NBS SPECIAL PUBLICATION 260-11 0 

U.S. DEPARTMENT OF COMMERCE/National Bureau of Standards 

Standard Reference Materials: 

Portland Cement Chemical 

Composition Standards 

(Blending, Packaging, and Testing) 

R. Keith Kirby and Howard M. Kanare 
~e National Bureau of Standards' was established by an act of Congress on March 3, 1901. The Bureau's overall 

~ ~oal is to strengthen and advance the nation's science and technology and facilitate their effective application for 

public benefit. To this end, the Bureau conducts research to assure international competitiveness and leadership of U.S. 

industry, science ar.d technology. NBS work involves development and transfer of measurements, standards and related 

science and technology, in support of continually improving U.S. productivity, product quality and reliability, innovation 

and underlying science and engineering. The Bureau's technical work is performed by the National Measurement 

Laboratory, the National Engineering Laboratory, the Institute for Computer Sciences and Technology, and the Institute 

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The National Measurement Laboratory 

Provides the national system of physical and chemical measurement; 

coordinates the system with measurement systems of other nations and 

furnishes essential services leading to accurate and uniform physical and 

chemical measurement throughout the Nation's scientific community, 

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produces, and distributes Standard Reference Materials; provides 

calibration services; and manages the National Standard Reference Data 

System. The Laboratory consists of the followin,2 centers: 

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Provides technology and technical services to the public and private sectors 

to address national needs and to solve national problems; conducts research 

in engineering and applied science in support of these efforts; builds and 

maintains competence in the necessary disciplines required to carry out this 

research and technical service; develops engineering data and measurement 

capabilities; provides engineering measurement traceability services; 

develops test methods and proposes engineering standards and code 

chan,2es; develops and proposes new en,2ineerin,2 practices; and develops 

and improves mechanisms to transfer results of its research to the ultimate 

user. The Laboratory consists of the following centers: 

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Conducts research and provides scientific and technical services to aid 

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operations in accordance with Public Law 89-306 (40 U.S.C. 759), 

relevant Executive Orders, and other directives; carries out this mission by 

mana,2in2 the Federal Information Processin2 Standards Pro,2ram. 

developing Federal ADP standards guidelines, and managing Federal 

participation in ADP voluntary standardization activities; provides scientific 

and technological advisory services and assistance to Federal agencies; and 

provides the technical foundation for computer-related policies of the 

Federal Government. The Institute consists of the following divisions: 

The ln.~titute for Moteri.ols Science. and Engineering 

Conducts research and provides measurements, data, standards, reference 

materials, quantitative understanding and other technical information 

fundamental to the processing. structure. properties and performance of 

materials; addresses the scientific basis for new advanced materials 

technologies; plans research around cross-cutting scientific themes such as 

nondestructive evaluation and phase diagram development; oversees 

Bureau-wide technical programs in nuclear reactor radiation research and 

nondestructive evaluation; and broadly disseminates generic technical 

information resulting from its programs. The Institute consists of the 

following Divisions: 

•Headquarters and Laboratories at Gaithersburg, MD, unless otherwise noted; mailing ·address 

Gaithersburg, MD 20899. 

2Some divisions within the center are loc1tted at Boulder, CO 80::\0':\ 3Located at Boulder, CO, with some elements at Gaithersburg, MD 

• Basic Standards2 

• Radiation Research 

• Chemical Physics 

• Analytical Chemistry 

• Applied Mathematics 

• Electronics and Electrical 

Engineering2 

• Manufacturing En,2ineering 

• Building Technology 

• Fire Research 

• Chemical Engineering3 

• Information Systems Engineering 

• Systems and Software 

Technology 

• Computer Security 

• System and Network 

Architecture • Advanced Systems 

• Ceramics 

• Fracture and Deformation3 

• Polymers 

• Metallurgy 

• Reactor Radiation 
Standard Reference Materials: 

Portland Cement Chemical 

Composition Standards 

(Blending, Packaging, 

and Testing) 

R. Keith Kirby (Retired) 

Office of Standard Reference Materials 

National Measurement Laboratory 

National Bureau of Standards 

Gaithersburg. MD 20899 

and 

Howard M. Kanare 

Construction Technology Laboratories 

Division of the Portland Cement Association 

Skokie, IL 60077 

U.S. DEPARTMENT OF COMMERCE, C. William Verity, Secretary 

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director 

Issued February 1988 
Library of Congress Catalog Card Number: 88-600503 

National Bureau of Standards Special Publication 260-110 

Natl. Bur. Stand. (U.S.), Spec. Publ. 260-110, 103 pages (Feb. 1988) 

CODEN:XNBSAV 

U.S. GOVERNMENT PRINTING OFFICE 

WASHINGTON: 1988 

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402-9325 
TABLE OF CONTENTS 

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

SRMs 177, 1011, 1013, 1014, 1015, and 1016 ....................... 2 

SRMs 633 through 639. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 

General Analytical Techniques .................................... 11 

SRMs 1880 and 1881 ............................................... 23 

Conclusions ...................................................... 34 

Acknowledgements ................................................. 36 

References ....................................................... 3 7 

Appendix A ....................................................... 38 

Appendix B ....................................................... 6 3 

Appendix C ....................................................... 70 

Appendix D ....................................................... 7 5 

Appendix E ....................................................... 7 7 

Appendix F ....................................................... 7 9 

Appendix G ....................................................... 8 2 

LIST OF TABLES 

1. Portland Cement SRMs ........................................ 4 

2. Results of the Homogeneity Tests on the 11 600 Series 11 SRMs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 

3. Results of the Analyses of Si02 ............................. 12 

4. Results of the Analyses of 11R203 11 Group ..................... 13 

5. Results of the Analyses of Fe203 ............................ 14 

fl. 'RPsttl t:~ of t:hP An::Jly~p_~ of Ti02 ......................... 14 

7. Results of the Analyses of P20S··· .......................... 14 

8. Results of the Analyses of ZnO .............................. 15 

9. Results of the Analyses of Cr203 ............................ 15 

10. Results of the Analyses of Al203 ............................ 16 

11. Results of the Analyses of Mn203 ............................ 17 

12. Results of the Analyses of the Calcium Group ................ 17 

13. ResulLs of the Analyses of SrO .............................. 18 

14. Results of the Analyses of MgO .............................. 19 

15. Results of the Analyses of GaO .............................. 19 

16 Result-s of the Analyses of S03 .............................. 20 

17. Results of the Analyses of K20 .............................. 20 

18. Results of the Analyses of Na20 ............................. 20 

19. Results of the Analyses of Fluoride ......................... 21 

20. Results of the Analyses of Ignition Loss .................... 21 

21. Final Results for the "600 Series" SRMs ..................... 22 

22. Homogeneity of Blended Cements, SRM 1880 .................... 24 

23. Prepackaging Homogeneity of SKM 1880 ........................ 2~ 

24. Results of the Analyses of Si02 ............................. 27 

25. Results of the Analyses of the "R203" Group ................. 28 

26. Recultc of the Analycco of Fcz03 ............................ 28 

27. Results of the Analyses of Ti02 ............................. 29 

iii 
28. Results of the Analyses of P205 ............................. 29 

29. Results of the Analyses of Al203 ............................ 29 

30. Results of the Analyses of Mn203 ............................ 30 

31. Results of the Analyses of the Calcium Group ................ 30 

32. Results of the Analyses of SrO .............................. 30 

33. Results of the Analyses of MgO .............................. 31 

34. Results of the Analyses of GaO .............................. 31 

35. Results of the Analyses of S03 .............................. 31 

36. Results of the Analyses of K20 .............................. 32 

37. Results of the Analyses of Na20 ............................. 32 

38. Results of the Analyses of Fluoride ......................... 32 

39. Results of the Analyses of Chloride ......................... 32 

40. Results of the Analyses of Ignition Loss. ____ . ___ .... _ ...... 33 

41. Final Results for SRMs 1880 and 1881 ........................ 33 

C-1 Summary of the Cooperative Test Program on the 

"600 Series" SRMs ........................................... 72 

F-1 Blaine Surface Area ......................................... 80 

F-2 Chemical Analysis of the SRM 1880 Cements 

Before Blending ............................................. 80 

G-1 Description of Flexible Packages as Received ................ 84 

G-2 Appearance of Packages After Tests .......................... 85 

G-3 Effect of High Humidity ..................................... 86 

G-4 Effect of C02 Atmosphere ................................... ~86 

G-5 Effect of Hot Environment ................................... 87 

LISTS OF FIGURES 

1. Relative values for many of the constituents of SRMs 177, 

1011, 1013 through 1016, 633 through 639, 1880, and 1881 .... 3 

2. Si~ving one of the "600 series" portland cements ............ 5 

3. Blending one of the "600 series" portland cements ........... 5 

4. Placing vials in a tray before with cement .................. 6 

5. Capping filled vials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 

6. Flame sealing the outer glass vials ......................... 8 

7. Flow sheet for the definitive analyses of the 

"600 series" SRMs ........................................... 11 

8. Scheme for mixing and blending SRM 1881 ..................... 26 

E-1 Packing case for SRMs 1880 and 1881 ......................... 78 

F-1 Results of particle size analysis of SRMs 1880 and 1881 ..... 81 

G-1 Schematic of typical laminated film ......................... 82 

iv 
Preface 

Standard Reference Materials (SRM's) as defined by the National 

Bureau of Standards (NBS) are well-characterized materials, produced in 

quantity and certified for one or more physical or chemical properties. 

They are used to assure the accuracy and compatibility of measurements 

throughout the Nation. SRM's are widely used as primary standards in 

many diverse fields in science, industry, and technology, both within the 

United States and throughout the world. They are also used extensively 

in the fields of environmental and clinical analysis. In many 

applications, traceability of quality control and measurement processes 

to the national measurement system is carried out through the mechanism 

and use of SRM's. For many of the Nation's scientists and technologists, 

it is therefore of more than passing interest to know the details of the 

measurements made at NBS in arriving at the certified values of the SRM's 

produced. An NBS series of papers, of which this publication is a 

member, called the NBS Special Publication - 260 Series, is reserved for 

this purpose. 

The 260 Series is dedicated to the dissemination of information on 

different phases of the preparation, measurement, certification, and use 

of NBS SRM's. In general, much more detail will be found in these papers 

than is ·generally allowed, or desirable, in scientific journal articles. 

This enables the user to assess the validity and accuracy of the 

measurement processes employed, to judge the statistical analysis, and to 

learn details of techniques and methods utilized for work entailing 

greatest care and accuracy. These papers also should provide sufficient 

additional information not found on the certificate so that new 

applications in diverse fields not foreseen at the time thP- SRM w~s 

originally issued will be sought and found .. 

Inquiries concerning the technical content of this paper should be 

directed to the author(s). Other questions concerned with the 

availability, delivery, price, and so forth, will receive prompt 

attention from: 

Office of Standard Reference Materials 

National Bureau of Standards 

Gaithersburg, MD 20899 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 

v 
OTHER NBS PUBLICATIONS IN TIDS SERIES 

Seward, R. W., ed., NBS Standard Reference Materials 

Catalog 1988-89, NBS Spec. Publ. 260 (January 1988) 

Michaelis, R. E., and Wyman, L. L., Standard Reference 

Materials: Preparation of White Cast Iron 

Spectrochemical Standards, NBS Misc. Publ. 260-1 

(June 1964). COM74-11061** 

Michaelis, R. E., Wyman, L. L., andFlitsch, R., Standard 

Reference Materials: Preparation of NBS CopperBase Spectrochemical Standards, NBS Misc. Publ. 

260-2 (October 1964). COM74-11063** 

Michaelis, R. E., Yakowitz, H., and Moore, G. A., Standard Reference Materials: Metallographic Characterization of an NBS Spectrometric Low-Alloy Steel 

Standard, NBS Misc. Publ. 260-3 (October 1964). 

COM74-11060** 

Alvarez, R., and Flitsch, R., Standard Reference 

Materials: Accuracy of Solution X-Ray 

Spectrometric Analysis of Copper-Base Alloys, NBS 

Misc. Publ. 260-5 (March 1965). PB168068** 

Shultz, J. I., Standard Reference Materials: Methods for 

the Chemical Analysis of White Cast Iron Standards, 

NBS Misc. Publ. 260-6 (July 1965). COM74-

11068** 

Bell, R. K., Standard Reference Materials: Methods for 

the Chemical Analysis of NBS Copper-Base 

Spectrochermical Standards, NBS Misc. Publ. 260-7 

(October 1965). COM74-11067** 

Richmond, M. S., Standard Reference Materials: 

Analysis of Uranium Concentrates at the National 

Bureau of Standards, NBS Misc. Publ. 260-8 

(December 1965). COM74-11066** 

Anspach, S. C., Cavallo, L. M., Garfinkel, S. B., 

Hutchinson, J. M. R., and Smith, C. N., Standard 

Reference Materials: Half Lives of Materials Used in 

the Preparation of Standard Reference Materials of 

Nineteen Radioactive Nuclides Issued by the National Bureau of Standars, NBS Misc. Publ. 260-9 

(November 1965). COM74-11065** 

Y akowitz, H., Vieth, D. L., Heinrich, K. F. J ., and 

Michaelis. R. R. Standard Reference Materials: 

Homogeneity Characterization of NBS Spectrometric 

Standards II: Cartridge Brass and Low-Alloy Steel, 

NBS Misc. Publ. 260-10 (December 1965). COM74-

11064** 

Napolitano, A., and Hawkins, E.G., Standard Reference 

Materials: Viscosity of Standard Lead-Silica Glass, 

NBS Misc. Publ. 260-11 (November 1966). 

vi 

Y akowitz, H., Vieth, D. L., and Michaelis, R. E., Standard Reference Materials: Homogeneity Characterization of NBS Spectrometric Standards III: White 

Cast Iron and Stainless Steel Powder Compact, NBS 

Misc. Publ. 260-12 (September 1966). 

Menis, 0., and Sterling, J. T., Standard Reference 

Materials: Determination of Oxygen in Ferrous 

Materials-SRM 1090, 1091, and 1092, NBS Misc. 

Publ. 260-14 (September 1966). 

Y akowitz, H., Michaelis, R. E., and Vieth, D. L., Standard Reference Materials: Homogeneity Characterization of NBS Spectrometric Standards IV: 

Preparation and Microprobe Characterization of W20% Mo Alloy Fabricated by Powder Metallurgical 

Methods, NBS Spec. Publ. 260-16 (January 1969). 

COM74-11062** 

Paule. R. C .. and Mandel. J .• Standard Reference 

Materials: Analysis of Interlaboratory Measurements 

on the Vapor Pressure of Gold (Certification of Standard Reference Material 745). NBS Spec. Publ. 260-

19 (January 1970). PB190071 ** 

Paule, R. C., and Mandel, J., Standard Reference 

Materials: Analysis of Interlaboratory Measurements 

on the Vapor Pressures of Cadmium and Silver, NBS 

Spec.Publ.260-21(January 1971).COM74-11359** 

Y akowitz, H., Fiori, C. E., and Michaelis, R. E., Standard Reference Materials: Homogeneity Characterization ofFe-3 Si Alloy, NBS Spec. Publ. 260-22 

(February 1971). COM74-11357** 

Napolitano, A., and Hawkins, E. G., Standard Reference 

Materials: Viscosity of a Standard Borosilicate Glass, 

NBS Spec. Publ. 260-23 (December 1970). COM71-

00157** 

Sappenfield, K. M., Marinenko, G., and Hague, J. L., 

Standard Reference Materials: Comparison of Redox 

Standards, NBS Spec. Publ. 260-24 (January 1972). 

COM72-SOOS8"'"' 

Hicho, G. E., Yakowitz, H., Rasberry, S. D., and 

Michaelis, R. E., Standard Reference Materials: A 

Standard Reference Material Containing Nominally 

Four Percent Austenite, NBS Spec. Publ. 260-25 

(February 1971). COM74-11356** 

Martin, J. F., Standard Reference Materials: National 

Bureau of Standards-US Steel Corporation Joint 

Prognam for Determining Oxygen and Nitrogen in 

Steel, NBS Spec. Publ. 260-26 (February 1971). PB 

81176620** 

Gamer, E. L., Machlan, L. A., and Shields, W. R., Standard Reference Materials: Uranium Isotopic Standard 

Reference Materials, NBS Spec. Publ. 260-27 (April 

1971). COM74-11358** 
Heinrich, K. F. J., Myklebust, R. L., ~berry, S.D., and 

Michaelis, R. E., Standard Reference Materials: 

Preparation and Evaluation of SRM's 481 and 482 

Gold-Silver and Gold-Copper Alloys for 

Microanalysis, NBS Spec. Publ. 260-28 (August 

1971). COM71-50365** 

Geller, S. B., StandardRelerence Materials: Calibration 

of NBS Secondary Standard Magnetic Tape (Computer Amplitude Reference) Using the Reference 

Tape Amplitude Measurement "Process A-Model 

2," NBS Spec. Publ. 260-29 (June 1971). COM71-

50282** 

Gorozhanina, R. S., Freedman, A. Y ., and Shaievitch, A. 

B. (translated by M. C. Selby), Standard Reference 

Materials: Standard Samples Issued in the USSR (A 

Translation from the Russian), NBS Spec. Publ. 260-

30 (June 1971). COM71-50283** 

Hust, J. G., and Sparks, L. L., Standard Reference 

Materials: Thermal Conductivity of Electrolytic Iron 

SRM 734 from 4 to 300 K, NBS Spec. Publ. 260-31 

(November 1971). COM71-50563** 

Mavrodineanu, R., and Lazar, J. W., Standard Reference 

Materials: Standard Quartz Cuvettes for High Accuracy Spectrophotometry, NBS Spec. Publ. 260-32 

(December 1973). COM74-50018** 

Wagner, H. L., Standard Reference Materials: Comparison of Original and Supplemental SRM 705, Narrow Molecnlar Weight Distribution Polystyrene, 

NBS Spec. Publ. 260-33 (May 1972). COM72-

50526** 

Sparks, L. L., and Hust, J. G., Standard Reference 

Materials: Thermal Conductivity of Austenitic Stainless Steel, SRM 735 from 5 to 280 K, NBS Spec. Pub I. 

260-35 (April1972.) COM72-50368** 

Cali, J.P., Mandel, J., Moore, L. J., and Young, D. S., 

Standard Reference Materials: A Referee Method for 

the Determination of Calcium in Serum NBS SRM 

915, NBS Spec. Publ. 260-36 (May 1972). COM72-

50527** 

Shultz,J.I.,Bell,R.K.,Rains, T.C.,andMenis,O.,Standard Reference Materials: Methods of Analysis of 

NBS Clay Standards, NBS Spec. Publ. 260-37 (June 

1972). COM72-50692** 

Clark, A. F., Denson, V. A., Host, J. G., and Powell, R. 

L., Standard Reference Materials: The Eddy Current 

Decay Method for Resistivity Characterization of 

High-Purity Metals, NBS Spec. Publ. 260-39 (May 

1972). COM72-50529** 

McAdie, H. G., Gam, P. D., and Menis, 0., Standard 

Reference Materials: Selection of Thermal Analysis 

Termperature Standards Through a Cooperative 

Study (SRM758, 759, 760),NBS Spec. Publ. 260-40 

(August 1972) COM72-50776** 

Wagner, H. L., and Verdier, P. H., eds., Standard 

Reference Materials: The Characterization of Linear 

Polyethylene, SRM 1475, NBS Spec. Publ. 260-42 

(September 1972). COM72-50944** 

Vii 

Y akowitz, H., Ruff, A. W ., and Michaelis, R. E., Standard Reference Materials: Preparation and 

Homogeneity Characterization of an Austenitic IronChromium-Nickel Alloy, NBS Spec. Publ. 260-43 

(November 1972). COM73-50760** 

Schooley, J. F., Soulen; R~:J., Jr., and Evans, G. A., Jr., 

Standard Reference Materials: Preparation and Use 

of Superconductive Fixed Point Devices, SRM 767, 

NBS Spec. Publ. 260-44 (December 1972). COM73-

50037** 

Greifer, B., Maienthal, E. J ., Rains, T. C., and Rasberry, 

S.D., Standard Reference Materials: Powdered LeadBased Paint, SRM 1579, NBS Spec. Publ. 260-45 

(March 1973). COM73-50226** 

Host, J. G., and Giarratano, P. J., Standard Reference 

Materials: Thermal Conductivity and Electrical 

Resistivity Standard Reference Materials: Austenitic 

Stainless Steel, SRM's 735 and 798, from 4 to 1200 

K, NBS Spec. Publ. 260-46 (March 1975). COM75-

10339** 

Host, J. G., Standard Reference Materials: Electrical 

Resistivity of Electrolytic Iron, SRM 797, and Austenitic Stainless Steel, SRM 798, from 5 to 280 K, 

NBS Spec. Publ. 260-47 (February 1974). COM74-

50176** 

Mangum, B. W.~ and Wise, J. A., Standard Reference 

Materials: Description and Use of Precision Thermometers for the Clinical Laboratory, SRM 933 and 

SRM 934, NBS Spec. Publ. 260-48 (May 1974). 

