robin participants were also checked for laboratoryto-laboratory (or day-to-day in the case of sieve residue) variability, box-to-box variability, and vial-to-vial 

variability. No significant box-to-box or vial-to-vial variability was detected except for the Wagner or sieve residue 

tests, and therefore it was determined that the samples were homogeneous for the ASTM measurements. Significant

vial-to-vial variability was observed using the Blaine test and the certified values reflect this source of uncertainty. 

Certification analyses for specific surface areas using ASTM Standard Test Methods C 115-96a and C 204-00 were

performed on two samples at each of the participating laboratories. SRM 114p Portland Cement Fineness Standard

was used for calibration. Raw data were submitted by each laboratory to NIST for tabulation and calculation of 

surface areas, which for the Blaine test, assumed a density of 3.15 g/cm3

. The density was measured twice at NIST: 

the results were 3.255 g/cm3 and 3.248 g/cm3. 

Certification analyses according to ASTM Standard Test Method C 430-96 for the 45 μm sieve residue were

performed at NIST on 40 samples from 20 vials of cement.

Laboratories performing certification analyses are members of the CCRL (http://www.ccrl.us) proficiency program.

The full list is provided in the report describing the details of the certification process [2]. 

 4

Certain commercial equipment, instruments, or materials are identified in this certificate in order to specify adequately

the experimental procedure. Such identification does not imply recommendation or endorsement by the National Institute of 

Standards and Technology, nor does it imply that the materials or equipment identified are necessarily the best available for the

purpose.

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Information Values: NIST information values are considered to be of interest to the SRM user, but are not

certified because insufficient information is available to assess adequately the uncertainty associated with the values

or only a limited number of analyses were performed. Information values for SRM 114q are given in Tables 2 and

3. Table 2 provides the approximate chemical composition determined by ASTM Standard Test Method C114-02.

The analysis of this cement (CCRL Portland Cement Proficiency Sample No. 150) was performed by 70 to 170 

laboratories; the number of participating laboratories depends on the value measured. 

Table 2. Information Values for Chemical Composition 

Compound Mass Fraction Compound Mass Fraction 

 (%) (%) 

 CaO 64.0 K2O 0.70 

 SiO2 20.7 TiO2 0.30 

 A12

O3 4.7 P2O5 0.12 

 Fe2O3 3.2 Na2O 0.07 

 SO3

 2.4 MgO 2.2 

 Loss on Ignition 1.67 

Table 3 provides the calculation of cement compounds according to ASTM C 150-02. 

Table 3. Information Values for Cement Compounds (Calculation from Table 2) 

 Compound Mass Fraction 

 (%) 

 C3S (tricalcium silicate) 60

 C2S (dicalcium silicate) 14

 C3A (tricalcium aluminate) 7 

 C4AF (tetracalcium alumino-ferrite) 10 

REFERENCES 

[1] Taylor, B.N.; Kuyatt, C.E.; NIST Technical Note 1297, Guidelines for Evaluating and Expressing the 

Uncertainty of NIST Measurement Results (1993). 

[2] Ferraris, C.F.; Avilés A.I.; Guthrie W.; Haupt, R.; Certification of SRM 114q; Phase I, NIST SP260-

161 (2005). 

Certificate Revision History: 24 March 2005 (This technical revision corrects the certified values and expanded uncertainties for the 

measurand); 23 March 2005 (Original certificate date).

Users of this SRM should ensure that the certificate in their possession is current. This can be accomplished by 

contacting the SRM Program at: telephone (301) 975-6776; fax (301) 926-4751; e-mail srminfo@nist.gov; or via 

the Internet http://www.nist.gov/srm. 

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