COM74-50533** 

Carpenter, B.S., and Reimer, G. M., Standard Reference 

Materials: Calibrated Glass Standards for Fission 

Track Use, NBS Spec. Publ. 260-49 (November 

1974). COM74-51185** 

Host, J. G., and Giarratano, P. J., Standard Reference 

Materials: Thermal Conductivity and Electrical 

Resistivity Standard Reference Materials: Electrolytic Iron, SRM's 734 and 797 from 4 to 1000 K,NBS 

Spec. Publ. 260-50 (June 1975). COM75-10698** 

Mavrodineo.nu, R., and Baldwin, J. R., Standard 

Reference Materials: Glass Filters As a Standard 

Reference Material for Spectrophotometry-Selec 

tion. Preparation. Certification. Use-SRM 930 NBS 

Spec. Publ. 260-51 (November 1975). COM75-

10339** 

Host, J. G., and Giarratano, P. J., Standard Reference 

Materials: Thermal Conductivity and Electrical 

Resistivity Standard Reference Materials 730 and 

799, from 4 to 3000 K, NBS Spec. Publ. 260-52 (September 1975). COM75-11193** 

Durst, R. A., Standard Reference Materials: Standardization of pH Measurements, NBS Spec. Pub I. 260-

5~ (December 1975. Revised). PB248127** 
Burlce, R. W., and Mavrodineanu, R., Standard 

Reference Materials: Certification and Use of Acidic 

Potassium Dichromate Solutions as an Ultraviolet 

Absorbance Standard, NBS Spec. Publ. 260-54 

(August 1977). PB272168** 

Ditmars, D. A., Cezairliyan, A., Ishihara, S., and 

Douglas, T. B., Standard Reference Materials: Enthalpy and Heat Capacity; Molybdenum SRM 781, 

from 273 to 2800 K, NBS Spec. Publ. 260-55 (September 1977). PB272127** 

Powell, R. L., Sparks, L. L., and Hust, J. G., Standard 

Reference Materials: Standard Thermocouple 

Material, Pt-67: SRM 1967, NBS Spec. Publ. 260-56 

(February 1978). PB277172** 

Barnes, J. D., and Martin, G. M., Standard Reference 

Materials: Polyester Film for Oxygen Gas Transmission Measurements SRM 14 70, NBS Spec;Publ. 260-

58 (June 1979). PB297098** 

Velapoldi, R. A., Paule, R. C., Schaffer, R., Mandel, J., 

and Moody, J. R., Standard Reference Materials: A 

Reference Method for the Determination of Sodium 

in Serum, NBS Spec. Publ. 260-60 (August 1978). 

PB286944** 

Verdier. PH .. and Wagner. H. L .• Standard Reference 

Materials: The Characterization of Linear 

Polyethylene (SRM 1482, 1483, 1484), NBS Spec. 

Publ. 260-61 (December 1978). PB289899** 

Soulen, R. J., and Dove, R. B., Standard Reference 

Materials: Temperature Reference Standard for Use 

Below 0.5 K (SRM 768), NBS Spec. Publ. 260-62 

(April1979). PB294245** 

Velapoldi, R. A., Paule, R. C., Schaffer, R., Mandel, J., 

Machlan, ~· A., and Gramlich, J. W., Standard 

Reference Materials: A Reference Method for the 

Determination of Potassium in Serum, NBS Spec. 

Publ. 260-63 (May 1979). PB297207** 

Velapoldi, R. A., and Mielenz, K. D., Standard 

Reference Materials: A Fluorescence Standard 

Reference Material Quinine Sulfate Dihydrate (SRM 

936), NBS Spec. Publ. 260-64 (January 1980). PB80-

132046** 

Marinenko, R. B., Heinrich, K. F. J ., and Ruegg, F. C., 

Standard Reference Materials: Micro-Homogeneity 

Studies of NBS Stamlan.l Reference Materials, NBS 

Research Materials, and Other Related Samples, NBS 

Spec. Publ. 260-65 (September 1979). PB300461 ** 

Venable, W. H., Jr., and Eclcerle, K. L., Standard 

Reference Materials: Didymium Glass Filters for 

Calibrating the Wavelength Scale of 

Spectrophotometers-SRM 2009, 2010, 2013, and 

2014, NBS Spec. Publ. 260-66 (October 1979). PB80-

104961** 

Velapoldi, R. A., Paule, R. C., Schaffer, R., Mandel, J., 

Murphy, T. J., and Gramlich, J. W., Standard 

Reference Materials: A Reference Method for the 

Determination of Chloride in Serum, NBS Spec. Publ. 

260-67 (November 1979). PB80-110117** 

viii 

Mavrodineanu. R .• and Baldwin. J. R.. Standard 

Reference Materials: Metal-On-Quartz Filters as a 

Standard Reference Material for Spectrophotometry 

SRM 2031, NBS Spec. Publ. 260-68 (April 1980). 

PB80-197486** 

Velapoldi, R. A., Paule, R. C., Schaffer, R., Mandel, J., 

Machlan, L.A., Garner, E. L., and Rains, T. C., Standard Reference Materials: A Reference Method for 

the Determination of Lithium in Serum, NBS Spec. 

Publ. 260-69 (July 1980). PB80-209117** 

Marinenko, R. B., Biancaniello, F., Boyer, P. A., Ruff, 

A. W., and DeRobertis, L., Standard Reference 

Materials: Preparation and Characterization of an 

Iron-Chromium-Nickel Alloy for Microanalysis, 

NBS Spec. Publ. 260-70 (May 1981). PB84-

165349** 

Seward, R. W., and Mavrodineanu, R., Standard 

Reference Materials: Summary of the Clinical 

Laboratory Standards Issued by the National Bureau 

of Standards, NBS Spec. Publ. 260-71 (November 

1981). PB82-135161** 

Reeder, D. J., Coxon, B., Enagonio, D., Christensen, R. 

G., Schaffer, R., Howell, B. F., Paule, R. C., and Mandel. J .• Standard Reference Materials~ SRM 900. Antiepilepsy Drug Level Assay Standard, NBS Spec. 

Publ. 260-72 (June 1981). PB81-220758 

Interrante, C. G., and Hicho, G. E., Standard Reference 

Materials: A Standard Reference Material Containing 

Nominally Fifteen Percent Austenite (SRM 486), 

NBS Spec. Publ. 260-73 (January 1982). PB82-

215559** 

Marinenko, R. B., Standard Reference Materials: 

Preparation and Characterization ofK -411 and K -414 

Mineral Glasses for Microanalysis: SRM 470, NBS 

Spec. Publ. 260-74 (April1982). PB82-221300** 

Weidner, V. R., and Hsia, J. J., Standard Reference 

Materials: Preparation and Calibration of First Surface Aluminum Mirror Specular Reflectance Standards (SRM 2003a), NBS Spec. Publ. 260-75 (May 

1982). PB82-221367** 

Hicho, G. E., and Eaton, E. E., Standard Reference 

Materials: A Standard Reference Material Containing 

Nominally Five Percent Austenite (SRM 485a), NBS 

Spec. Publ. 260-76 (August1982). PB83-115S68** 

Furukawa, G. T., Riddle, J. L., Bigge, W. G., and Pfieffer, E. R., Standard Reference Materials: Application 

of Some Metal SRM' s as Thennometric Fixed Points, 

NBS Spec. Publ. 260-77 (August 1982). PB83-

117325** 

Hicho, G. E., and Eaton, E. E., Standard Reference 

Materials: Standard Reference Material Containing 

Nominally Thirty Percent Austenite (SRM 487), NBS 

Spec. Publ. 260-78 (September 1982). PB83-

115576** 
Richmond,J.C.,Hsia,J.J., Weidner, V.R.,andWilmering, D. B., Standard Reference Materials: Second 

Surface Mirror Standards of Specular Spectral 

Reflectance (SRM's 2023, 2024, 2025), NBS Spec. 

Publ. 260-79 (October 1982). PB84-203447** 

Schaffer, R., Mandel, J., Sun, T., Cohen, A., and Hertz, 

H. S., Standard Reference Ma~als: Evaluation by 

an ID/MS Method of the AACC Reference Method 

for Serum Glucose, NBS Spec. Publ. 260-80 (October 

1982). PB84-216894** 

Burke, R. W., and Mavrodineanu, R., Standard 

Reference Materials: Accuracy in Analytical 

Spectrophotometry, NBS Spec. Publ. 260-81 (April 

1983). PB83-214536** 

Weidner, V. R., Standard Reference Materials: White 

Opal Glass Diffuse Spectral Reflectance Standards 

for the Visible Spectrum (SRM's 2015 and 2016), 

NBS Spec. Publ. 260-82 (April 1983). PB83-

220723** 

Bowers, G. N.,Jr., Alvarez,R., Cali,J. P.,Eberhardt,K. 

R., Reeder, D. J., Schaffer, R., and Uriano, G. A., 

Standard Reference Materials: The Measurement of 

the Catalytic (Activity) Concentration of Seven Enzymes in NBS Human Serum SRM 909, NBS Spec. 

Publ. 260-83 (June 1983). PB83-239509** 

Gills, T. E., Seward, R. W., Collins, R. J., and Webster, 

W. C., Standard Reference Materials: Sampling, 

Materials Handling, Processing, and Packaging of 

NBS Sulfur in Coal Standard Reference Materials 

2682, 2683, 2684, and 2685, NBS Spec. Publ. 260-84 

(August 1983). PB84-109552** 

Swyt, D. A., Standard Reference Materials: A Look at 

Techniques for the Dimensional Calibration of Standard Microscopic Particles, NBS Spec. Publ. 260-85 

(September 1983). PB84-112648** 

Hicho, G. E., and Eaton, E. E., Standard Reference 

Materials: A Standard Reference Material Containing Two and One-Half Percent Austenite, SRM 488, 

NBS Spec. Publ. 260-86 (December 1983). PB84-

143296** 

Mangum, B. W., Standard Reference Materials: SRM 

1969: Rubidium Triple-Point - A Temperature 

Reference Standard Near 39.30 oc, NBS Spec. Publ. 

260-87 (December 1983). PB84-149996** 

Gladney, E. S., Burns, C. E., Perrin, D. R., Roelandts, I., 

and Gills, T. E., Standard Reference Materials: 1982 

Compilation of Elemental Concentration Data for 

NBS Biological, Geological, and Environmental 

Standard Reference Materials, NBS Spec. Publ. 260-

88 (March 1984). PB84-218338** 

Hust, J. G., Standard Reference Materials: A FineGrained, Isotropic Graphite for Use as NBS Thermophysical Property RM's from 5 to 2500 K. NBS 

Spec. Publ. 260-89 (September 1984). PB85-

112886** 

ix 

Hust, J. G., and Lankford, A. B., Standard Reference 

Materials: Update of Thermal Conductivity and 

Electrical Resistivity of Eleetrolytic Iron, Tungsten, 

and Stainless Steel, NBS Spec. Publ. 260-90 (September 1984). PB85-115814** 

Goodrich, L. F., Vecchia, D. F., Pittman, E. S., Ekin, J. 

W., and Clark, A. F.; Standard Reference Materials: 

Critical Current Measurements on an NbTi Superconducting Wire Standard Reference Material, NBS 

Spec. Publ. 260-91 (September 1984). PB85-

118594** 

Carpenter, B. S., Standard Reference Materials: 

Calibrated Glass Standards for Fission Track Use 

(Supplement to NBS Spec. Publ. 260-49), NBS Spec. 

Publ. 260-92 (September 1984). PB85-113025** 

Ehrstein, J.R., Standard Reference Materials: Preparation and Certification of Standard Reference 

Materials /for Calibration of Spreading Resistance 

Probes, NBS Spec. Publ. 260-93 (January 1985). 

PB85-177921** 

Gills, T.E.,Koch, W.F.,Stolz,J. W.,Kelly, W.R.,Paulsen, P. J., Colbert, J. C., Kirklin, D. R., Pei, P.T.S., 

Weeks, S., Lindstrom, R. M., Fleming, R. F., Greenberg, R. R., and Paule, R. C., Standard Reference 

Materials: Methods and Procedures Used at the National Bureau of Standards to Certify Sulfur in Coal 

SRM' s for Sulfur Content, Calorific Value, Ash Content, NBS Spec. Publ. 260-94 (December 1984). 

PB85-165900** 

Mulholland, G. W., Hartman, A. W., Hembree, G. G., 

Marx, E., and Lettieri, T. R., Standard Reference 

Materials: Development of a 1 J.Ull Diameter Particle 

Size Standard, SRM 1690, NBS Spec. Publ. 260-95 

(May 1985). SN003-003-02665-4 * 

Carpenter, B. S., Gramlich, J. W., Greenberg, R. R., 

Machlan, L. A., DeBievre, P., Eschbach, H. L., 

Meyer, H., Van Audenhove, J., Connolly, V. E., 

Trahey, N. M., and Zook, A. C., Standard Reference 

Materials: Unanium-235 Isotopic Abundance Standard Reference Materials for Gamma Spectrometry 

Measurements, NBS Spec. Publ. 260-96 (September 

1986). PB87-108544** 

Mavrodineanu, R., and Gills, T. E., Standard Reference 

Materials: Summary of the Coal, Ore, Mineral, Rock, 

and Refactory Standards Issued by the National 

Bureau of Standards, NBS Spec. Publ. 260-97 (September 1985). SN003-003-026HH-3• 

Hust, J. G., Standard Reference Materials: Glass Fiberboard SRM for Thermal Resistance, NBS Spec. Pub I. 

260-98 (August 1985). SN003-003-02674-3* 

Callanan, J. E., Sullivan, S. A., and Vecchia, D. F., Standard Reference Materials: Feasibility Study for the 

Development of Standards Using Differential Scanning Calorimetry, NBS Spec. Publ. 260-99 (August 

1985). SN003-003-02675-l* 
Taylor, J. K., Standard Reference Materials: Handbook 

for SRM Users, NBS Spec. Publ. 260-100 (September 1985). PB86-110897** 

Mangum, B. W., Standard Reference Materials: SRM 

1970, Succinonitrile Triple-Point Standard: A 

Temperature Reference Standard Near 58.08 oc, NBS 

Spec. Publ. 260-101 (March 1986). SN003-003-

02722-7* 

Weidner, V. R., Mavrodineanu, R., Mielenz, K. D., 

Velapoldi, R. A., Eckerle, K. L., and Adams, B., Standard Reference Materials: Holmium Oxide Solution 

Wavelength Standard from 240- 650 nm, SRM 2034, 

NBS Spec. Publ. 260-102 (July 1986). PB86-

245727** 

Rust, J. G., Standard Reference Materials: Glass 

Fiberblanket SRM for Thermal Resistance, NBS 

Spec. Publ. 260-103 (September 1985). SN003-003-

02687-5* 

Mavrodineanu, R., and Alvarez, R., Standard Reference 

Materials~ Summary of the Biological and Botanical 

Standards Issued by the National Bureau of Standards, NBS Spec. Publ. 260-104 (November 1985). 

SN003-003-02704-9* 

Mavrodineanu, R., and Rasberry, S. D., Standard 

Reference Materials: Summary of the Environmental 

Research, Analysis, and Control Standards Issued by 

the National Bureau of Standards, NBS Spec. Publ. 

260-105 (March 1986). SN003-003-02725-1* 

Koch, W. F., ed., Standard Reference Materials: 

Methods and Procedures Used at the National Bureau 

of Standards to Prepare, Analyze, and Certify SRM 

2694, Simulated Rainwater, and Recommendations 

for Use, NBS Spec. Publ. 260-106 (July 1986). PB86-

247483** 

Hartman, A. W., Standard Reference Materials: SRM 

1965, Microsphere Slide (10 JliD Polystyrene 

Spheres), NBS Spec. Publ. 260-107 (In Preparation). 

Mavrodineanu, R., and Gills, T. E., Standard Reference 

Materials: Summary of Gas Cylinder and Permeation 

Tube Standard Reference Materials Issued by the National Bureau of Standards, NBS Spec. Publ. 260-108 

(May 1987). 

Candela. G. A .. Chandler-Horowitz. D .. Novotny. D. B .. 

Marchiando, J. F., and Belzer, B. J., Standard 

Reference Materials: Preparation and Certification of 

an Ellipsometrically Derived Thickness and Refractive Index Standard of a Silicon Dioxide Film (SRM 

2530), NBS Spec. Publ. 260-109 (In Preparation). 

Kirby, R. K., and Kanare, H. M., Standard Reference 

Materials: Portland Cement Chemical Composition 

Standards (Blending, Packaging, and Testing), NBS 

Spec. Publ. 260-110 

X 

Gladney, E. S., O'Malley, B. T., Roelandts, 1., and Gills, 

T. E., Standard Reference Materials: Compilation of 

Elemental Concentration Data for NBS Clinical, 

Biological, Geological, and Environmental Standard 

Reference Materials, NBS Spec. Publ. 260-111 

(November 1987). 

*Send order with remittance to Superintendent of 

Documents, U.S. Government Printing Office, 

Washington, DC 20102. Remittance from foreign 

countries should include an additional one fourth of 

the purchase price for postage. 

**May be ordered from: National Technical Information Services {NTIS), Springfield, VA 22161. 
INTRODUCTION 

The portland cement Standard Reference Materials (SRMs) are primarily intended 

for use in the calibration of instrumental methods used in the chemical 

analysis of commercial portland cements. When necessary, these SRMs can also 

be used to check the determination of major component concentrations (silica, 

alumina, calcium oxide; and magnesia) by classical chemical methods. 

The National Bureau of Standards (NBS) produced the first portland cement 

standard (SRM 177) in 1958. To meet the needs of the cement industry's growing 

use of instrumental methods of analysis, such as x-ray fluorescence and atomic 

absorption, a series of five standards (SRMs 1011, 1013, 1014, 1015, and 1016) 

was made available in 1962. When this supply was exhausted, it was replaced by 

a new series of seven standards (SRMs 633 through 639) which became available 

in 1973. 

A provisional certificate for these seven SRMs was based on a cooperative test 

program in which 14 laboratories participated, including NBS and the Portland 

Cement Association (PCA). Although eight of these laboratories used "wet 

chemistry" for the major constituents (NBS measurements were made by x-ray 

fluorescence), none of the tests achieved the measurement precision achieved by 

NBS and PCA on the previous series of five SRMs. Accordingly, in 1974 NBS 

placed a contract with PCA to perform, with the aid and consultation of the 

Erlin, Hine Associates, a "definitive analyses" of the seven standards. These 

analyses resulted in the final certification in 1977. 

In 1981 a questionnaire was distributed by the American Society for Testing and 

Materials (ASTM) to the members of its committee on cement, ASTM Committee C-1, 

to solicit suggestions for the chemical composition of two new SRMs. The 

majority of nearly 50 responses to the questionnaire indicated that there was a 

need to fill in some blank areas in the ranges for some constituents, such as 

S03, and to extend the range for some constituents, such as K20. Under 

contract to NBS, the PCA proceeded to obtain, blend, package, and analyze these 

standards. Subsequently, SRMs 1880 and 1881 were certified in 1982 and 1983, 

respectively. 

The purpose of this paper is to present a detailed description of the blending, 

packaging, testing, and characterization of the portland cement SRMs. 

l 
SRMs 177, 1011, 1013, 1014, 1015, and 1016 

While most of the information on these standards was not fully documented, the 

following facts are known: The cements were selected on the basis of analyses 

conducted at NBS by B. Leonard Bean of the Inorganic Building Materials Section 

and were packaged in essentially the same manner as at present--i.e., the 

samples were placed in stoppered glass vials and then flame sealed in outer 

glass vials. Each of these standards took several days to vial with the 

possible result that the water content may have changed between the initial and 

final vialed units due to changes in the ambient relative humidity. This may 

have caused the larger-than-usual variation of the loss-on-ignition values. 

Cooperative testing programs provided the data for certification. In the case 

for SRM 177, thirteen laboratories provided the analyses while ten laboratories 

provided analyses in the "1000 series". In all cases, average values for the 

concentration of the constituents were used for the certification, but only 

after a careful technical and statistical analysis eliminated some values. It 

is interesting to note that the certificates for the "1000 series" SRMs were 

"provisional" which meant that there may have been some doubt about the average 

values. 

Figure 1 presents values for many of the constituents of the portland cement 

standards. Copies of the certificates are shown in Appendix A. 

2 
SRM 1880, 1881 

0'------------------------~~ SRM 633-63Q 

·------------·--·-----~------·-· 

SRM 1880, 1881 

0-----------------0 SRM 633-639 

SRM 1011-1016 ~----------------·----··-·--------·· SRM 1011-1016 

58 

0----------~-----o-----o-------o 

sg 60 61 62 63 

Percent CaO 

SRM 1880, 1881 

O:J 

• SRM177 

64 65 

SRM 633~39 

·--·-··--------------------·----·-· 

66 

SRM 1011-1016 

0------0--0------------~)-------------~ 

• SRM177 

Percent MgO 

SRM 1880, 1881 

!J~ -------0 SRM 633-639 

67 18 

o-----·--o--o----------------------~ 

• SRM177 

19 20 21 22 23 24 

Percent Si02 

SRM 1880, 1881 

o----------------------0 SAM 633~39 

·-·------·-·-·---------·----· 

2 

O----Q-----0-Q-'> SRM 1011-1016 

• SRM177 

Percent Fe203 

SRM 1880, 1881 

0-0 SRM 633-639 

·--·-----·-----··---------·-------------· ··1·---------------------------------· 

0.0 

SRM 1011-1016 

o------------------~--o----o-----------o o---o--o SRM 1011-1016 

• SRM177 • SRM177 

6 

Percent Al203 Percent 503 

SRM 1880. 1881 SRM 1880, 1881 

c-----o o------------o SRM 633~39 

·--·-·----··---· GRM ~3-639 ·--·-·-·-----------------------------·· SRM 1011-1016 

o-------o-o------------------~ 

SRM 1011-1016 

0 o-----o--o--o---------------------o 

0.2 0.4 

Figure 1. 

• SRM177 

0.6 

Percent 1<20 

0.5 

0.8 1.0 1.2 

SRM 1880, 1881 

0------o 

0.0 

• SRM177 

0.1 0.2 

8RM 033-<iJ!I 

·-----·-·-------------· 

o--o-o-o----0 SRM 1011-1o16 

• SRM 177 

1.0 1.5 2.0 2.5 3.0 

Percent Loss-on-Ignition 

0.3 0.4 0.5 

Percent Na20 

3.5 

Relative values for many of the constituents of SRMs 177. 

1011, 1013 through 1016, 633 through 639, 1880, and 1881. 

0.6 

25 

0.7 
SRMs 633 THROUGH 639 

With the approaching depletion of stock of the "1000 series", it became 

necessary to select cements for the replacement series of standards. 

Accordingly, a letter was sent to all cement producers requesting information 

on the chemical composition of portland cements currently being produced. 

Response to this letter was favorable but unfortunately either most of the 

plants had no information on minor constituents or in some cases the 

information supplied was unreliable. The information was sufficient, however, 

to allow Bruce Foster of the NBS Cement and Concrete Research Laboratory to 

select seven cements, see Table 1, including an expansive type portland cement. 

White cements were ruled out because of their virtual absence of iron. 

177 

1011 

1013 

1014 

1015 

1016 

633 

634 

635 

636 

637 

638 

639 

1880 

1881 

Table 1. Portland Cement SRMs Percent by Weight 

64.2 

66.6 

64.3 

63.4 

61.5 

65.3 

64.5 

62.6 

59.8 

63.5 

66.0 

62.1 

65.8 

63.1 

58.7 

21.9 

21.0 

24.2 

19.5 

20~6 

21.0 

21.9 

20.7 

18.4 

23.2 

23.1 

21.5 

21.6 

19.8 

22.2 

5.3 

5.4 

3.3 

6.4 

5.0 

5.0 

3.8 

5.2 

6.3 

3.0 

3.3 

4.4 

4.3 

5.0 

4.2 

2.4 

2.1 

3.1 

2.5 

3.3 

3.7 

4.2 

2.8 

2.6 

1.6 

1.8 

3.6 

2.4 

2.9 

4.7 

1.6 

1.8 

1.8 

2.7 

2.3 

2.3 

2.2 

2.2 

7.1 

2.3 

2.4 

2.3 

2.5 

3.4 

3.6 

2.4 0.2 

1.1 0.1 

1.4 0.1 

2.8 0.3 

4.2 0.1 

0.4 0.2 

1.0 0.3 

3.3 0.1 

1.2 0.2 

4.0 0.0 

0.7 0.1 

3.8 0.1 

1.3 0.2 

2.7 0.1 

2.6 0.1 

0.3 

0.2 

0.2 

0.2 

0.3 

0.3 

0.2 

0.3 

0.3 

0.2 

0.2 

0.2 

0.3 

0.2 

0.2 

0.6 0.1 

0.3 0.1 

0.3 0.2 

1.0 0.2 

0.9 0.2 

0.0 0.6 

0.2 0.6 

0.4 0.2 

0.4 0.1 

0.6 0.1 

0.2 0.2 

0.6 0.1 

0.1 0.6 

0.9 0.3 

1.2 0.0 

1.2 

1.1 

1.0 

0.8 

1.7 

1.2 

0.8 

1.6 

3.2 

1.2 

1.7 

1.0 

1.0 

1.4 

2.0 

Three 94-lb bags of each cement were donated by the producers. Upon receipt, 

the three bags ot cement were sifted through a No. SO wire-cloth sieve to 

remove oversize particles and to break up conglomerates (see Figure 2). The 

cement was then placed in a 4 cubic-foot double cone blender (see Figure 3) and 

mixed for four hours. The cement was then scooped from the blender into 

plastic bags so that all of the bags contained representative samples of the 

mixed cement. The bags were than placed in containers which were sealed and 

set aside until the cement was packaged in vials. 

4 
Figure 2. 

Sieving one of the 

"600 series" portland 

cements. 

5 

Figure 3. 

Blending one of the 

"600 series" portland 

cements. 
Rather than fill the vials one at a time, as in the past, a technique was 

developed in which about 400 vials were placed in a tray (see Figure 4) filled 

with cement, vibrated to settle the cement, and capped (see Figure 5.) 

Figure 4. Placing vials in a tray before filling with cement. 

6 
Figure 5. Capping filled vials. 

Using this technique. the cement for one of the standards could be packaged in 

one day. Packaging was carried out in February when the humidity was low. The 

filled and capped vials were stored in 15 or 16 sealed cans until they could be 

flame-sealed in the outer glass vials. Flame sealing was accomplished with the 

automatic sealer shown in Figure 6. 

The homogeneity of each standard was tested by comparing the calcium and sulfur 

variation between two vials taken from each of the containers. The 32 

specimens were prepared by briquetting and were then analyzed (repeating each 

measurement four times) by normal x-ray fluorescence methods. The data 

obrainPn in these tests are given in Appendix B and are summarized in Table 2. 

The data indicate that each of the cement standards was sufficiently 

homogeneous. The reason for measuring the variations of the calcium and sulfur 

content is that in the production of portland cement, gypsum (which contains 

most of the sulfur) is added to and ground with the cement clinker (which 

contains calcium, the most abundant element) to help control the setting time 

of the concrete. Therefore, if these elements are homogeneously distributed in 

t:he st:andards, iL is a guuu iudication that the mixiug was cumtJleLe aud LhaL 

the other constituents are also uniformly distributed. 

7 
Figure 6. Flame sealing the outer glass vials. 

As with the earlier SRMs, a cooperative test program was set up involving NBS, 

PCA, the Army Corps of Engineers, and ten cement manufactures. ·fhese 13 

laboratories are listed in Appendix C along with a comparative summary of their 

results prepared by William G. Hine*. The methods used were primarily 

instrumental with the "1000 series" used for calibration. Only two 

laboratories performed wet analytical procedures that were considered to be 

reasonably accurate, according to and using methods specified in ASTM Cll4, 

Standard Methods for Chemical Analysis of Hydraulic Cement [1]. Even in these 

* Erlin, Hine Associates 

811 Skokie Boulevard 

Northbrook, IL 60062 

8 
tests however corrections were not made for in~omplete separations. Five 

other' laborato~ies used shortO:.cut modifications of 'the ASTM'· standard methods. 

One laboratory used the Jugovic [2] method which is a combination of 

colorimetric and complexometric methods in which the samples are fused with 

sodium hydroxide and then dissolved in hydrochloric acid. Seven laboratories, 

including NBS, used x-ray fluorescence techniques in which all but one used 

pelletized samples. That laboratory fused the cements with lithium borate: 

Two laboratories used atomic absorption techniques in which the cements are 

fused with lithium metaborate and then dissolved in nitric acid [3]. 

Table 2. Results of the Homogeneity Tests on the "600 Series" SRMs 

CaO so3 

SRM n Std Dev Coef of Var Std Dev Coef of Var 

633 32 0.069% by wt. 0.105% 0.015% by wt. 0.67% 

634 32 0.057 0.091 0.012 0.56 

635 32 0.094 0.158 0.028 0.40 

636 30 0.111 0.176 0.019 0.82 

637 30 0.085 0.129 0.011 0.47 

638 30 0.077 0.124 0.016 0.68 

639 29 0.115 0.175 0.020 0.79 

The results of this cooperative test program were used for the "provisional" 

certification of the "600 series" in 1974 (see Appendix C). More than 3000 

individual determinations were reported for the constituents in the seven SRMs. 

The certified values were obtained by a critical evaluation of the analytical 

methods and the reported data. Because the results of this test program did 

not provide the accuracy necessary to meet the needs of an ASTM method of 

analysis, NBS contracted with PCA (with William G. Hine acting as consultant) 

to provide for the "definitive analyses" of these SRMs. For this work, wet 

chemistry techniques were used to provide the basic measurement of the major 

components and instrumental techniques were used not only to measure the lesser 

components but to also determine impurity levels in the precipitates and 

filtrates to provide corrections for the wet chemistry results. 

In general, x-ray fluorescence (XRF) and atomic absorption spectroscopy (AAS) 

techniques were used. The particular XRF employed allowed dete~tion of 

elements of atomic number 12 (magnesium) and above with greatly varying 

sensitivity. Limited· experimentation with various precipitates indicated the 

detection limits to range from 0.4 milligram for magnesium oxide (equivalent to 

0.08 percent in the SRM), to 0.2 milligram for silica (0.04 percent), to less 

than 0.01 milligram (0.02 percent) for elements of the fourth period of the 

Periodic Table of Elements. 

AAS was employed where the sensi-tivity of this technique allowed detection of 

0.1 milligram (0.02 percent) of a constituent. Analyses for sodium and 

potassium, for example, were frequently made by this technique. Because of its 

suitability for analyzing liquids, AAS was also used to examine the filtrates 

from each precipitation step. By the use of standard addition techniques, it 

was demonstrated that a sensitivity of 0.1 milligram (0.02 percent) was 

achievable for the analyzed elements. 

9 
Finally, optical emission spectroscopy (capable of detecting elements in the 

parts per million or less level) was employed in a few instances (e.g., the 

ammonium hydroxide group precipitate of SRM 635). This method was used as 

check on the XRF results. 

10 
GENERAL ANALYTICAL TECHNIQUES 

The scheme of the analytical program is shown.in Figure 7. A 0.5-g sample was 

used in all cases. Newly opened vials of the SRM were used for determinations 

of all the major components. For minor components, previously opened vials 

were occasionally used. 

~ SAM Cement C0.5 gram sample; dt.'Composition and dissolution by hydrocnloric acid).l 

I 

I Double dehydration of the cement solution to precipitate out the Si02 • J 

I PRECIPITATE of impure Si02 • Fll TRATE contains remaining cement elements. 

X-ray fluorescence (XRF) analysis used to det~t im· Colorimetric analysis used to determine unprecipi· 

puritiC$ in the precipitate. tated (soluble) Si02 in filtrate. 

I .. HF" treatment of Si02 precipitate removes Si02 

.(by evolution as SiF4 ). 

fh::oldue remain5 (wntain5 the i'1•JJuriti=). 

I RESIDUE ignited, weighed, fused, and added to fil· 

trate from dehydration. 

I 

I 

I Double precipitation of NH4 0H (R2 0 3 ) group J (AI:z03 , Fe2 0 3 , P2 0 5 , Ti02 , ZnO, Cr2 0 3 , and ZrOI. 

I PRECIPITATE ignited and weighed as R2 0 3 group. FILTRATE contains CaO, MgO, Mn2 0 3 , K2 0, Na2 0, 

Sro, S03 , etc. I .X-ray fluorescence analysis used to detect ZnO, Atomic absorption analysis used to detect unprecipi· 0 2 0 3 , Zr and other impurities. tated Al:z03 and Fe2 0 3 • 

l Removal of manganese (by co-precipitation method of Peck) prior to the calcium J group determination. 

I PRECIPITATE of Mn02 discarded. FILTRATE (contains CaO, MgO, K2 0, Na 2 0, $0 3 , 

No XRF analysis for impurities performed because etc.) Atomic absorption analysis used to detect un· 

P"ecioitate was too small. precipitated manoanese 

I Double precipitation of calcium group (CaO and SrO) with ammonium oxalate. J 

I PRECIPITATE ignited and weighed as CaO and SrO. Fll TRATE (contains MgO, K2 0, Na2 0, $0 3 , etc.) 

Atomic absorption analysis used to determine the Atomic absorption analysis used to detect unprecipi· 

&mount of SrO in pr{'('ipitatf"_ tatod CaO. 

I Double precipitation of magnesium (as magnesium ammonium phosphate). J 

I PRECIPITATE ignited i1nd weil)hcd as M!J:!P2 0 7 • fll TRATE (cont<~ins K2 0, Na2 0, S0 3 , etc. I Impurities such as CaO detected IJy XRF. Atomic i1b· 

IOI'ption used to determine amount of CiiO in prccipi· Atomic ai.Jsorption an.1lysis usct.l to detect unprccipi· 

. tJte. tated CclO ilnU M!]O in the filtrate . 

Figure 7. Flow sheet for the analyses of the "600 series" SRMs. 

11 
Silica 

Si02 was determined by classical double dehydration techniques given in the 

ASTM Cll4 method. After dissolution of the sample, silicic acid is dehydrated 

by fuming with an appropriate acid. The solution is filtered and the silica is 

ignited, weighed, and then volatilized with hydrofluoric acid (HF). The 

residue is ignited and weighed; the loss in weight represents silica. The 

results of these analyses are presented in Table 3. Because the substances 

remaining after "HF" treatment are re-introduced into the filtrate from the 

silica precipitate, and since silica is determined by "difference", 

contaminants have little or no effect on the analysis. Nevertheless, two sets 

of silica precipitates were examined qualitatively by XRF techniques. 

Aluminum, chromium, iron, and titanium were detected in some precipitates. No 

significant error is apparent resulting from these contaminants. 

The presence of small amounts of fluoride (less than about 0.3 percent) or 

boron (less than 0.1 percent) will not cause significant errors by 

volatilization during ignition of the silica precipitate prior to "HF" 

treatment. Since these SRMs contain 0.08 percent or less of fluoride and less 

than 0.01 percent boron, very little error is likely to result. 

Table 3. Results of the Analyses of Si02, % by wt. 

Gravimetric AAS 

SRM Average n Std Dev Average n Std Dev 

633 21.88 7 0.023 21.88 5 0.062 

634 20.73 8 0.024 20.79 5 0.091 

635 18.41 9 0.030 18.37 5 0.065 

636 23.22 10 0.024 23.29 5 0.078 

637 23.07 9 0.046 23.09 5 0.078 

638 21.48 7 0.035 21.51 5 0.049 

639 21.61 7 0.034 21.63 5 0.116 

An extensive analytical program to detect and quantitate silica rema1n1ng in 

the filtrate was undertaken using procedures based on the "molybdenum blue" 

method. In every case, the optical absorbance of the sample "blank" solution 

was at least three fourths of that of the sample indicating that the amount of 

silica unprecipitated is less than 0.02 percent. 

XRF analyses of the ammonium hydroxide ("R203") group precipitate, and of the 

calcium and magnesium precipitates, did not detect silica at a detection limit 

of 0.04 percent. 

Atomic absorption results, also shown in Table 3, are in good agreement with 

the gravimetric data. 

"R2Q3" Group (Aluminum. Iron. Phosphorus. Titanium. Chromium and Zinc) 

The combined group, "R203", was determined by the classical double 

precipitation method given in ASTM Cll4 using ammonium hydroxide as 

precipitant--followed by ignition to convert all elements to the oxide form. 

12 
The solutions from the silica determination, after combining with residue from 

the "HF" volatilization step, were used for this analysis. The data are given 

in Table 4. 

Table 4. Results of the Analyses of the "R2o3n Group, % by wt. 

SRM Average n Std Dev 

633 8.47 3 0.076 

634 8.54 3 0.053 

635 9.40 4 0.043 

636 4.92 4 0.071 

637 5.55 4 0.062 

638 8.42 3 0.053 

639 7.09 3 0.023 

Two sets of mixed oxide precipitates were analyzed by XRF spectroscopy. The 

group members aluminum, iron, titanium, zinc, and chromium, were detected in 

all the specimens. Zirconium was detected in six of the samples; calcium in 

two, and nickel possibly in one. Phosphorus is known to be present in all the 

precipitates, but analysis for it was not carried out. 

Using standard addition techniques, reanalysis by XRF indicated that the 

quantities of nickel present were less than 0.01 percent. Using AAS 

procedures, and standards prepared to contain amounts of iron and aluminum 

approximately equal to those in the sample, the amounts of calcium, magnesium, 

potassium, and sodium oxides in the precipitates were found to be less than 

0.01 percent. 

Because of questionable aluminum data for SRM 635 (to be discussed later), the 

precipitate for this sample was also analyzed by optical emission 

spectrographic methods. The only impurity of consequence was silicon. 

However, since the soluble silica data revealed no unusual amounts of silica in 

the solution from the silica removal step, this interference is small (0.02 

p~rc~nt or l~ss). 

One set of filtrates from the "R203" group precipitate step was analyzed by AAS 

methods for aluminum and iron. These elements were not detected in the 

filtrate - indicating complete precipitation. 

Iron Oxide 

Fe203 was determined on separate samples by the volumetric titration method 

given in ASTM Cll4 standard methods of analysis. These data are given in Table 

5. The values reported are verified by the AAS data. It is noted that both 

methods give similar results. 

13 
Table 5. Results of the Analyses of Fe203, % by wt. 

Volumetric AAS 

SRM Avera~e n Std Dev Avera~e n Std Dev 

633 4.20 3 0.006 4.25 5 0.019 

634 2.84 3 0.010 2.87 5 0.022 

635 2.61 3 0.012 2.63 5 0.017 

636 1.61 3 0.006 1.62 5 0.011 

637 1.80 3 0.006 1.81 5 0.015 

638 3.55 3 0.000 3.58 5 0.030 

639 2.40 3 0.000 2.40 5 0.016 

Titania 

Ti02 was determined on separate samples by a colorimetric method using Tiron 

reagent, as developed by others and refined for cement by Jugovic. The data 

are given in Table 6. The Tiron method is more sensitive than the classical 

peroxide method given in ASTM Cll4. 

Table 6. Results of the Analyses 

of Ti02, % by wt. 

SRM Avera~e n Std Dev 

633 0.238 3 0.003 

634 0.293 3 0.004 

635 0.319 3 0.006 

636 0.178 3 0.006 

637 0.210 3 0.005 

638 0.252 3 0.004 

639 0.316 3 0.003 

Phosphorus Oxide 

P205 was determined on separate samples by the "molybdenum blue" colorimetric 

method given in the ASTM standard method. The data are given in Table 7. 

Table 7. Results of the 

Analyses of P205, % by wt. 

SRM Avera~e n Std Dev 

633 0.238 3 0.002 

634 0.095 3 0.001 

635 0.169 3 0.001 

636 0.084 3 0.001 

637 0.244 3 0.001 

638 0.062 3 0.001 

639 0.082 3 0.001 

14 
Zinc Oxide 

ZnO was determined on separate samples by AAS,, using a standard addition 

technique [4]. The values are given in Table 8. 

Chromium Oxide 

T~hle R. Results of the 

Analyses of ZnO, % by wt. 

SRM Average n Std Dev 

633 0.005 1 

634 0.024 1 

635 0.007 1 

636 0.027 1 

637 0.012 1 

638 0.095 2 0.007 

639 0.007 1 

Cr203 was determined on separate samples by AAS, using a standard addition 

technique [4]. The data are given in Table 9. 

Alumina 

Table 9. Results of the 

Analyses of CrzOJ, % by wt. 

SRM Average n Std Dev 

633 0.008 2 0.001 

634 0.076 2 0.001 

635 0.005 2 0.000 

636 0.006 2 0.001 

637 0.010 2 0.001 

638 0.010 2 0.000 

639 0.005 2 0.000 

Al203 was determined by difference ("R203" percent minus "X203" percent), 

subtracting the amounts of iron, titanium, phosphorus, zinc, and chromium 

oxides from the ammonium hydroxide group total. The data are given in Table 

10. Alumina was also determined by AAS and the values are in good agreement 

(generally within 0.02 percent) except for SRM 635 which differs by 0.16 

percent. 

15 
Table 10. Results of the Analyses of Al203, % by wt. 

Determination b~ Difference AAS 

SRM "R2Q3~ "X2Q3~ Al2Q3 Std Dev Average n Std Dev 

633 8.47 4.69 3.78 0.062 3.79 5 0.029 

634 8.54 3.33 5.21 0.044 5.18 5 0.044 

635 9.40 3.11 6.29 0.038 6.13 5 0.052 

636 4.92 1.90 3.02 0.062 3.07 5 0.029 

637 5.55 2.27 3.28 0.054 3.24 5 0.015 

638 8.42 3.97 4.45 0.044 4.48 5 0.026 

639 7.09 2.81 4.28 0.019 4.29 5 0.023 

An extensive analytical program was carried out to determine a cause for this 

large difference. Several "R203" precipitates for this sample were analyzed by 

XRF spectroscopy in the hope of disclosing previously undetected components. 

None were detected. Similar analyses were made by optical emission 

spectroscopy. In this case, other elements were detected--boron, vanadium, 

copper, lead, tin, nickel, molybdenum, and silver. However, the amount of each 

of these elements present was much less than 0.01 percent. 

The possibility of interference in either gravimetric or atomic absorption 

methods by the large amounts of sulfate exists, but experiments designed to 

determine the effect of sulfate on the atomic absorption intensities for 

aluminum failed to disclose significant interference. 

Manganese Oxide 

Mn203 was determined on separate samples by AAS. The data are given in Table 

11. Experience indicates that the atomic absorption analysis for manganese in 

cement is much more precise and accurate than that given by the method in ASTM 

Cll4. 

Prior to the calcium group determination, manganese was not removed by the 

usual bromine oxidation procedure because it was found that substantial amounts 

of manganese (particularly in SRM 635) remained in solution until the calcium 

precipitation step. When this manganese was detected in the calcium oxide 

precipitate, a search was made for a more quantitative method for its removal. 

The coprecipitation (or zirconium collector) method of Peck [5] was found to be 

excellent, and was used for succeeding analyses. The method removes the 

manganese prior to the calcium determination step by coprecipitating it with 

zirconium hydroxide. 

Manganese separated by the method of Peck was determined by dissolution and 

quantitation by AAS using pure manganese standards. The results are also 

listed in Table 11. These data show that only a small amount of manganese is 

lost by the Peck procedure. Some is undoubtedly entrapped in the mixed oxide 

group ("R203") precipitate and some remains unprecipitated until the calcium or 

magnesium steps. 

16 
Table 11. Results of the Analyses of Mn2o3, % by wt. 

Se~arate Sam~les Recovered Sam:Qles 

SRM Avera&e n Std Dev Avera&e n Std Dev 

633 0.04 3 0.006 0.03 2 0.000 

634 0.28 3 0.006 0.26 2 0.028 

635 0.09 3 0.000 0.07 4 0.017 

636 0.12 3 0.006 0.11 3 0.000 

637 0.06 3 0.000 0.04 4 0.006 

638 0.05 3 0.000 0.04 4 0.006 

639 0.08 3 0.006 0.07 4 0.000 

Calcium Group_ 

CaO (+ SrO) was determined by the classical double precipitation method 

employing oxalate. Most of the strontium is also precipitated in this 

procedure, and the term "calcium group" is applied. The results are given in 

Table 12. 

Table 12. Results of the Analyses 

of Calcium Group, % by wt. 

SRM Average n Std Dev 

633 64.75 6 0.047 

634 62.65 5 0.072 

635 59.98 6 0.047 

636 63.53 8 0.057 

637 66.10 5 0.126 

638 62.11 5 0.087 

639 65.85 6 0.072 

Analyses of the calcium group precipitate, after removal of manganese by the 

Peck method, were made by XRF spectroscopy. No manganese was found in the 

precipitates. 

The filtrate from the calcium group precipitation step was analyzed for calcium 

by AAS. Calcium was detected, but because of the large amounts of ammonium 

salts, quantitative analysis could not be easily made. However, since calcium 

appeared in the magnesium precipitate, analysis of the latter was chosen as the 

more suitable method for determining the unprecipitated calcium. 

Strontium Oxide 

SrO was determined on separate samples by the use of AAS. The date are given 

in Table 13. There is no ASTM Cll4 method for the determination of strontium. 

The ignited oxide precipitates of the calcium group were dissolved in acid and 

strontium determined by AAs using standards containing approximately equivalent 

amounts of calcium and acid. The data, also given in Table 13, suggest that 

17 
the calcium group precipitation step is not quantitative for SrO. 

Table 13. Results of the Analyses of SrO, % by wt. 

Se~arate Sam~les GaO Preci~itate 

SRM Average n Std Dev Average n Std Dev 

633 0.31 3 0.006 0.28 4 0.013 

634 0.12 3 0.010 0.11 4 0.008 

635 0.21 3 0.010 0.18 4 0.006 

636 0.04 3 0.000 0.04 5 0.000 

637 0.09 3 0.006 0.08 4 0.005 

638 0.07 3 0.006 0.06 4 0.010 

639 0.15 3 0.006 0.12 4 0.015 

Magnesia 

MgO wa~ dP-~P-rmin~d by the classical double precipitation method using ammonium 

phosphate, with ignition to the pyrophosphate. The analytical data are given 

in Table 14. It is noted that these values are useful for comparison with ASTM 

Gll4 results. However, the inclusion of calcium in the precipitate (as noted 

above) causes these data to be slightly erroneous. 

The magnesium oxide precipitates were analyzed by XRF spectroscopy. Small 

amounts of calcium were detected in each. The precipitates were dissolved in 

acid and analyzed by AAS, using standard solutions containing approximately 

equivalent amounts of magnesium and acid. The amounts of calcium determined 

(0.02 to 0.04 percent) were used to correct both the calcium and magnesium 

values. 

The percent of GaO in MgO in Table 15 must be multiplied by the appropriate 

conversion factor (0.6674) before it is used for correcting the MgO value in 

Table 14. The reason for this is as follows: Calcium occurs in the Mg2P207 

precipitate as calcium phosphate, Ca3(P04)2. The w~ight of calcium oxide in 

the Mg2P207 (as determined by AAS) is multiplied by 1.8437. This value is 

subtracted from the weight of Mg2P207 before the percent MgO is calculated. 

The factor 1.8437 is obtained by dividing the molecular weight of Ca3(P04)2 by 

3 times the molecular weight of calcium oxide. 

The filtrate from the magnesium precipitation step was analyzed by AAS for 

calcium and magnesium. While neither was detected, the severe interference of 

large amounts of ammonium ion in the filtrate makes this determination 

uncertain. 

18 
Table 14. Results of the Analyses of MgO, % by wt. 

G:t:a.Yime:tric CaO in AAS 

SRM Average !! Std Dev MgO Difference Average !! Std Dev 

633 1.06 4 0.026 0.02 1.04 1.07 5 0.012 

634 3.33 5 0.023 0.03 3.30 3.39 5 0.022 

635 1.26 3 0.053 0.03 1.23 1.28 5 0.011 

636 3.98 6 0.035 0.03 3.95 3.99 5 0.020 

637 0.68 3 0.031 0.01 0.67 0.71 5 0.004 

638 3.86 5 0.059 0.03 3.83 3.88 5 0.030 

639 1.28 5 0.030 0.02 1.26 1.30 5 0.007 

AAS data are also given in Table 14 for comparison purposes. The results 

obtained are slightly higher than the corrected gravimetric results. The 

reason for this difference is not known for certain, but may be due to small 

positive errors in the MgO certified values of the "1000 series" SRMs which 

were used to prepare the AAS calibration curves. 

Calcium Oxide 

CaO was determined by "difference" (calcium group minus the strontium 

determined in the group precipitates). To this net calcium oxide must be added 

the amount that was unprecipitated. Fortunately, it is coprecipitated with 

magnesium, and can be determined. This determination was discussed above under 

the magne'sium oxide determination. However, this correction is not made during 

an ASTM Cll4 referee analysis, and thus for comparative purposes, "uncorrected11 

data, as well as corrected data need to be reported. These data are given in 

Table 15 along with the calcium oxide values determined by AAS. These values 

agree with the corrected CaO values. 

Table 15. Results of the Analyoco of CaO, <e by wt. 

SrO Uncor- CaO 

+ rected in AAS. 

SRM CaO SrO CaO MgQ_ CaO Std Dev Average n Std Dev 

633 64.75 0.28 64.47 0.03 64.50 0.044 64.53 5 0.14 

634 62.65 0.11 62.54 0.04 62.58 0.065 62.70 5 0.14 

635 59.98 0.19 59.79 0.04 59.83 0.043 59.77 5 0.11 

636 63.53 0.04 63.49 0.05 63.54 0.050 63.57 5 0.16 

637 66.10 0.08 66.02 0.02 66.04 0.113 66.05 4 0.14 

638 62.11 0.06 62.05 0.04 62.09 0.078 62.08 5 0.12 

639 65.85 0.12 65.73 0.03 65.76 0.067 65.70 5 0.10 

Sulfur Trioxide 

S03 was determined on separate samples by ASTM Cll4 referee method (using a 

precipitation with barium chloride) and as total sulfur (using an induction 

furnace to evolve sulfur oxides, which were determined by titration). These 

results are listed in Table 16. 

19 
Since silica and iron are reported to cause interference under certain 

circumstances with the determination of S03, a procedure in which most of the 

silica and the ammonium hydroxide group elements were removed (either by 

dehydration or by precipitation with ammonia) was used before precipitation of 

sulfur as barium sulfate. 

The agreement of results between the gravimetric and the total sulfur, except 

for SRM 635, indicates that no significant sulfide sulfur exists in the SRMs. 

An ASTM Cll4 sulfide determination was made on SRM 635 and none was found. 

Table 16. Results of the 

Analyses of S03, % by wt. 

SRM Average n Std Dev Average n Std Dev 

633 2.20 2 0.000 2.20 3 0.046 

634 2.21 2 0.028 2.18 3 0.012 

635 7.07 2 0.028 7.23 3 0.115 

636 2.31 2 0.000 2.30 2 0.042 

637 2.38 2 0.014 2.40 2 0.021 

638 2.34 2 0.021 2.37 2 0.014 

639 2.48 2 0.021 2.46 2 0.000 

Potassium and Sodium Oxides 

These alkalies were determined on separate samples by AAS. The results are 

given in Tables 17 and 18. Atomic absorption was selected as a matter of 

convenience. This method and flame photometry, as designated in ASTM Cll4, 

should give comparable results. 

Table 17. Results of the Table 18. Results of the 

Analyses of K20, % by wt. Analyses of Na20, % by wt. 

SRM Average n Std Dev SRM Average n Std Dev 

633 0.17 5 0.000 633 0.64 5 0.010 

634 0.42 5 0.007 634 0.15 5 0.005 

635 0.45 5 0.004 635 0.07 5 0.005 

636 0.59 5 0.009 636 0.11 5 0.004 

637 0.25 5 0.005 637 0.15 5 0.004 

638 0.59 5 0.005 638 0.13 5 0.004 

639 0.06 5 0.000 639 0.65 5 0.004 

Fluoride 

Fluorine (as fluoride ion) was determined on separate samples by an ionselective electrode procedure developed at PCA by W.F. Mivelaz [6], in which a 

calomel reference electrode, a specific ion meter, and two standard fluoride 

solutions (0.01 and 0.10 percent fluorine) are used. In this procedure, the 

sample is dissolved in an acidified alum solution and the fluoride ion is freed 

by the addition of sodium citrate which complexes the aluminum. The results 

are given in Table 19. 

20 
Table 19. Results of the Analyses 

of Fluoride, % by wt. 

SRM Average n Std Dev 

633 0.08 4 0.000 

634 0.08 4 0.006 

635 0.04 4 0.006 

636 0.06 4 0.006 

637 0.04 4 0.005 

638 0.04 4 0.005 

639 0.02 3 0.000 

To determine if boron would interfere, known amounts of boric acid were 

introduced into some samples. No interference was observed. 

Miscellaneous Element 

Determinations of barium, boron, chloride, and zirconium were made on separate 

samples. All were less than 0.01 percent. 

Ignition Loss 

Loss-on-ignition (1000 °C for 30 minutes) was determined on separate samples 

using the ASTM Cll4 method. The data are given in Table 20. 

Summary 

Table 20. Results of the Analyses 

of Ignition Loss, % by wt. 

SRM Average n._ Std Dev 

633 0.75 3 0.006 

634 1.62 3 0.036 

635 3.24 3 0.017 

636 1.16 3 0.026 

637 1.69 3 0.055 

638 0.95 3 0.036 

639 1.00 3 0.025 

The results of all analyses are given in Table 21 along with the pooled 

standard deviations for the seven cements. These pooled standard deviations 

were determined as 

where it was assumed that the prec1s1on was the same for all of the cements. 

These results formed the basis for the certification of SRMs 633 through 639. 

21 
Table 21. Final Results for the "600 Series" SRMs, % by wt. 

Component SRM sP 

633 634 635 636 637 638 639 

CaO 64.50 62.58 59.83 63.54 66.04 62.09 65.76 0.07 

Si02 21.88 20.73 18.41 23.22 23.07 21.48 21.61 0.03 

Al203 3.78 5.21 6.29 3.02 3.28 4.45 4.28 0.06 

Fe203 4.20 2.84 2.61 1.61 1.80 3.55 2.40 0.01 

so3 2.20 2.21 7.07 2.31 2.38 2.34 2.48 0.02 

MgO 1.04 3.30 1.23 3.95 0.67 3.83 1.26 0.04 

K20 0.17 0.42 0.45 0.59 0.25 0.59 0.06 0.01 

Ti02 0.24 0.29 0.32 0.18 0.21 0.25 0.32 0.01 

Na20 0.64 0.15 0.07 0.11 0.15 0.13 0.65 0.01 

SrO 0.31 0.12 0.21 0.04 0.09 0.07 0.15 0.01 

Pzo.J 0. 21, 0.10 0.17 0.08 0. 2ft 0.06 0.08 <0.01 

Mn203 0.04 0.28 0.09 0.12 0.06 0.05 0.08 0.01 

F 0.08 0.08 0.04 0.06 0.04 0.04 0.02 0.01 

ZnO 0.01 0.02 0.01 0.03 0.01 0.10 0.01 <0.01 

Cr203 0.01 0.08 0.01 0.01 0.01 0.01 0.01 <0.01 

Ign Loss 0.75 1.62 3.24 1.16 1.69 0.95 1.00 0.04 

Total 100.1 100.0 100.0 100.0 100.0 100.0 100.2 

Sp is the pooled standard deviation for the seven SRMs. 

22 
SRMs 1880 and 1881 

It became apparent that for the portland cement SRMs to be more useful to the 

cement industry in calibrating instrumental mefhods, some new standards should 

be certified with compositions that either filled in some blank areas in the 

composition ranges or extended them (see Figure 1). Accordingly, a 

questionnaire was distributed to members of ASTM Committee C-1 on Cement that 

solicited suggestions for the chemical composition of two new SRMs. A copy of 

the letter is reproduced in Appendix D. The majority of nearly 50 responses 

expressed the following desires: 

1. so3 content should be greater than 2.50%, preferably near 

3.00% or 3.50%. 

2. K20 content should be between 0.6% and 1.0%. 

3. Na20 content should be between 0.2% and 0.6%. 

4. MgO content should be approximately 2.5% or 5.0%. 

5. Fe203 content should be approximately 3.25% or 5.0%. 

6. Al203 content should be approximately 4.8% or 5.2%. 

7. Si02 content should be approximately 20% or 22%. 

8. CaO content should be approximately 63% or greater than 66%. 

A few respondents requested a low-iron, high-alumina cement, while a few other 

respondents wanted higher levels of trace elements (such as Cr, Zn, and Mn) 

than appeared in the "600 series" SRM. Several respondents suggested use of 

cements with which they were familiar, none of which appeared to satisfy the 

majority's requests. Therefore, it was decided to locate two or more cements 

that either alone or blended together would meet the needs of the majority of 

surveyed respondents. 

After evaluating typical analyses from more than a dozen commercially available 

cements, approximately 200 kg of Type I portland cement was obtained from the 

St. Marys Cement Company in St Marys, Ontario, and the Texas Cement Company in 

Buda, Texas co be issued as SRM 1880. XRF analyses of each cemenc 1nd1caced 

that a 50:50 blend would produce a standard with levels of most elements very 

close to the desired concentration (see Appendix F). 

To eliminate segregation of the packaged SRM, the cements were ground and 

classified separately in a Vortec M-1 impact mill and Vortec C-13 air 

classifier until all of the cement particles were between 0.5 and 45 ~m as 

measured by a Micromeritics Sedi Graph* particle size analyzer (see Appendix 

F). 

Approximately 100 kg of each cement was weighed and transferred to a 19-ft. 

steel ribbon blender and mixed for 2-1/2 hours. One-third of the cement was 

transferred to a plastic-lined 55-gal steel drum; the next third was caught in 

a plastic-lined 30 gal steel drum; and the final third wao tranoferred to the 

same 55-gal drum. The cement in the smaller drum was then tested for 

* In order to adequately describe materials and experimental procedures. it was 

occasionally necessary to identify commercial products by manufacturer's name 

or label. In no instance does such identification imply endorsement by the 

National Bureau of Standards nor does it imply that the particular products or 

equipment is necessarily the best available for the purpose. 

23 
homogeneity by analyzing 18 grab samples for sulfur, iron, and loss-on-ignition 

in accordance with ASTM Cll4 refer procedures (see Table 22). To improve the 

homogeneity, the cement was returned to the blender and mixed for four 

additional hours and then transferred as before. Six grab samples from the 30-

gal drum were analyzed for iron with the results indicated in Table 22. These 

results verified that the cement was well blended and ready for packaging. 

Table 22. Homogeneity of Blended Cements. s~ 1880. % by wt. 

2-1L2 Hours 6-1L2 Hours 

Blender S03 Fe203 Ign. Loss Fe203 

Top 3.69±0.014 2.93±0.000 1.40±0.010 2.81±0.000 

Middle 3.68±0.021 2.91±0.028 1.36±0.005 2.82±0.021 

Bottom 3.68±0.000 2.94±0.057 1.38±0.017 2.81±0.014 

The approximate composition of the second cement standard was selected after 

considering the survey responses and the final composition of S~ 1880. In 

consultation with cement industry representatives, it was decided that SRM 1881 

should have greater than 1% K20, greater than 4.5% Fe203, and a S03 level near 

3.75%. After evaluating typical analyses from many commercially available 

cements, it was decided that a research cement identified as LTS-41 came 

closest to the desired composition. This cement had been obtained in 1941 and 

stored in steel drums in PCA since that time. It was manufactured by the 

former Alpha Portland Cement Company in Birmingham, Alabama. By testing the 

cement for loss-on-ignition, it was concluded that the cement had not gained 

significant moisture during storage. 

To discourage segregation of the packaged S~, the cement was ground and 

classified in a Vortec M-1 impact mill and Vortec C-13 air classifier until the 

cement particles were less than 40 ~m (see Appendix F). Approximately 72 kg of 

cement was processed in this manner. 

Because additional gypsum was needed to increase the S03 content to the desired 

level of 3.75%, several methods of blending (homogenizing) the cement with 

gypsum were studied, including paddle mixing and ball milling. A 0.14-m mortar 

mixer with rubber wiper blades was tried first with 91 kg of a test cement and 

1.6 kg of gypsum. After mixing for 60 minutes there seemed to be a difference 

between samples taken from the top and bottom of the mixer. These samples were 

tested for total sulfur using a Leco sulfur analyzer. A 0.07-m ceramic-lined 

mill was tried next with equal charges (22 kg) of cement and gypsum and alumina 

balls (equal weights of l-in, 3/4-in, and 1/2-in diameters). After milling for 

60 minutes the blending was questionable. A 0.14-m steel-lined ball mill was 

tried next using the same ratio of balls to the cement charge. The results 

obtained in this test were more encouraging. Based on these results and 

discussions with members of the PCA staff, it was decided to use a ratio of 3 

to 1 of high-density (90%) alumina balls to the cement and gypsum charge in the 

steel-lined mill. 

To simulate·the particle size distribution of gypsum typically found in 

cements, the gypsum was first ground to high fineness in a small (0.03 m) steel 

ball mill with 34 kg steel balls graded from 1/2 in to 7/8 in. Approximately 4 

kg gypsum was added and ground at 70 rpm for 7500 revolutions. The mill was 

24 
stopped every 1500 revolutions and the gypsum scraped from the inner mill wall. 

The gypsum was discharged through a grate by turning the mill an additional 200 

revolutions. This finely ground gypsum contained 2.1% greater than 200 mesh 

(70 ~m). The entire batch was brushed through a 200 mesh sieve yielding about 

3.9 kg with a Blaine specific surface area of 10,725 cm3/g (density- 2.37 

gjcm3, bed porosity- 0.50). 

The ground and classified cement was split into three batches of 24 kg each, 

homogenized separately for 10 minutes and then discharged into separate 

containers. Chemical analysis on composite grab samples indicated 1.67% S03 in 

the cement. To achieve the desired level of S03, approximately 1.2 kg of Terra 

Alba gypsum was added to each batch. 

Each 24-kg batch of the cement was then blended separately in the steel-lined 

ball mill with 66-kg alumina balls graded as previously described. The mill 

was turned at 30 rpm for 15 minutes, stopped, the inner wall scraped, and the 

mill turned for an additional 15 minutes. The mill was then stopped, a 

discharge grate attached, and the mill turned for 5 minutes to discharge the 

cement. This blended cement was returned to its original container. Each of 

the three batches was homogenized in this manner and cross-blends between the 

batches were made according to the scheme shown in Figure 8. Grab samples 

taken from different locations in the mill during blending indicated 

satisfactory homogenization was achieved. 

After blending, 12 grab samples of about 10 g each were taken to check the 

homogeneity. Because the cement was in three 5-gal cans, two samples were 

taken from the upper and lower halves of each can. Briquets were pressed from 

6 g of each sample for XRF analysis for calcium, sulfur, and iron. The results 

of these preliminary homogeneity analyses are shown in Table 23. These results 

verified that the cement was well blended and ready for packaging. 

Table 23. Prepackaging Homogeneity of SRM 1881, % by wt. 

so3 Fe2Q3 

Can 1 2 3 1 2 3 1 2 3 

Top 60.00 60.02 59.95 3.90 3.88 3.90 5.00 4.98 4.97 

Bot. 60.03 59.88 60.19 3.90 3.92 3.94 5.00 4.99 5.00 

SRMs 1880 and 1881 were packaged in one-dram stoppered shell vials, flame 

sealed within slightly larger shell vials, using the same method as the 

previous cement standards. A small glass wool disc placed in the out~r viul 

protected the bottom of the inner vial during the flame sealing. "See Appendix 

E for complete descriptions of the packaging materials. 

During the first phase of preparing these two SRMs, PCA investigated the 

possibility of packaging the cements in modern flexible materials. See 

Appendix G for details on this study. 

25 
BATCH #I BATCH #2 BATCH #3 

. CROSS-BATCH #I CROSS-BATCH =11=2 CROSS-BATCH #3 

Figure 8. Scheme for mixing and blending the cement for SRM 1881 

26 
An auger-type apparatus was used to fill each vial with cement. A 4-gal 

hopper was manually loaded with cement and the vials were then filled by 

pressing a foot pedal to discharge the cement into o~e vial at a time. 

Approximately 20 vials per minute could be fil'led, each with 5 g of cement. 

The mass of cement going into each vial was checked with an electronic 

analytical balance several times each day. The vial was then stoppered and 

placed upside-down into a larger outer vial. The glass-wool pad was pushed 

down into the outer vial so that it rested against the bottom of the inner 

vial. The vials were then placed on a conveyor to the flame sealing machine. 

The sealing machine could seal about 18 vials per minute. The controls for 

flame size and temperature and vial rotation speed were all adjusted to produce 

uniform, hemispherical glass seals. 

As the vials were conveyed away from the sealing machine, they were placed by 

hand into cardboard trays. Usually, one operator performed this work for 30 

minutes and then exchanged places with the person operating the filling 

machine. Two additional people worked to cap and insert the vials. Three 

people could fill and seal about 3,000 vials per day. An entire lot of 10,000 

vials was packaged in three and one-half days. 

The methods used in the chemical analysis of SRMs 1880 and 1881 were the same 

as those used for the "600 series" SRMs, including the checking of precipitates 

and filtrates for impurities. A 0.5-g sample was used in all cases. For the 

majority of the analyses, tests were performed on some of ten samples chosen by 

stratified random selection such that each sample represented a single case of 

the stor.ed cement. Ten of the 12 cases were pick~d at random. The ten samples 

permitted the chemists to perform analyses in sets of six (five unknowns and 

one blank or standard sample). 

Silica 

Si02 was determined by the classical double dehydration technique. The results 

of these determinations, as well as the confirming AAS results, are indicated 

in Table 24. 

Table 24. Results of the Analyses of Si02, % by wt. 

Gravimetric AAS 

SRM Average n Std Dev Average n Std Dev 

1880 19.82 7 0.053 19.68 5 0.079 

1881 22.25 4 0.029 22.22 5 0.069 

The combined group "R203" was determined by the classical double precipitation 

method. See Tables 25 through 29 for the·results. 

27 
Iron Oxide 

Table 25. Results of the Analyses 

of the "R203" Group, % by wt. 

1880 

1881 

Average 

8.47 

9.19 

n 

7 

4 

Std Dev 

0.066 

0.026 

Fe203 was determined on separate samples by the volumetric titration method and 

confirmed by AAS. See Table 26. 

Titania 

1880 

1881 

Table 26. Results of the Analyses 

of Fez03, % by wt. 

Volumetric 

Average n Std Dev 

2.91 

4.68 

3 

4 

0.006 

0.005 

AAS 

Average n 

2.88 

4. 71 

5 

5 

Std Dev 

0.010 

0.030 

TiOz in SRM 1880 was determined by a colorimetric method using Tiron reagent. 

In SRM 1881 it was also determined by XRF using standard additions. The ASTM 

Cll4 colorimetric method (complexation with Tiron) produces slightly low 

values. This procedure requires a correction due to interference by iron in 

the sample. Extensive investigations of this method during the analysis of 

these SRMs revealed the precise amount of correction to be applied. It also 

revealed the existence of some unknown interference which produces low values 

for Ti02 in cements. In checking the notes made during the original definitive 

analyses of the "600 series" cements, it was found that all values obtained by 

the T1ron method had been adjusted to agree with check samples f.cum "1000 

series" cements, which had been analyzed for Ti02 by the classical peroxide 

method. 

To determine accurate values for Ti02 in these SRMs, analyses were performed by 

the method of standard additions using both XRF and colorimetry. Samples were 

fused with NaOH for colorimetry or with Li2B407 for XRF. Standard additions of 

Ti02 (using SRM 154b) were made in increments of 0.25% up to a total of 1.25% 

TiOz for both methods. The net optical absorbances and net XRF intensities 

were plotted linearly against concentration. The concentrations of Ti02 in the 

samples were determined by extrapolation to zero measurement response. The 

results are given in Table 27. Additional tests of the "600 series" cements 

indicated that the present values are correct. 

28 
Phosphorus Oxide 

Table 27. Results of the Analyses 

of Ti02, %by wt. 

1880 

1881 

Colorimetric XRF 

Average n Std Dev 

0.230 

0.248 

10 

2 

0.003 

0.002 0.217 

P205 was determined on separate samples by the "molybdenum blue" colorimetric 

method. See Table 28 for the results. 

Zinc Oxide 

Table 28. Results of the P205, % by wt. 

1880 

1881 

Average _n 

0.292 10 

0.091 4 

Std Dev 

0.001 

0.001 

ZnO was determined on separate samples by AAS using a standard addition 

technique. The value for each SRM was found to be 0.01 percent. 

Chromium Oxide 

Cr203 was determined on a separate sample by AAS. The value for each SRM was 

found to be less than 0.01 percent. 

Alumina 

Al203 was determined by difference (subtracting thP- amount:~ of Fe203, Ti02, 

P205, and ZnO from the "R203" group amount) and confirmed by AAS. See Table 29 

for the results. 

Table 29. Results of the Analyses of Al203, % by wt. 

By Difference 

SRM "R2Q3.:_ "X2Q3.:_ A12Q3 St:d Dev Average n Std Dev 

1880 8.47 3.44 5.03 0.064 5.05 4 0.037 

1881 9.19 5.03 4.16 0.030 1,. 21 5 0.034 

Manganese Oxide 

Mn203 was determined on separate samples by AAS. See Table 30 for the results. 

29 
Calcium Group 

Table 30. Results of the Analyses 

of Mn203, % by wt. 

1880 

1881 

Average n 

0.08 5 

0.26 5 

Std Dev 

0.000 

0.000 

GaO t SrO was determined by the classical double precipita.tluu meLhuu u~lug 

ammonium oxalate. See Table 31 for the results. 

Strontium Oxide 

Table 31. Results nf An:4lyses 

of the Calcium Group, % by wt. 

1880 

1881 

Average n 

63.09 6 

58.65 4 

Std Dev 

0.064 

0.054 

The value of SrO for certification was determined on separate samples by AAS. 

The amount of SrO in the Calcium oxide precipitate was also determined by AAS. 

These values are given in Table 23. 

Magnesia 

1880 

1881 

Table 32. 

Separate 

Average n 

0.06 5 

0.11 5 

Results 

of SrO, % 

Samples 

Std Dev 

0.005 

0.000 

of the Analyses 

by wt. 

CaO Precipitate 

Average n Std Dev 

0.04 7 0.004 

0.09 3 0.002 

MgO was determined by the classical double precipitation method. This value is 

corrected for the small amount of CaO in the precipitate as determined by AAS. 

This corrected value is confirmed by measurements on separate samples by AAS. 

See Table 33 for the results. 

30 
Table 33. Results of the Analyses of ~gO, % by wt. 

Gravimetric CaO in MS 

Average n Std Dev Mgo* Difference Average n Std Dev 

1880 

1881 

2.75 

2.70 

7 

4 

0.032 

0.009 

*see correction factor on page 20. 

Calcium Oxide 

0.06 

0.07 

2.69 

2.63 

2.65 

2.65 

5 

5 

0.014 

0.008 

CaO was determined by difference (subtracting the amount of strontium in the 

group precipitate and adding the amount of calcium in the magnesium 

precipitate). See Table 34 for the results. 

Table 34. Results of the Analyses of CaO, % by wt. 

SrO SrO CaO 

+ in in 

SRM CaO GaO J1gQ_ GaO Std Dev 

1880 63.09 0.04 0.09 63.14 0.07 

1881 58.65 0.09 0.11 58.67 0.06 

Sulfur Oxide 

S03 was determined on separate samples using a precipitation with barium 

chloride. The amount of S03 in a composite sample of SRM 1881 was also 

determined by ion chromatography calibrated against standard sulfate solutions. 

These results are indicated in Table 35. 

Table 35. Results of the Analyses of S03, % by wt. 

Gravimetry Chromatography 

SRM Average n Std Dev 

1880 

1881 

3.37 

3.65 

Potassium and Sodium Oxides 

5 

5 

0.013 

0.021 3.69 

These alkalies were determined on separate samples by AAS. See Tables 36 and 

37 for the results. 

31 
Table 36. Results 

Analyses of KzO, % 

SRM Avera~e n 

1880 0.91 5 

1881 1.17 5 

Fluoride 

of the 

by wt. 

Std Dev 

0.007 

0.009 

Table 37. Results of the 

Analyses of NazO, % by wt. 

1880 

1881 

Avera~e 

0.28 

0.04 

n 

5 

5 

Std Dev 

0.000 

0.000 

Fluurlut:! wa.~ ut:!Lt:!rmiut:!u uu ~t:!}Jarate samples by a specific ion electrode 

procedure. The results are indicated in Table 38. 

Table 38. Re~nlt'~ of t'he Analy~e~ 

of Fluoride, % by wt. 

SRM Avera~e n Std Dev 

1880 0.104 10 0.0008 

1881 0.094 5 0.0004 

Chloride 

Chloride was determined on separate samples by a potentiometric titration 

procedure [6]. In this procedure the sample is decomposed in nitric acid, 

filtered, and titrated potentiometrically with silver nitrate using a Ag/AgS 

electrode. See Table 39 for the results. 

Table 39. Results of the Analysis 

of Chloride, % by wt. 

SRM Avera~e n Std Dev 

1880 0.016 9 0.0015 

1881 0.005 5 0.0005 

Miscellaneous Elements 

No significant amounts (less than 0.01 percent) of barium, boron, and zirconium 

were found. 

I~nition Loss 

Loss-on-ignition (1000 °C for 30 minutes) was determined on separate samples. 

See Table 40. 

32 
Table 40. Results of Ignition 

Loss, !! by wt. 

SRM Average n Std Dev 

1880 1.38 4 0.019 

1881 2.01 5 0.018 

The combined results of all these analyses are given in Table 41 along with the 

pooled standard deviations for the two cements. These results formed the basis 

for the certification of SRMs 1880 and 1881. 

Table 41. Final Results for 

SRM:s 1880 and 1881, % by wt. 

SRM 

Constituent 1880 1881 2pGaO 63.14 58.67 0.06 

Si02 19.82 22.25 0.05 

Al203 5.03 4.06 0.06 

Fe203 2.91 4.68 0.01 

so3 3.37 3.65 0.02 

MgO 2.69 2.63 0.03 

K20 0.91 1.17 0.01 

Ti02 0.23 0.25 <0.01 

Na20 0.28 0.04 <0.01 

SrO 0.06 0.11 <0.01 

P2os 0.29 0.09 <0.01 

Mn203 0.08 0.26 <0.01 

F 0.10 0.09 <0.01 

Cl 0.02 0.01 <0.01 

ZnO 0.01 0.01 

Cr203 <0.01 <0.01 

Ign Loss 1.38 2.01 0.02 

Total 100.2 100.0 

Sp is the pooled standard deviation for the two SRMs. 

33 
Conclusion 

Du~ing the preparation of SRMs 1880 and 1881, several methods of blending 

(homogenizing) the cements were studied. The effectiveness of a ribbon-type 

blender, a paddle mixer, a rotating drum mixer, a ceramic pebble, and steel 

ball mills were tested. The paddle and drum mixers performed poorly, actually 

causing a segregation in the samples. The pebble mill performed well with a 

ball-charge to sample weight ration of 3:1. However, extended time in the ball 

mill produced a sample of greater fineness. Thus, of the blenders tested, the 

ribbon blender worked best, yielding flowable powders; unfortunately, it is 

tedious to thoroughly clean because of the arrangement of the ribbon blades. A 

systematic study should be made to determine the effectiveness of twin-shell 

"V-blenders" with high-speed intensifier bars. 

The traditional flame sealed glass vials are excellent containers for portland 

cement SRMs. Samples of cement which were sealed in glass vials and stored in 

a 100%-relative-humidity room for two years showed no increase in loss onignition or change in specific area. A sample of SRM 114, Portland Cement 

Fineness Standard, which had been sealed in glass vials for more than three 

decades is still being used. The filling and sealing of glass vials, however, 

is a slow process. On the other hand, flexible packages offer the advantages 

of light weight, a large surface for labelling, high-speed filling and sealing 

with automated apparatus, and they will not break if dropped. The use of 

flexible packages, however, are doubtful. See Appendix G for a study of their 

performance under extreme conditions. While they can provide good barriers 

against moisture and carbon dioxide, they are not intended for long-term 

storage of materials, because the plastic films may deteriorate. Therefore, 

developments in the flexible packaging industry should be monitored. When 

plastic laminates become available with extended life, they should be carefully 

tested for their suitability as containers. It is noted that the Cement 

Association of Japan has begun to use flexible packages for their portland 

cement fineness standards. · 

Since the completion of SRMs 1880 and 1881, a computer program was written by 

R. Paule, P. Pella, and G. Y. Tao of NBS which performs a rigorous within and 

between analysis of variance. This program eliminates the use of "judgement" 

when assessing the variability of homogenized samples. It is based on 

performing duplicate XRF analyses of samples fused with lithium tetraborate. 

The program should be employed in evaluating the blending of cement SRMs in the 

future. 

Significant interferences found during the course of the analytical studies 

are: 

(1) Approximately 0.1% CaO is found in the MgO precipitate. This correction 

should be made for accurate MgO determinations. 

(2) The gravimetric procedure for GaO has been replaced in ASTM Cll4-83a with a 

titration procedure. Because the gravimetric procedure is subject to 

interferences from strontium and magnesium, future analyses for 

certification of calcium in cements should be based on the titration and 

other instrumental methods. 

34 
(3) The gravimetric aluminum determination is also subject to interferences, 

notably through the presence of phosphorus, tita~ium, and iron. If present 

in sufficient quantities, chromium, zinc, and copper also interfere. Thus, 

future analyses for aluminum in cements should be based on instrumental 

methods. 

(4) The colorimetric method for titanium (using Tiron reagent) described in 

ASTM Cll4 and studied during the characterization of SRM 1881 gives values 

that are consistently several hundredths of a percent low. The influence 

of iron on the determination was investigated and its Influence is now 

known. It does not, however, account for the remaining consistently low 

values. Further work is needed on this method. 

The analytical program has demonstrated that several interferences exist that 

must be taken into account to obtain the most accurate values when performing 

gravimetric determinations.· On the other hand, instrumental analysis has 

reached a high level of reliability, precision and accuracy so that many 

analyses previously performed by classical methods can be replaced by 

techniques such as atomic absorption/emission, x-ray fluorescence, neutron 

activation, mass spectroscopy, and plasma emission. 

P~rhaps the most significant difficulty in performing classical gravimetric 

analyses is simply that fewer and fewer chemists practice these methods and the 

precision and accuracy of these techniques depend on the skill of the analyst. 

It is a tribute to the analysts who participated in this program, notably 

Robert F. Crow of the PCA laboratories, that the gravimetric results are in 

excellent agreement with those of the instrumental techniques. 

35 
Acknowledgements 

The preparation, packaging, and characterization of these portland cement SRMs 

was accomplished through the close cooperation of many people and 

organizations. Special credits are given to those listed below. 

NBS Staff 

Leonard Bean 

Bruce E. Foster 

Harry H. Ku 

Robert E. Michaelis 

Stanley D. Rasberry 

PCA Staff 

Robert F. Crow 

N. R. Greening 

Ernst: LaBonde 

Joseph Leonard 

Hugh Love 

Mick McCann 

William F. Mivelaz 

Robert Monger 

Celestino Palmiano 

Heinz Seiler 

Charles Wilk 

William G. Hine of Erlin, Hine Associates 

ASTM Committee C-1 on Cement 

The many cement manufacturers who contributed the cements from which the SRMs 

were made and for extensive laboratory time in performing analyses. 

36 
References 

[1] ASTM Cll4-69, Standard Methods for Chemical Analysis of Hydraulic Cement, 

American Society for Testing and Materials, Annual Book of ASTM Standards, 

Part 9.-

[2] Jugovic, Z. T., Application of Spectrophotometric and EDTA Methods for 

Rapid Analysis of Cement and Raw Materials, in Analytical Techniques for 

Hydraulic Cement and Concrete, ASTM Standard Technical Publication, STP No. 

395, 1966, pp. 65-93. 

[3] Crow, R. F. and Connolly, J. D., Atomic Absorption Analyses of Portland 

Cement and Raw Mix Using a Lithium Metaborate Fusion, Journal of Testing 

and Evaluation (ASTM), Vol. 1 (No. 5), September 1973, pp. 382-393. 

[4] Crow, R. F. and Connolly, J. D., Analysis of Portland Cement, Prog. Analyt. 

Atom. Spectrosc., Vol. 1, 1979, p. 349. 

[5] Peck, L. C., Systematic Analysis of Silicate, U. S. Geological Survey 

Bulletin 1170, 1964. 

(6] Mivelaz, W. F. et al., Test Methods of the PCA Analytical Chemistry 

Laboratories, Portland Cement Association, February 1980, Sec. 4, pp. 1-20. 

Copies of the reports 

(1) Cooperative Analyses of the "600 series" SRMs. 

(2) Definitive Analysis of the "600 series" SRMs. 

(3) Preparation and Analysis of SRM 1880. 

(4) Pr~par:~t:i on :~nrl Analy.cds of SRM 1881. 

can be obtained from the Office of Standard Reference Materials, National 

Bureau of Standards. 

37 
Appendix A 

Copies of the certificates: 

SRM 177 

1011 

1013 

1014 

1015 

1016 

633 

634 

635 

636 

637 

638 

639 

1880 

1881 

38 
UNITED STATES DEPARTMENT OF COMMERCE 

WASHINGTON 25, D. C. 

~ttoual1Jjureau of a>tanbarbs 

€ettifitatt of §nalpsts 

Standard Sam pie 177 

Portland Cement 

ANALYST SiOs AJ,O, Fe,01 •TiOt PtO, bCaO SrO MgO so, Mn,o, NatO K,O •Lou on Ianldon 

1--------- 21.91 5.26 { d 2.4-3 1 

2.4.0 

1, _________ 21.88 5.28 ; 2. 39 

J ______ ID 21.96 5.20 2. 38 

•------ 21.90 0 5.38 2.40 

5---------- 21.96 e~~5.SO 2. 38 

6 _________ 121.91 1 5.26 '2. 37 

7 _____ 21.93 5.25 2 . .39 

8 ______ 21.85 5.26 2.39 

9-...------ 4 21.97 5.24: 2. 36 

( ·-- 21.90 l,o5.76 12.45 

11---·- 21.93 5.36 2.36 

12 ____ 21.94: 5.31 2.38 

13 _____ • 21.87 5.30 2.37 

Average_ 21.92 5.27 2.39 

• a.o. pbatometric aaetJ.ocl (ASTM Spec. Cll._S6T). 

• AU nliMII b CaO illdllde SrO. • 1 1 M&ted at ~ to t,oooe C. for IS min. in a CDftrecl platiaaa crucible (ASTM Spec. Cll4-S3). • NH.CNS-plaot.ometric. 

• Mob'bcla.....Wae p .. a 1 •rico t J11ame ~ S. AuL a.e., '1'1, 913 (19SS). • Periodate p~ 

0.26 •0.05 

.28 ~t.OS 

• 28 { k,04 } •.04 

.25 ...................................... 

__ ... ____ ............... .03 

.28 -------------

.24: .04 

.22 .04 

.27 { ~t.OS } •.05 

................................... .05 

.u .03 

.26 .04 

.25 .05 

0.26 O.<K 

64.29 •o.os 2 • .f3 

6l.28 1

.05 2.4-2 

6l . .fl -~·--... --... 2.46 

6l.27 ... ............................... _ 2.4:5 

6l.37 -----~--- 2.4:8 

1 6l.26 -------- 12.51 

6l.37 ------·--- 2.50 

6l.40 --------·-- 2.37 

r()ol.56 ------- 2.4:8 

16l.35 --------- 12.4:8 

64.27 ------·--- 2 • .f() 

M.l8 ---·-... --... 2.4:8 

64:.38 ------ •2.4:4: 

64:.32 0.05 2.4:5 

---

l.S9 •0.05 { 110.15 1.15 

110.57 } •. 55 1.11 

1. 59 .OS •.14 1.57 1.11 

1.56 .04 1.14 1.57 1.15 

1.63 •.Of. P.IS P. 59 1.19 

1. 56 .Of. ·---·----- ----------· 1.19 

lJ. 55 •.05 P.J3 P.56 l 1. ()4. 

1.60 .06 D.12 P,56 1.17 

1. 55 .03 •.12 •.60 1.17 

1.62 •.Of. P.l3 P, 56 1.16 

11.60 .06 •.13 1• 58 11.14 

l.SS .(){ { •.12 •. 51 1 l.lB P.}2 P, 55 

1.61 .Of. { I 16 } r,P.ll P.57 1.14 

1.60 .06 P.1j P, 58 1.15 

1.59 0.05 0.14- 0.57 1.15 

• Gra'rimetric. ........... MaPJQr. 

• Omitted from ...... nlae iudada no. or PJOa. • Flame plilotoawtric: (ASTM Spec. Cll4-S6T). 

tkra~ clehTdratioo with HCO. with iaternniq 

r Not iudacled ia tbe • ....._ 

AulYtt 1 reported ().()04.perc:ent U,O • 

List of Analysts 

l. Keith M. Sappenfield and R. A. Paulson, Analytical 

Chemistry Sectio~ National Bureau of Standards. 

2. Jo~eph R. Spann and J. J. Diamond, Concreting 

Materials Section, National Bureau of Standards. 

3. Harold Allen, Nonbitum.inous Section, Bureau of 

Public Roads, Washington, D. C. 

4. F. S. Reagel and 0. E. Brown, Marquette Cement 

Manufacturing Co., Chicago, Ill. 

5. W. J. Limbach, Southwestern Portland Cement Co., 1 Fairborn, Ohio. 

~'· ,{alter H. Price, Division of Engineering Laboratories, 

Bureau of Reclamation, Denver, Colo. 

WASHINGTON, D. C., November 25, 1957. 39 

7. F. P. Diener and 0. A. Ellingson, Universal Atlas 

Cement Co., New York, N.Y. 

8. L. R. lndermuehle, Southwestern Portland Cement 

Co., Victorville, Calif. 

9. K. E. Palmer, Ideal Cement Co., Fort Collins, Colo. 

10. L. R. Pritchard, Lone Star Cement Corporation, New 

York, N.Y. 

11. W. C. Hanna and Leon Loomis, California Portland 

Cement Co., Colton, Calif. 

12. W. J. McCoy and 0. L. Eshenour, Lehigh Portland 

Cement Co. Research Laboratory, Coplay, Pa. 

13. J. H. Walker, Portland Cement Association, Chicago, 

Ill. 

A. V. AsTIN, Dirtcuw. 
U. S. DEPARTMENT OF COMMERCE 

NATIONAL BUREAU OF STANDARDS 

WASHINGTON, D. C. 20234 

PROVISIONAL CERTIFICATE OF ANALYSIS 

STANDARD SAMPLE 1011 

PORTLAND CEMENT 

Percent 

Si02 ----------------------------- 21.03 

Al203·---------------------------- 5.38 

Fe2o3----------------------------- 2.01 

0.25 

.33 

CaO (+SrO) ----------------------- 66.60 

SrO ------------------------------ 0.11 

MgO ------------------------------ 1.12 

803 ------------------------------ 1.75 

Mn203 ---------------------------- 0.03 

Na2o ----------------------------- .08 

K2o ·-·--------------------------- .26 

Li20 ----------------------------- (.002) 

Rb20 ----------------------------- (.001) 

Loss on Ignition ---------------·- 1.13 

Valuea in parentheses are not certified but are given as added information. 

Washington, D. c. 

A. A. Bates, Chief 

Building Research Division 

Revised Certificate, April 24 1 1964 

Original Certificate January 17, 1962 

USCMI·NBS·DC 

40 
U S. DPpArt .. nt' of Commf>r('P 

Maurice~.B. Stans ~refi~ ., ~ ... 

r-,.,. .. onal Bare;u of' Star.dards L. M. Bral'll!leCARb, Director 

(!Iertifirafe of !'nalt!sis 

STANDARD REFERENCE MATERIAL 1013 

Portland Cement 

Percent 

Si0 2 •••••••••••••••••••••••••••••••• 24.1 7 

Al 2 0 3 ••••••••••••••••• ~ • • • • • • • • • • • • • 3.30 

Fe2 0 3 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 3.07 

Ti02 •••••••••••••••••••••••••••••• ,• • 0.20 

P2 0 5 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • .20 

CaO ( + SrO) o o o o o o o o o o o o o o o o o o o o o o r.· ~ 64~34 SrO 0 o o o 0 o o o o o o o o o o o o o o o o o ~~ o ~~ ~;{)8 

MgO o o o o o o o o o o o o o o o o o o o o o o ~ '~0 o o o 1.39 

~~:o3° 0 : : : : : : : : : : : : : : ~0 ° : : : :. : : : : ~:~~ 

Na20 ...... No o \0~ ~0 o o • o o o o o 0 o 0 0 0 0 o20 

K20 .... 

0

. . .· .. 't .................. 32 

Li2 0 .... (~ . . . . . . . . . . . . . . . . . . . . . . . (.001) 

Rb2 0 ~l· ~. . . . . . . . . . . . . . . . . . . . . . . . (.004) 

L~~ 00 oo .......... oo .. ooooooo 0 99 

Values in parentheses are not certified but are given as added information. 

Washington, D. C. 20234 

january 17, 1962 

(Revised April 24, 1964) 

(Reprinted M~rch 16, 1970) 

41 

A. A. Bates, Chief 

Building Research Division 
U. S. Department of Commerce 

Maurice H. Stans 

Sec:rebry 

' 'lational Bue~.; of Standards . M. BrallKCRitb, Dire<:tor 

aiertifirate nf J\nalusis 

Standard Reference Material 1014 

Portland Cement 

Percent 

Si02 ••••••••••••.•••••••••••••••••••••••••••• 19. 4g 

Al 20 3 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 6.:38 

Fe203 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . 2.5() 

Ti02 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 0.25 

p 205 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .32 

CaO <+SrO> ••••.••...•.•••••••••••••.••.••••.•• 63.36 

SrO ••••••••.••••••••••..••••••••••••••••••• ~ 

~:::::::::::::::::::::::::::::~~ 270 

Mn203 ......................... ·o~\ ~ .... 0.07 

Na20 .......•........... ~ ~-~ . . . . . • . . . • • .24 

K~O •••••..••••• ~. -~ \ ~ ~ • • • • • • • • • • • • • • .99 

~~~: : : : : : : ~o· : : ~~:: .. : : : : : : : :: : :: :: ::: ::: ::::: 

Loss o~~ V . . . . . . . . . . . . . . . . . . . . . . . . . . . .81 

Values ~ntheses are not certified but are given as added infonnation. 

Washington, D. C. 20234 

January 17, 1962 

(Revised April 24, 1964) 

(Reprinted June 18, 1971) 

42 

A. A. Bates, Chief 

Building Research Division 
U. S • DEAPR'IMENT OF C<11MERCE 

NATIONAL BUREAU OF STANDARDS 

WASHINGTON, D.C. 20234 

PROVISIONAL CERTIFICATE OF ANALYSIS 

STANDARD SAMPLE 1015 

PORTLAND CEMENT 

SiO 2 ---------------------------

Al 2 3 0 ---------------------------

Percent 

20.65 

5.04 

3.27 

0.26 

P205 --------------------------- .OS 

CaO (+ SrO) -------------------- 61.48 

SrO 0.11 

MgO 4.25 

2.28 

Mn2o3--------------------------- 0.06 

-~~-~-----~~~~~------------ .16 

.87 

(.004) 

(.005) 

Loss on Ignition --------------- 1.70 

Values in parentheses are not certified but are given as added information. 

Washington, D. c. 

A. A. Bates, Chief 

Building Research Division 

Revised Certificate, April 24, 1964 

Original Certificate January 17, 1962 

USCOl+l-NBS-DC 

4J 
U. 8. Depart~ of Commerce 

c. 'ii!Ltth 

•• ~donal ~.·· · ... Standard• 

A. v.~.:-,.. 

C!trtificatt of Snalp5is 

SiQ;z 

STANDARD SAMPLE 1016 

PORTLAND CEMENT 

Percent 

Al203------------------------ 4.97 

Fe2o3------------------------ 3.71 

0.34 

P2o5 ------------------------ .13 

CaO (+SrO)------------------- 6~~ 

sro --------------------~~ 

::: ~~~~~~~~~~~~--~ 2::~ Mn203---~-~ ---------- 0.04 

~~~~~~~~~~~~~~~~~~~~~ ~:: ~20 ------------------------(.012) 

Rb2o -----------------------*(N.D.) 

Loss on Ignition------------ 1.20 

Values in parentheses are not certified but are given as added 

information. 

*N.D.= not·detected, but less than 0.001% 

Washington, D. C. 

A. A. Bates, Chief 

Building Research Division 

Revised Certificate April 24, 1964 

Original Certificate January 17, 1962 

Certificate Reprinted January 17, 1969 

USCOMM-NBS-DC 44 
U.S. ~-:bf Commerce 

~o~driae 

i~1 Nalional ~=:~f~ Ernest AID&ier', Director 

Nattnnal fSurtau nf ~anbarbs 

Qttttifitatt nf Analysts 

Standard Reference Material 633 

Portland Cement 

(Cap Color is Red) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the "true" value based on the results of a ·definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, with W. 0. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the "true" value by more than ± 1 in the last significant figure reported; 

for a subscript figure, the deviation is not expected to be more than ± S. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

Caa' 64.50 N~O 0.64 

Si02 21.8g SrO .31 

~03 3.78 P20S .24 

Fe2o 3 4.20 Mn20 3 .04 

so3 2.2o F .08 

Mgoa 1.04 ZnO .01 

JSO 0.17 Cr20 3 .01 

Ti02 .24 lgn. loss .1s 

Totalb 100.06 

•u the procedures of ASTM C 114 are followed a smaU amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 64.47 

MgO 1.06 

bA ~;orrcction ha3 been made for the: amount of fluoride prc:3c:nt. Thi3 ~;orrcction, which wa3 3ubtractc:d from the: y033 total, wa3 dctccmincd iJY 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). · 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

dated 2-24-77 and 6-12-74) 

{Over) 

45 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Lone Star 

Cement Corporation by S. D. Rasberry, M. M. Darr, and J. McKay by x-ray fluorescence analysis. The cement was 

sampled at 16locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements 

for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens. An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE ANALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major constituents CaO, Si02, AI2o3 and MgO. (The methods were essentially 

those of ASTM Cll4 using a 0.5-g sample.) Fe20 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for ISO, N~O, SrO, M~0 , ZnO and Cr20 3• Colorimetric techniques were used to determine Ti02 

and P20 5 while_ fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

l000°C~ In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric, gravimetric, potentiometric, optical emission elements were determined to 

be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of 100.060Jo of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration _procedures may be adopted to minimize biases. 

46 
U.S. Departi\\tm .Of Commerce 

M~~~'B.ald,rige 

;-···; :~~~~ .................. . 

Nauonal 'U,urcau of-Standards 

Ernest A'mbti:r. Dir~tor 

National Jlureau nf!;tanbarbs 

<tterttftcatt nf Analusis 

Standard Reference Material 634 

Portland Cement 

(Cap Color is Gold) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the "true" value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, with W. G. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the "true" value by more than ± 1 in the last significant figure reported; 

for a subscript figure, the deviation is not expected to be more than ± 5. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

caoa ~2.58 Na20 0.15 

Si02 20.73 SrO .12 

Al20 3 5.21 P20, .10 

Fe20 3 2.84 Mn203 .28 

503 2.21 F .08 

MgOa 3.30 ZnO .02 

K20 0.42 Cr20 3 .08 

Ti02 .29 lgn. loss 1.62 

Totalb 100.00 

•u the procedures of ASTM CI14 are followed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 62.54 

MgO 3.33 

b A correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). 

The Lcchnkal and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

{Revision of certificates 

dated 2-24-77 and 6-12-74) 

(Over) 

47 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Universal 

Atlas Cement Division of United States Steel Corporation by S. D. Rasberry, M. M. Darr, and J. McKay by x-ray 

fluorescence analysis. The cement was sampled at 16 locations and two briquettes were prepared for each one. 

Calcium and sulfur, chosen as key elements for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trend-elimination statistical design was employed in measuring the 

specimens. An analysis of these data indicated the homogeneity was satisfactory. Following these measurements the 

cement was thoroughly blended and packaged in hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of Standard Reference Materials. 

DEFINITIVE ANALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major constituents CaO, Si02, Al2

0 3 and MgO. (The methods were essentially 

those of ASTM C114 using a 0.5-g sample.) Fe2

0 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K20, Na2

0, SrO, Mn20 3, ZnO and Cr2o3• Colorimetric techniques were used to determine Ti02 

and P20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric, gravimetric, potentiometric, optical emission elements were determined to 

be less than 0.01 wtOfo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of 100.0007o of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration procedures may be adopted to minimize biases. 

48 
U.S. DepartiMm·:i>r Commerce 

M"f.'>~'¥se 

!~ NatioDal ~'ot Swxwds Emat ~-Director 

Nattnnal Jlur.eau nf ~anbarbs 

Qt.ertiftca:t.e nf .Analysts 

Standard Reference Material 635 

Portland Cement 

(Cap Color is Blue) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the ''true'' value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, with W. G. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not exJ'eeted to deviate from the "true" value by more than ± 1 in the last significant figure reported: 

for a subscript figure, the deviation is not expected to be more than ± 5. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

caoa 59.83 N~O 0.07 

Si02 18.41 SrO .21 

Al203 6.29 P20s .17 

Fe20 3 2.61 Mn20 3 .09 

so3 7.07 F .04 

MgOa 1.23 ZnO .01 

K20 0.45 Cr20 3 .01 

Ti02 .32 Ign. loss 3.24 

Totalb 100.03 

11f the procedures of ASTM C 114 are followed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 59.79 

MgO 1.26 

bA correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

dated 2-24-77 and 6-12-74) 

(Over) 

49 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Penn-Dixie 

Cement Corp. by S.D. Rasberry, M. M. Darr, and J. McKay by x-ray fluorescence analysis. The cement was sampled 

at 16locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens. An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE Al"iALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major constituents CaO, Si02, AI20 3 and MgO. (The methods were essentially 

thoseof ASTM C114 using a 0.5-g sample.) Fe20 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K20, N~O, SrO, Mn2o3, ZnO and Cr20 3. Colorimetric techniques were used to determine Ti02 

and P 20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric. gravimetric. potentiometric. optical emission element~ were determined to 

be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of lOO.OJOJo of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration procedures may be adopted to minimize biases. 

50 
U.S. [)epartri1Cnf of Commerce 

Mal~laLBildri&e ~· 

:.~>:!! .. ! National ~ ot Stalldards 

Ernest ~;riuector 

Nntinnnl Jiurtnu nf .&tunbnrbs 

C!ttrtificntt nf Anulgsis 

Standard Reference Material 636 

Portland Cement 

(Cap Color is Yellow) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the "true" value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, with W. G. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the "true~' value by more than ± 1 in the last significant figure reported; 

for a subscript figure, the deviation is not expected to be more than ± 5. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

CaQii 63.54 Na20 0.11 

Si02 23.; SrO .04 

Al20 3 3.02 P20s .08 

Fe2o 3 1.61 Mn20 3 .12 

so3 2.3. F .06 

Mgo• 3.95 ZnO .03 

K20 0.59 Cr20 3 .01 

Ti02 .18 lgn. loss 1.16 

Totcilb 100.00 

au the procedures of ASTM Cll4 are followed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given below for CaO and MgO should be used. 

CaO 63.49 

MgO 3.98 

b A correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). 

The technical and support aspects involved in the preparation. certification. and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

do.ted 2-24-77 and 6-12-74) 

(Over) 

51 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Arizona 

Portland Cement Co. by S.D. Rasberry, M. M. Darr, and J. McKay by x-ray fluorescence analysis. The cement was 

sampled at 16locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements 

for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens. An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE ANALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major constituents CaO, Si02, AI20 3 and MgO. (The methods were essentially 

those of ASTM Cll4 using a 0.5-g sample.) Fe20 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy technique~ were used for JSO, N~O, SrO, M~0 , ZnO and Cr2o3• Colorimetric techniques were used to determine Ti02 

and P 20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric. gravimetric. potentiometric. optical emission elements were determined to 

be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of lOO.OOOJo of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration procedures may be adopted to minimize biases. 

52 
U.S. Depart~i-~f Commerce 

Ma'~e!fge i ·· .. ,..·,.-.·. ! 

National ~ea11 of $taadards 

Ernat Amttler-tOuector 

NutinnulfSurtuu nf ~unburbs 

artrtificutt nf .Analysis 

Standard Reference Material 637 

Portland Cement 

(Cap Color is Pink) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the "true" value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, with W. G. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the ''true'' value by more than ± 1 in the last significant figure reported; 

for a subscript figure, the deviation is not expected to be more than ± S. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

caoa 66.04 N"lO 0.1S 

Si02 23.07 SrO .09 

Al20 3 .3.28 P20s .24 

Fe20 3 1.80 Mn2o3 .06 

so3 2.38 F .04 

MgOa 0.6, ZnO .01 

K20 .2S Cr20 3 .01 

Ti02 .21 lgn. loss 1.69 

Totalb 99.97 

au the procedures of ASTM C 114 are followed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 66.02 

MgO 0.68 

bA correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. St~nley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

dated 2-24-77 and 6-12-74) 

(Over) 

53 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Kaiser Cement & Gypsum Corp. by S.D. Rasberry, M. M. Darr, and J. McKay by x-ray fluorescence analysis. The cement was 

sampled at 16 locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements 

for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens. An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE ANALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet, chemical 

gravimetric methods were used for the major constituents CaO, Si02, AI2o3 and MgO. (The methods were essentially 

those of ASTM Cll4 using a 0.5-g sample.) Fe2o3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn20 3, ZnO and Cr20 3• Colorimetric techniques were used to determine Ti02 

and P 2o 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric, gravimetric, potentiometric, optical emission elements were determined to 

be less than 0.01 wtOJo: Cl. Ba. Zr. B. V. Ni. Mo. Sn. Pb. Cu. and Ag. The total of 99.97 OJo of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration procedures may be adopted to minimize biases. 

54 
U.S. Department of Commerce 

~ae 

NatioDal ~~~ ~ of Studards Emal·~..- 1>irector 

Nntinnul iiur.euu nf ~unburbs 

Q!ertificatt nf Anuluuts 

Standard Reference Material 638 

Portland Cement 

(Cap Color is Green) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The value listed for a constituent is the present best estimate of the "true" value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening. W. F. 

Mivelaz and R. F. Crow, with w.· G. Hime of Erlin, Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the "true" value by more than ± 1 in the last significant figure reported; 

for a subscript figure, the deviation is not expected to be more than ± 5. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

caoa 62.09 N~O 0.13 

Si02 21.48 SrO .07 

Al203 4.4' P2o, .06 

Fe20 3 3.55 Mn20 3 .05 

so3 2.34 F .04 

MgO~~ 3.83 ZnO .10 

K20 0.59 Cr20 3 .01 

Ti02 .25 Ign. loss .9s 

Totalb 99.97 

•If the procedures of ASTM Cll4 are foliowed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 62.05 

MgO 3.86 

b A correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the perceilt fluoride by the ratio·of the atomic weight of oxygen to the molecular weight of fluorine (0.421). 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

dated 2-24-77 and 6-12-74) 

(Over) 

55 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Marquette 

Cement Corporation by S.D. Rasberry, M. M. Darr, and J. McKay by x-ray fluorescence analysis. The cement was 

sampled at 16 locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements 

for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens: An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE ANALYSIS PROGRAM OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major constituents CaO, Si02, AI20 3 and MgO. (The methods were essentially 

those of ASTM Cll4 using a 0.5-g sample.) Fe20 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K20, N~O, SrO, Mn2o3, ZnO and Cr2

o3. Colorimetric techniques were used to determine Ti02 

and P 20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric, gravimetric, potentiometric, optical emission elements were deteonined to 

be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of 99.97 OJo of the certified constituents in the cement corroborates the evaluation and i.ndicates that significant biases have not been introduced. 

CAUTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Alternatively, interelement effect calibration procedures may be adopted to minimize biases. 

56 
U.S. Oepanmeru of Commer.;.:e 

M~~d;ige 

!~~ 

Nauonal ll11reau of.Standarcis 

Ernest ~bier. Director 

Natinnal ilurrau nf @1anbarils 

Qt.ertificat£ nf .Analv.sis 

Standard Reference Material 639 

Portland Cement 

(Cap Color is Clear) 

This Standard Reference Material (SRM) is intended for use in checking chemical methods of analysis and in 

calibration of instrumental methods of analysis. 

The ·value listed for a constituent is the present best estimate of the "true" value based on the results of a definitive 

analysis program carried out in the laboratories of the Portland Cement Association by N. R. Greening, W. F. 

Mivelaz and R. F. Crow, \\ith W. G. Hime of Erlin~ Hime Associates acting as consultant. The certified value for a 

constituent is not expected to deviate from the "true" value by more than ± 1 in the last significant figure reponed; 

for a subscript figure, the deviation is not expected to be more thel!l ± 5. Based on the resUlts of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

caoa 65.76 N~O 0.65 

Si02 21.61 SrO .15 

Al203 4.28 P205 .08 

Fe2o3 2.40 M~03 .08 

so3 2.4g F .02 

Mgoa 1.26 ZnO .01 

K..,O .. 0.06 Cr20 3 .01 

Ti02 .32 lgn. loss l.Oo 

Totalb 100.16 

1 If the procedures of ASTM Cll4 are followed a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values given 

below for CaO and MgO should be used. 

CaO 65.73 

MgO 1.28 

b A correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined bv 

multiplying the oercent fluoride by the ratio of the atomic weight of oxygen to the molecular weight of fluorine (0.421). ' 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by B. E. Foster, R. E. Michaelis, and 

C. L. Stanley. 

Washington, D.C. 20234 

December 15, 1983 

(Revision of certificates 

dated 2-24-77 and 6-12-74) (Over) 

57 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
HOMOGENEITY TESTING: ~1easurements were· made at NBS on the portland cement supplied by the Centex Cement Corporation by S. D. Rasberry, ~1. :VI. Darr, and J. McKay by x-ray fluorescence analysis. The cement was 

sampled at 16 locations and two briquettes were prepared for each one. Calcium and sulfur, chosen as key elements 

for checking inhomogeneity, were determined by making four independent measurements on each briquette. A trendelimination statistical design was employed in measuring the specimens. An analysis of these data indicated the 

homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in 

hermetically sealed glass vials by personnel of the Cement and Concrete Research Laboratory and the Office of 

Standard Reference Materials. 

DEFINITIVE Al'IAL YSIS PROGR . .L\1\1 OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical 

gravimetric methods were used for the major ~onstituents CaO, Si02, Al20 3 and ;vtgO. (The methods were essentially 

those of AST~l C 114 using a 0.5-g sample.) Fe20 3 was determined by dichromate titration and S03 by precipitation in 

an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn20 3, ZnO and Cr20 3• Colorimetric techniques were used to determine TiO~ 

and P20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 

1000°C. In each determination duplicate measurements were made on two to ten randomly selected samples. Through 

the use of various techniques (colorimetric. gravimetric, potentiometric, optical emission elements were determined to 

be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of 100.160io of the certified constituents in the cement corroborates the evaluation and in.dicates that significant biases have not been introduced. 

C1)UTION: To obtain the most accurate results by x-ray fluorescent methods of analysis, the user should compare his 

samples to the particular SRM that is most nearly the same in overall chemical composition. Nternatively, interelement effect calibration procedures may be adopted to minimize biases. 

58 
~ ntinnnl !ilurtnu nf ~btndnrds 

C!Itrtifitnft nf ~nnlusis 

Standard Reference Material 1880 

Portland Cement 

(Cap Color is Black) 

This Standard Reference Material (SRM) is intended for use in evaluating chemical methods of analysis and in the 

calibration of instrumental methods of analysis. SRM 1880 consists ofthree sealed vials oftype 1 Portland cement, each 

containing approximately 5 grams. 

The certified value listed for a constituent is the present best estimate of the "true'" value based on the results of a 

definitive analysis program carried out in the laboratories of the Portland Cement Association. The certified value for a 

constituent is not expected to deviate from the "true'" value by more than ± 1 in the last significant figure reported; for a 

subscript figure, the deviation is not expected to be more than ± 5. Based on the results of homogeneity testing, 

maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weight Constituent Percent by Weight 

Ca08 63.14 Na20 0.28 

Si02 19.82 SrO .06 

Ah03 5.03 P20s .29 

Fe201 2.91 Mn?Ol .08 

S03 3.37 F .10 

Mg08 2.69 Cl .02 

K.zO 0.91 ZnO .01 

Ti02 .23 lgn. loss 1.38 

Totalb 100.28 

•If the procedures of ASTM Cll4 are followed, a small amount of CaO will remain in the MgO precipitate. In this case 

the uncorrected values given below for CaO and MgO should be used: 

CaO 63.0s 

MgO 2.7s 

b A correction has been made for the amount of fluoride present. This correction. which was subtracted from the gross 

total, was determined by multiplying the percent fluoride by the ratio .Jfthe atomic weight of oxygen to twice the a.tomic 

weight of fluorine (0.421). Correction of the total for the small amount of chloride was negligible (<0.0 I%). 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by R.K. Kirby. 

Washington. DC 20234 

February 10, 1984 

(over) 

Stanley D. Rasberry. Chief 

Office of Standard Reference Materials 
Acknowledgements 

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

performed under the direction of H. M. Kanare of the Chemical/ Physical Research Department, Portland Cement 

Association (PCA), Skokie, Illinois. The cement was ground and blended with the aid of C. Wilk, J. Leonard, and 

H. Love. The packaging operations were performed by E. LaBonde, J. Loneard, M. McCann, C. Palmiano, and 

C. Wilk. Homogeneity testing was performed by C. Palmiano. The definitive analyses were conducted by R. Crow, 

E. LaBonde, and H. Seiler. 

Preparations 

This SRM was blended from equal parts of Type I Portland cement supplied by the St. Mary's Cement Company in 

Canada and the Texas Cement Company. Before blending, each cement was ground in an impact mill until all particles 

were between 0.5 and 45 .urn as selected with an air classifier. The size distributions of the two cements, as determined 

with a sedimentation apparatus, were quite similar. Tests indicated that after 6 I 12 hours of blending the mix was 

homogeneous. 

Homogeneity Testing 

Following the packaging of the cement in hermetically sealed glass vials the homogeneity was determined by measuring 

36 samples selected in a stratified random process. X-ray fluorescence analysis was used to determine the differences in 

calcium, sulfur, and iron by four replicate measurements on each briquette. 

Definitive Analysis 

"Wet" chemical gravimetric methods were used for the major constituents CaO, Si02, Ah03 and MgO. (The methods 

were essentially those of ASTM Cll4 using a 0.5-g sample.) Fe203 was determined by dichromate titration and S03 by 

precipitation in an acid solution. Atomic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn203 

and ZnO., Colorimetric techniques were used to determine Ti02 and P20s. Fluoride was determined by an ion selective 

electrode method and chloride was determined by a potentiometric titration method. Loss on ignition was determined at 

·1000 °C. In each determination duplicate measurements were made on three to ten randomly selected samples. Through 

the use of various techniques (colorimetric, gravimetric, and AAS) the presence of the following trace elements were 

determined to be less than 0.0 t wt. %: Ba, Zr, B, and Cr. The total of 100.28% oft he certified constituents in the cement 

corroborates the evaluation and indicates that significant biases have not been introduced. 

Caution 

To obtain the most accurate results by x-ray fluorescence methods of analysis, the user should compare his samples to the 

particular S R M's that are most nearly the same in overall chemical composition. Alternatively, interclemcnt effect 

calibration procedures may be adopted to minimize biases. 

60 
~ atinnal lJlureau of ~tandards 

Standard Reference Material 1881 

Portland Cement 

(Cap Color is White) 

This Standard Reference Material (SRM) is intended for use in evaluating chemical methods of analysis and in the 

calibration of instrumental methods of analysis. SRM 1881 consists of three sealed vials of type I Portland Cement, 

each containing approximately 5 grams. 

The certified value listed for a constitutent is the present best estimate of the "true" value based on the results of a 

definitive analysis program carried out in the laboratories of the Portland Cement Association. The certified value 

for a constituent is not expected to deviate from the "true" value by more than ± 1 in the last significant figure 

reported; for a subscript figure, the deviation is not expected to be more than ± 5. Based on the results of 

homogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures. 

Constituent Percent by Weidtt Constituent Percent by Weiiht 

Caoa 58.67 Na20 0.04 

Si()z 22.2s SrO 11 

Ah03 4.16 P20s 0.09 

Fe203 4.68 Mn203 0.26 

S03 3.6s F 0.09 

Mg(il 2.63 Cl 0.01 

K20 1.17 Ign.loss 2.01 

Ti02 0.2s Totalb 100.04 

ZnO 0.01 

a If the procedures of ASI'M C114 are followed, a small amount of CaO will remain in the MgO precipitate. In this case the uncorrected values 

given below for CaO and MgO should be used: 

CaO 58.65 

MgO 2.70 

b '\ correction has been made for the amount of fluoride present. This correction, which was subtracted from the gross total, was determined by 

multiplying the percent fluoride by the ratio of the atomic weight of oxygen to twice the atomic weight of fluorine (0.421). 

The technical and support aspects involved in the preparation, certification, and issuance of this Standard Reference 

Material were coordinated through the Office of Standard Reference Materials by R.L. McKenzie. 

Gaithersburg, MD 20899 

December 7, 1987 

(Revision of certificate 

dated 2-10-84) 

(over) 

61 

Stanley D. Rasberry, Chief 

Office of Standard Reference Materials 
Acknowledgements 

The preparation of this material ·anJ the coordination of technical measurements leading to certification were 

performed under the direction of H. M. Kanare of the Chemical/ Physical Research Department, Portland Cement 

Association (PCA), Skokie, Illinois. The cement was ground and blended with the aid of R. Monger. The packaging 

operations were performed by M. McCann, R. Mong~r. C. Palmiano, and C. Wilk. Homogeneity testing was performed 

by J. Leonard and C. Palmiano. The definitive analyses were conducted by R. Crow and H. Seiler. 

Preparations 

This S R M was blended from a Portland cement supplied by the Portland Cement Association and 5 wt.% of Terra Alba 

gypsum. Before blending, the ..-:cmcnt was ground in an impact mill until all particles were smaller than 4Q ~mas selected 

with an air classifier and the gypsum was ground in a steel-ball mill to pass a 200-mesh sieve (<75}-Lm). Tests indicated 

that after blending the mix was sufficiently homogeneous. 

Homogeneity Testing 

Following the packaging of the cement in hermetically sealed glass vials the homogeneity was determined by measuring 

36 s.::~mples s.elec.terl in ::1 str::~tified random process. X-ray fluorescence analysis was used to determine the differences in 

calcium, sulfur, and iron by four replicate measurements on each briquette. 

Definitive Analysis 

"Wet" chemical gravimetric methods were used for the major constituents CaO, Si02, Ah03 and MgO. (The methods 

were essentially those of ASTM Cl14 using a 0.5-g sample.) Fe203 was determined by dichromate titration and SOJ by 

precipitation in an acid solution. At~ic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn203 

and ZnO. Colorimetric techniques were used to determine Ti02 and P20s. Fluoride was determined by an ion selective 

electrode method. Loss on ignition was determined at 1000 °C. In each determination duplicate measurements were 

made on three to ten randomly selected samples. Through the use of various techniques (colorimetric, gravimetric, and 

AAS) the presence of the following trace elements were determined to be less than 0.01 wt .. %: Ba, Zr, B, Cl, and Cr. The 

total of I 00.04% of the certified constituents in the cement corroborates the evaluation and indicates that significant 

biases have not been introduced. 

·Caution 

To obtain the most accurate results by x-ray fluorescence methods of analysis, the user should compare his samples to the 

particular SRM's that an: most m:arly tht: samt: in ovt:rall chemical composition. Altt:rnativcly, interelcment effect 

calibration procedures may be adopted to minimize biases. 

62 
Appendix B 

Summaries of the homogeneity tests for 

SRMs 633 

634 

635 

636 

637 

638 

639 

1880 

1881 

are given in this appendix. 

The tests on the "600 series" cements were made by measuring the variation of 

calcium and sulfur with normal x-ray fluorescence methods using the "1000 

series" cements as standards. The packaged vials of each cement were stored in 

15 or 16 cans and two vials were taken from each can totaling 30 or 32 

specimens. Each specimen were prepared by briquetting. All of these specimens 

were satisfactory except one from SRM 639 which proved to be defective and was 

not included in the results. The following tables indicate the average value 

of four measurements for each element on each specimen. The run-order of the 

measurements used a trend elimination sequence. Because an analysis on the two 

vials from each can did not indicate they were 11 duplicates", each vial was 

considered to be an independent sample. 

The tests on SRMs 1880 and 1881 were made by measuring the variation of 

calcium, sulfur, and iron with normal x-ray fluorescence methods. Thirty-six 

vials of each cement were selected in a stratified random process from the 

cases in which they were stored. A specimen from each vial was prepared by 

briquetting and four measurements were made for each element. Using one of the 

specimens as a machine standard, the others were mea.:surt:!u u:slng a. LLt:!IlU 

elimination sequence. The following tables indicate the average value of four 

measurements for each element on each specimen. 

63 
SRM 633 

CaO 

64.95% by wt. 64.87% by wt. 

64.97 65.09 

64.90 65.09 

64.98 65.06 

64.97 65.02 

65.01 64.99 

64.92 65.19 

65.06 65.00 

65.06 64.93 

65.03 65.02 

64.88 65.04 

65.05 64.91 

65.01 64.99 

64.95 64.97 

65.03 65.05 

64.96 65.05 

Average 65.00% by wt. 

Std. Dev. 0.069% by wt. 

Coef. of Var. 0.105% 

SRM 634 

63.20% by wt. 

63.16 

63.19 

63.29 

63.21 

63.13 

63.18 

63.12 

63.22 

63.22 

63.09 

63.15 

63.25 

63.23 

63.21 

63.13 

63.21% by wt. 

63.22 

63.29 

63.13 

63.29 

63.18 

63.14 

63.20 

63.22 

63.23 

63.23 

63.12 

63.22 

63.17 

63.33 

63.25 

Average 63.20% by wt. 

Std. Dev. 0.057% by wt. 

Coef. of Var. 0.091% 

so3 

2.181% by wt. 

2.180 

2.206% by wt. 

2.191 

2.215 

2.208 

2.196 

2.218 

2.194 

2.177 

2.197 

2.192 

2.202 

2.194 

2.192 

2.189 

2.205 

2.178 

2.229 

2.208 

2.232 

2.214 

2.176 

2.189 

2.200 

2.203 

2.195 

2.202 

2.190 

2.209 

2.217 

2.221 

2.200% by wt. 

0.015% by wt. 

0.67% 

so3 

2.180% by wt. 

2.200 

2.183% by wt. 

2.194 

2.181 

2.200 

2.193 

2.180 

2.203 

2.204 

2.195 

2.212 

2.191 

2.227 

2.213 

2.204 

2.215 

2.194 

64 

2.189 

2.192 

2.196 

2.199 

2.211 

2.220 

2.201 

2.191 

2.227 

2.193 

2.206 

2.195 

2.205 

2.204 

2.200% by wt. 

0.012% by wt. 

0.56% 
SRM 635 

CaO so3 

59.54% by wt. 59.47% by wt. 6.795% by wt. 6.827% by wt. 

59.72 59.80 6.778 6.803 

59.90 59.69 6.774 6.777 

59.73 59.78 6.814 6.798 

59.88 59.83 6.748 6.772 

59.65 59.79 6.803 6.814 

59.70 59.59 6.842 6.794 

59.69 59.71 6.782 6.837 

59.68 59.72 6.803 6.835 

59.67 59.68 6.776 6.824 

59.62 59.53 6.778 6.824 

59.61 59.73 6.870 6.779 

59.67 59.70 6.752 6.820 

59.78 59.64 6.778 6.845 

59.68 59.76 6.774 6.804 

59.77 59.72 6.784 6.798 

Average 59.70% by wt. 6.800% by wt. 

Std. Dev. 0.094% by wt. 0.028% by wt. 

Coef. of Var. 0.158% 0.40% 

SRM 636 

CaO so3 

63.91% by wt. 63.89% by wt. 2.193% by wt. 2.189% by wt. 

63.81 64.20 2.178 2.180 

63.94 63.74 2.158 2.209 

63.76 63.85 2.192 2.213 

63.84 63.69 2.195 2.220 

63.82 63.91 2.179 2.213 

63.75 63.81 2.206 2.191 

63.80 63.87 2.203 2.196 

63.77 63.74 2.206 2.198 

63.78 63.63 2.201 2.212 

63.66 63.68 2.199 2.213 

63.72 63.62 2.224 2.225 

63.74 63.85 2.183 2.160 

63.84 63.83 2.217 2.236 

63.74 63.81 2.183 2.230 

Average 63.80% by wt. 2.200% by wt. 

Std. Dev 0.111% by wt. 0.019% by wt. 

Coef. of Var. 0.176% 0.82% 

65 
SRM 637 

CaO so3 

66.34% by wt. 66.48% by wt. 2.428% by wt. 2.397% by wt. 

66.36 66.47 2.407 2.401 

66.40 66.39 2.399 2.405 

66.37 66.45 2.392 2.420 

66.44 66.54 2.391 2.407 

66.27 66.40 2.404 2.406 

66.35 66.22 2.415 2.412 

66.42 66.46 2.385 2.387 

66.53 66.27 2.407 2.398 

66.46 66.32 2.401 2.394 

66.54 66.30 2.382 2.403 

66.52 66.30 2.399 2.398 

66.40 66.49 2.381 2.401 

66.39 66.42 2.402 2.378 

66.35 66.34 2.400 2.400 

Average 66.40% by wt. 2.400% by wt. 

Std. Dev. 0.085% by wt. 0.011% by wt. 

Coef. of Var. 0.129% 0.47% 

SRM 638 

CaO so3 

62.15% by wt. 62.07% by wt. 2.400% by wt. 2.423% by wt. 

62.15 62.24 2.363 2.397 

62.15 62.00 2.415 2.413 

62.06 62.12 2.408 2.402 

62.13 62.10 2.410 2.402 

61.96 62.09 2.396 2.381 

62.31 62.17 2.389 2.365 

62.06 62.15 2.392 2.393 

62.09 62.02 2.398 2.389 

62.08 61.98 2.384 2.420 

62.08 62.14 2.414 2.413 

61.97 62.10 2.423 2.387 

62.11 62.06 2.414 2.425 

62.01 62.21 2.380 2.396 

62.05 62.16 2.402 2.406 

Average 62.10% by wt. 2.400% by wt. 

Std. Dev. 0.077% by wt. 0.016% by wt. 

Coef. of Var. 0.124% 0.68% 

66 
SRM 639 

66.64% by wt. 

66.49 

66.54 

66.70 

66.33 

66.71 

66.46 

66.66 

66.38 

66.59 

66.47 

66.62 

66.49 

66.35 

66.46 

66.75% by wt. 

66.66 

66.67 

66.53 

66.65 

66.57 

66.52 

66.45 

66.62 

66.40 

66.60 

66 ·'·'· 66.58 

66.41 

Average 66.50% by wt. 

Std. Dev. 0.115% by wt. 

Coef. of Var. 0.175t 

2.527% by wt. 

2.475 

2.502% by wt. 

2.519 

2.520 

2.503 

2.525 

2.492 

2.475 

2.478 

2.532 

2.487 

2.525 

2 .1~ 90 

2.522 

2.515 

2.513 

67 

2.498 

2.503 

2.509 

2.514 

2.514 

2.534 

2.500 

2.531 

2.532 

2.539 

2.542 

2.487 

2.500% by wt. 

0.020% by wt. 

0.79% 
SRM 1880 

GaO so3 Fe2Q3 

63.11%.by wt. 3.338% by wt. 2.809% by wt. 

63.52 3.332 2.814 

63.02 3.371 2.802 

63.12 3.361 2.807 

63.17 3.324 2.810 

63.25 3.361 2.828 

63.22 3.334 2.817 

63.16 3.355 2.809 

63.08 3.381 2.807 

63.27 3.365 2.811 

62.88 3.353 2.796 

63.14 3.381 2.812 

62.94 3.343 2.811 

63.34 3.368 2.808 

63.10 3.362 2.826 

63.04 3.326 2.826 

63.06 3.356 2.800 

63.08 3.301 2.802 

63.12 3.349 2.811 

63.07 3.328 2.814 

63.16 3.347 2.806 

62.98 3.359 2.805 

63.14 3.353 2.803 

63.02 3.376 2.804 

63.14 3.353 2.816 

63.58 3.374 2.818 

62.89 3.358 2.814 

63.42 3.332 2.827 

63.01 3.321 2.794 

63.08 3.310 2.803 

63.18 3.360 2.818 

63.03 3.364 2.807 

63.39 3.355 2.812 

63.27 3.327 2.804 

62.84 3.327 2.791 

Average 63.14% by wt. 3.349% by wt. 2.810% by wt. 

Std. Dev. 0.168% by wt. 0.021% by wt. 0.0089% by wt. 

Coef. of Var. 0.265% 0.60% 0.32% 

68 
SRM 1881 

CaP S03 Fe2Q3 

60.14% by wt. 3.869% by wt. 5.007% by wt. 

59.99 3.681* 4.970 

60.11 3.833 4.984 

59.98 3.824 4.990 

60.06 3.864 4.980 

60.03 3.868 4.993 

60.05 3.858 5.011 

60.01 3.875 4.994 

60.12 3.862 4.998 

60.04 3.796 4.970 

59.95 3.841 4.975 

59.93 3.856 4.981 

60.34 3.756 4.988 

60.16 3.881 4.997 

60.15 3.886 5.010 

59_91 1_R?9 4_9R5 

60.16 3.754 4.996 

60.27 3.896 4.998 

60.10 3.789 4.997 

59.92 3.820 5.002 

59.95 3.873 4.982 

59.77 3.773 4.969 

60.06 3.881 4.993 

59.96 3.860 4.973 

60.09 3.837 4.999 

60.15 3.843 4.997 

59.84 3.790 4.970 

59.95 3.780 4.98)_ 

59.95 3.792 4.974 

59.92 3.833 4.984 

60.04 3.827 4.989 

59.98 3.841 4.989 

60.12 3.851 4.997 

60.14 3.823 4.985 

60.08 3.774 4.986 

Average 60.04% by wt. 3.833% by wt. 4.988% by wt. 

Std. Dev. 0.115% by wt. 0.039% by wt. 0.0116% by wt. 

Coef. of Var. 0.193% 1.02% 0.23% 

*Value not included in the statistics. 

69 
Appendix C 

Results of the Cooperative Test Program for the Chemical Analysis of SRMs 633 

through 639 

PARTICIPATING LABORATORIES 

Atlantic Cement Co. 

P.O. Box 3 

Ravena, NY 12143 

Methods (W,F,J) 

Aah Grove Cement Co. 

640 Southwest Blvd. 

Kansas City, KS 66103 

Methods (X,A) 

California Portland Cement Co. 

P.O. Box 947 

Colton, CA 92324 

Methods (W,F,A) 

Capitol Cement 

P.O. Box 412 

San Antonio, TX 78218 

Methods (W,A) 

Department of the Army 

Waterways Experiment Station 

Corps of Engineers 

P.O. Box 631 

Vicksburg, MS 39180 

Methods (W,F) 

Marquette Cement 

20 North Wacker Drive 

Chicago, IL 60606 

Methods (W,F,C) 

National Bureau of Standards 

Analytical Chemistry Division 

Gaithersburg, MD 20899 

Method (X) 

Pacific Western Ind., Inc. 

P.O. Box 1247 

Lebec, CA 93243 

Methods (W,A,C) 

Penn-Dixie Cement Corp. 

P.O. Box 152 

Nazareth, PA 18064 

Method (X) 

Portland Cement Association 

5420 Old Orchard Road 

Skokie, IL 60077 

Methods (W,J,A,C) 

Southwestern Portland Cement Co. 

P.O. Box 937 

Victorville, CA 92392 

Method (X) 

St. Mary's Cement Co. Ltd. 

P.O. Box 68 

Bowmanville, Ontario 

Canada 

Methods (W,F,C) 

Universal Atlas Cement 

Buffington Station 

Gary, IL 46401 

Methods (J,F) 

70 
A summary of the results of the cooperative test program is given in Table C. 

The complete data of this program as reported by William G. Hine of Erlin, Hine 

Associates is available from the National Bureau of Standards, Office of 

Standard Reference Materials. The code for the'methods used in this program 

are as follows: 

A Atomic Absorption 

C Colorimetry 

F Flame Photometry 

J Jugovic 

W Wet 

X X-Ray Fluorescence 

The deviations reported in the table were determined by 

n 

t 2 [ ~ 2 Xi - Xcert] 

i 

where Xi are the n individual measurements made on each of the seven cements 

and Xcert are the final certified values for that component. The ranges are 

determined by 

- Xcert ] [ - Xcert ] 

i max i min 

The values for the deviations and ranges for S03 as determined by x-ray 

fluorescence do not include the values obtained on SRM 635 

(-7% S03) for which the deviations reached 1.8%. 

A copy of the preliminary certificate that was based on the results of this 

program is also provided. 

71 
Table C-1. Summary of the Cooperative Test P~ogram on the "600 Series" SRMs, % by wt. 

-- CaO Si02 A1203 Fe203 803 MgO 

c c c c:: c c:: 0 0 0 0 0 0 •r-4 •r-4 •r-4 •r-4 •r-4 •r-4 

-o +-J "'0 u ""0 +-J ""0 +-J ""0 .u ""0 u 0 C1J Q) 0 C1J Q) 0 C1J C1) 0 ca Q) 0 C1J v 0 C1J <lJ 

.c ·r-4 00 ..c: ·.-1 00 ..c ·.-1 00 ..c •.-1 00 ..c •.-1 (I{) ..c •r-4 OJ u :> c +J :> c +-J :> c:: +-J :> c .u :> c +J :> c: 

Lab ~ Q) C1J (]) Q) ca C1) C1) ca C1) C1) ca Q) C1) 10 Q) Q) C1:: 

Q cG ~ Q cG l: ~ ~ X: 0 ~ X: ~ IZ X: ~ 0:: 

7 w 0.0 0.3 w -0.07 O.OB w +-0.1 0.2 w +0.02 0.03 w -0.04 0.07 w +0.10 0.14 

8 w 0.0 0.4 w -0.18 0.13 w 0.0 0.1 w +0.08 0.20 w -0.08 0.12 w +0.06 0.20 -....J 12 w 0.0 0.6 w 0.00 0.36 w -0.1 0.2 w +0.04 0.05 w -0.01 0.12 w +0.07 0.28 I'V 5 w 0.0 0.1 w +0.10 0.08 w 0.0 0.4 w 0.00 0.02 w +0.04 0.04 

l w +0.2 0.2 w -0.13 0.09 w +0.3 0.3 w +0.16 0.07 w -0.06 0.09 w -0.04 0.08 

4 w -0.2 0.3 w -0.03 0.37 w +0.1 0.2 w -0.04 0.05 w -0.06 0.12 w +0.08 0.15 

13 w +0.2 0.4 w +0.09 0.28 w -0.2 0.3 w +0.11 0.12 w -0.04 0.12 w -0.04 0.21 

6 w +0.4 0.9 w -0.09 0.39 A -0.1 0.4 A +0.11 0.09 w -0.20 0.18 A +0.01 0.18 

5 A 0.0 0.2 A +0.10 0.08 A 0.0 0.3 A +0.02 0.04 w -0.01 0.06 A +0.05 0.06 

10 J +0.1 0.3 J -0.02 0. 25 J -0.1 0.4 J 0.00 0.07 J +0.01 0.14 J +0.06 0.20 

2 X +0.2 0.6 X +0.20 1.09 X +0.1 0.2 X +0.04 0.18 X +0.02 0.13 X +0.16 0.57 

ll X -0.3 0.6 X +0.17 0.54 X +0.1 0.5 X +0.15 0.36 X -0.11 0.11 X +0.32 0.29 

3 X -0.1 0.7 X -0.18 0.57 X -0.1 0.4 X +0.11 0.22 X -0.24 0.08 X -0.09 0.23 

9 X +0.4 1.1 X -0.03 1.14 X +0.1 0.6 X +0.04 0.13 X -0.09 0.51 

l X +0.2 0.5 X +0.09 0.79 X 0.0 0.3 X +0.03 0.18 X -0.04 0.22 X -0.03 0.25 

8 X +0.1 0.7 X -0.16 0.52 X 0.0 0.2 X +0.14 0.14 X 0.00 0.06 X +0.12 0.37 

12 X +0.5 1.7 X +0.12 0.64 X +0.1 0.5 X -0.03 0.24 X +0.08 0.14 X +-0.05 0.24 
Table C-1. (Continued) 

1\20 Ti<n N820 SrO P20S Mn203 Ign Loss 

c c c: t:: t:: t:: c 0 0 0 0 0 0 0 ....... •r-1 ·~ •r-1 •r-1 •r-1 •r-1 

"0 <.-J '"0 ~ '"0 ~ '"0 4.1 ~ ~ '"0 4.1 "0 4.1 

0 ~ <lJ 0 ~ Q) 0 10 QJ 0 co QJ 0 co QJ 0 ~ QJ 0 ·~ 

•.-1 til ..c •r-1 0.0 ..c ·~ 0.0 ..c •r-1 0.0 ..c •r-1 0.0 ..c •r-1 0.0 ..c: •r-1 

u :> t:: 4.1 > c:: ~ > c: +-J > c:: +-J > c:: .j.J > c:: 4.1 > ::.J QJ co QJ Q) co Q) Q) co QJ QJ co QJ QJ co QJ QJ co Q) Q) 

Lab :s 0 c:r: ~ t:'l p:: ~ ~ p:: ):! t:'l p:: ~ 0 p:: ):! 0 p:: ~ 0 

7 r -0.01 0. Otl w 0.00 0.02 F -0.01 0.04 w 0.00 0.02 w -0.01 0.01 +0.01 0.07 

8 r 0.00 0.07 c -0.01 0.05 F -0.07 0.16 w 0.00 0.23 w 0.00 0.01 w -0.01 0.02 +0.05 0.28 

12 f' 0.00 0.03 J -0.02 0.02 F -0.01 0.02 J 0.00 0.01 w +0.01 0.03 +0.06 0.07 

5 

1 (" +0.01 0. 03 c -0.03 0.05 F +0.01 0.06 c +0.01 0.08 w +0.01 0.13 +0.04 0.11 ..._,j 

w 4 r -0.01 0.04 A 0.00 0.08 F 0.00 0.07 A +0!02 0.03 . w 0.00 0.01 A +0.03 0.09 +0.02 0.13 

13 f\ 0.00 0.10 c -0.02 0.17 A -0.04 0.09 c -o.04 0.13 c +0.02 0. 04 -0.02 0.10 

6 f\ 0.00 0. 03 A -0.06 0.16 A -0.01 0.04 A 0.00 0.03 w +0.03 0.14 A 0.00 0.03 +0.01 0.14 

5 f\ 0.00 0.03 J 0.00 0.01 A 0.00 0.01 A 0.00 0.01 c 0.00 0.01 A 0.00 0.00 0.00 0.02 

10 F -0.01 0.05 J +0.01 0.03 F +0.01 0.04 J 0.00 0.01 J 0.00 0.03 -0.02 0.10 

2 X +0.01 0.03 X 0.00 0.03 A -0.01 0.08 X 0.00 0.04 X +0.01 0.08 X 0.00 0.02 +0.04 0.14 

ll X +0.03 0. 20 X +0.01 0.05 X +0.05 0.18 X -0.01 0.02 +0.03 0.14 

3 X +0.03 0.05 X 0.00 0.07 X -0.08 0.06 

9 X +0.01 0.06 X 0.00 0.01 X 0.00 0.03 X +0.01 0.03 X +0.01 0. 07 

1 X 0.00 0.02 X 0.00 0.04 X +0.03 0.05 

8 X -0.01 0. 04 X -0.01 0.03 X +0.01 0.01 

12 X +0.01 0.05 
U. S. Department of Commerce 

Frederick B. Dent 

Secretary 

National Bureau of Standards 

Richard W. Roberta, Director ~ational lJlureau nf ~tandards 

<!I ertifitate nf ~nalt!sis 

Standard Reference Materials 633-639 

Portland Cements 

These SRM's are fine powders and are intended for use both in checking chemical methods of 

analysis and in calibration with instrumental methods of analysis. 

SR!\1 No. 633 634 6.35 636 637 638 639 

CAP COLOR RED GOLD BLUE YELLOW PINK GREEN CLEAR 

Constituent Percent by Weight 

Al20 3 3.7 4 5.2 6.2 3.1 3.3 4.5 4.3 

CaO 64.5 62.6 59.8 63.5 66.0 62.1 65.8 

MgO 1.04 3.4 L25 4.0 0.72 3.84 1.2g 

Ti02 0.24 0.30 0.32 0.17 .21 0.25 0.31 

Si02 21.9 2D.7 18.5 23.2 23.1 21.4 21.6 

so3 2.18 2.16 7.0 2.3 2.33 2.3 2.4 

Pz05 0.24 0.10 0.17 0.09 0.25 0.06 0.08 

Mn20 3 .04 .28 .09 .12 .06 .05 .08 

K20 .165 .43 .45 .57 .245 .59 .05 

Na20 .64 .14 .07 .10 .13 .12 .6~ 

SrO .31 .12 .22 .04 .10 .07 .15 

Fe20 3 4.2 2.87 2.65 1.62 1.8o 3.58 2.42 

lgn. loss 0.75 1.61 3.25 1.16 1.6a 0.95 1.0 

Total 99.95 99.91 99.97 99.97 99.93 99.81 a 100.13 

a One laboratory reported 0.11 ZnO in this SRM, thus increasing the total to 99.92%. 

PRELIMINARY CER'l'lFlCATION~ This Certificate is "preliminary" because additional analvtical 

work is planned that will improve the accuracy of some of the values listed. The value listed. for a 

constituent is the. present best estimate of the "true" value based on the results of the analytical 

program. The values are not expected to deviate from the ~'true" values by more than ± 1 in the last 

significant figun~ reported; for subscript figures, the deviation is not expected to be more than ±S. 

Based on the results of homo~eneity testing, maximum variations within and among samples arf' 

estimated to be less than the uncertainty figures given above. 

Washington, D.C. 20234 

June 12, 1974 

74 

J. Paul Cali, Chief 

Office of Standard R cferencc \late rials 
Appendix D 

Letter sent to members of ASTM Committee C-1 soliciting their help in selectin~ 

the new SRMs. 

75 
Dear ASTM Member: 

Two new po~tland cement chemical standard reference materials are being 

produced by the Portland Cement Association for the National Bureau of 

Standards. These will supplement the seven samples currently available from 

NBS (SRM 633-639). 

We would like to know what chemical composition you think these new standard 

cements should have. For your reference, we have attached a copy of the 

Certificate of Analysis for SRM 633-639. Please write your suggestions for the 

proposed cement standards below the certified values, and return to: 

Howard Kanare 

NBS Cement Standards Project 

Portland Cement Association 

5420 Old Orchard Road 

Skokie, Illinois 60077 

We would appreciate your reply before March 15, 1981. Thank you for your 

suggestions. 

Sincerely, 

R. F. Gebhardt 

Chairman 

C-01.23 on Chemical Analysis 

76 
Appendix E 

List of Equipment and Packaging Materials Used in Preparing SRMs 1880 and 1881. 

Vortec Impact Mill, Model M-1 

Vor~ec Air Classifier, Model C-14 

Micromeritics Sedi-Graph Particle Size Analyzer 

Paul 0. Abbe Steel-Ribbon Blender, Model 7 

Mateer-Burt Auger-Type Power Filler, Model 31-A 

Kimble Type III Flint-Glass Flat-Bottom Shell Vial 

(15-rnrn O.D. x 45-rnrn height) 

TLB Plastics Corp. High-Density Polyethylene Cap 

(fits one dram shell vial) 

Kimble Type III Flint-Glass Flat-Bottom Shell Vial 

(19-rnm O.D. x 100-mm height) 

Glass Fiber Pad (Filter Disc) 

(12.5-rnm dia. x 0.5-rnrn thick) 

Flame Sealing Machine (NBS Property) 

Rigaku XRF Spectrometer, Model 3061, 

X-Rays: 40-kv, 70-rnA water-cooled rhodium target tube fitted with 

a Rh-plated beam defining cone. 

Sample: Pressed powder briquet, 30 x 3 rnm in aluminum cap, pressed 

at 50,000 psi, spining sample holder with 25-rnrn diameter 

copper mask. 

Counting Typical Counts 

Element Crystal Line Detector Time Per Measurement 

Ca LiF(200) K FPC* 20 sec. 510,000 

Fe LiF(200) K sc 40 sec. 260,000 

s Ge K FPC* 20 sec. 240,000 

*Flow Proportional Counter with P-10 gas at 0.05 scfh. 

Cardboard Shipping Boxes and Trays (285 vials per tray) 

77 
Row l 

-------------

Tray 8 

--------------- Tray A 

Figure E-l. Packing case for SRMs 1880 and 1881 

78 

I 

I 

I 

I 

I 

I 

---End 
Appendix F 

Some miscellaneous information is provided in this appendix including values 

for the Blaine surface area given in Table Fl. 

79 
Table Fl. Blaine Surface Area* 

SRM Average n Std Dev 

633 3015 cm2/g 3 32 cm2/g 

634 3485 3 144 

635 4840 3 122 

636 3609 3 88 

637 5678 3 134 

638 3735 3 49 

639 3356 3 76 

1016 3305 3 46 

*Data reported by Norman H. Suhr of the Pennsylvania State University. 

Table F2. Chemical Analysis of the SRM 1880 Cements Before Blending, 

% by wt. 

Cement A 

Cement B 

CaO 

61.31 

64.24 

Si02 

20.25 

19.63 5.64 2.86 

NOTE: All analyses by x-ray fluorescence 

80 

so3 

3.73 

3.21 

MgO 

4. 33 

1.13 0.91 0.13 
0 

(\"') 

0 

1""""4 

0 

E 

:1 

Figure F-1. Results of particle size analysis of SRMs 1880 and 1881. 

81 
Appendix G 

Flexible Packaging Study* 

The intent of this study was to determine if modern flexible packages could 

preserve the properties of cement. Such packages are widely used for the 

storage of foodstuffs, medicine, and electronic equipment. 

The potential advantages of flexible packages include: 

(1) high speed filling and sealing; 

(2) low-volume storage compared to glass; 

(3) reduced weight; 

(4) reduced breakage in shipping and handling; 

(5) ease of shipping through automated labelling; and 

(6) ease of identification through prelabelling. 

Water vaporproof flexible packages generally are composed of several 

laminations of different materials, each serving a specific function. A 

schematic of a typical laminated film is shown in Figure Cl. These laycra can 

be coextruded (dry lamination) or, more commonly, attached 

(inner surface) 

THIN LAYERS OF HEAT SEALABLE FACE 

t~if~6~L~S~I~~,?, &,< f,?. ,-€,£, r ~~o%~~~ylene, polypropylene) 

~------ ----- .__.00035 in. AI FOIL 

(outer surface) 

Figure Gl. Schematic of typical laminated film 

EXTERIOR SUBSTRATE 

( .003") 

(Kroft paper, polyolefin, 

mylar) 

with thin. layers of adhesives. The outer substrate provides mechanical 

strength, abrasion resistance, and a surface for labelling. The aluminum foil 

is the actual barrier to moisture and gas transmission. The heat-sealable face 

can be any number of thermoplastic materials, usually polyethylene, 

polypropylene, or a proprietary plastic film. 

*Conducted by PCA under contract to NBS. 

82 
The plan of this investigation was to encase portland cement samples in Vqrious 

types of commercially available flexible packages a~d then test them under 

average conditions including heat, moisture, high C02, and mechanical abuse. 

The contents of the packages would then be an.alyzed for changes by measuring 

properties such as specific surface area and ignition loss. The packages would 

be examined for degradation, including maceration, delamination, splitting or 

cracking, and discoloration. 

A commonly used military specification (MIL-B-131E) was considered as a general 

guide to the testing of the flexible packages. This specification lists the 

required physical properties for a packaging material to be qualified as a 

"water vaporproof, flexible, heat-sealable, barrier material". However, the 

determination of the maximum permissible water vapor transmission rat~ (WVTR) 

as required in this specification would not be an acceptable test for the 

protection of cement. Therefore, modifications of the test procedures were 

imposed to evaluate the various types of flexible pa~kRges under extremely 

adverse conditions. 

Eight types of flexible packaging films were made available for testing. Six 

to twelve pouches were made from each film, filled with approximately 15 g of 

portland cement, and heat sealed. The descriptions of the packets are given in 

Table Gl. 

One or two samples of each type of. package were placed into each of the 

environmental chambers listed below: 

A. Fog Room (73 °F and 100% R.H.). Packages placed on a wire mesh 

shelf. 

B. High C02 Atmosphere (73 °F, 71% R.H., and 100% C02). 

Packages placed on a wire mesh shelf above saturated (SrCl2•6H20) solution 

inside a 3-liter glass jar. 

Note: This humidity is nearly the optimum for carbonation of cement. 

C. Hot Room (100 °F and 20% R.H.). Packages placed in loosely covered 

cardboard box. 

D. Cold Room (0 °F). Packages placed in loosely covered cardboard box. 

Packages remained in these chambers for 14 to 28 days. They were then removed 

and inspected. The packages that did not appear badly degraded were then 

opened and the cements were tested for ignition loss in accordance with ASTM 

Cll4. Tests for specific surface area using the Blaine Air Permeability 

apparatus were found to be not sensitive enough to serve as an indicator of 

changes in cement properties. 

83 
Table G-1. Description of Flexible Packages as Received 

ID# 

1 

2 

3 

4 

5 

6 

7 

8 

Empty 

Inner Package 

Outer Sealing Weight 

Substrate Barrier Film (3-l/2"x5")2 Appearance 

Saran/nylon Saran/nylon Polyethylene 2.5 g Smooth, transparent 

fairly flexible 

White Kraft paper Foil Polyethylene 3.1 g Semi-gloss, smooth: 

opaque, stiff 

Brown Kraft paper Foil Polyethylene 4.4 g Matte finish, 

opaque, stiff 

Tyvek (TM) Foil Polyethylene 3.9 g Op(:l.que, whlLe, 

Polyolefin semi-gloss, stiff 

Brown 'Kraft paper PolyethylenEl 2.7 g Matte finish, opaqt 

fairly flexible 

Mylar (TM) Foil/ Polyethylene 3.4 g Silver, glossy, 

Mylar(TM) opaque, fairly, 

stiff 

Gold lacguer/ Metallized Polyethylene 1.4 g Glossy, gold, 

Mylar(TM) nylon opaque, very 

flexible 

White Kraft paper Foil Surlyn(TM) 3.9 g Semi-gloss, opaque 

fairly stiff 

aFor reference, an empty glass vial and cap as used for the cement 

SRMs weighed about 14.0 g. 

84 
Table G-2. Appearance of Packages After Tests 

Package ID 

1 

2 

3 

4 

6 

7 

8 

Test A (Fog Room) 

Severe delamination of Saran; allaround edge curl; slight discoloration 

Slight maceration; very slight edge 

curl; no delamination 

Some staining; no edge curl; some 

wrinkles no delamination 

Appearance as received 

Slight maceration; some staining; 

some wrinkling 

Appearance as received 

Major edge curl; severe delamination 

of gold-lacquered top layer 

Minor edge curl, some wrinkling 

no discoloration 

85 

Test C (Hot Room) 

Slight edge curl; 

slight discoloration 

Appearance as received 

Appearance as received 

Appearance as received 

Appearance as received 

Appearance as received 

Test D (Cold 

Appearance as 

received 

Very slight e 

curl 

Appearance as 

received 

Appearance as 

received 

Appearance as 

received 

Appearance as 

received 

Slight edge curl All-around ed 

curl 

Appearance as received Moderate edge 
Selected packages from Test C (Hot Room) were opened and the cement extracted 

with hot CHCl3 using a procedure previously developed at PCA. The weights of 

the CHCl3-soluble residues were determined and their infrared spectra were 

recorded. 

To measure resistance to physical abuse, selected packages were attached to a 

high-speed vibrating table (Syntron Jogger J-lA) for about six hours. The two 

sides of the packages were then separated by cutting just inside all four 

seams, and the inner surfaces were rubbed together with cement in between to 

abrade the heat-sealable films. These inner surfaces were then cleaned by 

swabbing with alcohol, and examined by scanning electron microscopy. A glass 

vial containing cement was similarly vibrated and examined for comparison. 

The appearances of the packages after removal from test chambers A, C, and D 

are given in Table G2. Packages 1 and 7 were badly delaminated after Test A. 

All other packages appeared good although the paper layers were slightly 

macerated. Ignition losses were measured for all packages after removal from 

test chamber A following two days of drying at 73 oF and 40% R.H. The results 

of these tests are given in Table G3. After analyzing these results and 

considering their appearance, Packages 1, 3, 5, and 7 were elirnirrnled from 

further consideration. 

Table G3. Effect of High Humidity 

Package Ignition Loss Package Ignition Loss 

Control 0.72% by wt. 5 1.37% by wt. 

1 2.00 6 0.71 

2 0.71 7 0.89 

3 0.99 8 0.67 

4 0.72 

Packages 2, 4, 6, and 8 were removed from test chamber B and after drying, 

ignition losses were determined. See Table G4. 

Table G4. Effect of High C02 Atmosphere 

Package Ignition Loss 

2 0.66% by wt. 

4 0.68 

6 0.72 

8 0.68 

All of these packages appeared to prohibit carbonation of the cement under the 

conditions of the test, and should therefore be considered good barriers to the 

transmission of moisture and C02 at room temperatures. Packages having 

polyethylene and Surlyn(TM) as the inner heat sealable surface were removed 

from test chamber C and conditioned at 73 oF and 40% R.H. for two days before 

the cement was extracted with CHCl3. The weights of the CHCl3-soluble residues 

are given in Table GS. Infrared spectra of the top two residues indicated only 

hydrocarbons in the cements, typical of trace residues found in commercial 

86 
portland cements. The infrared spectrum of the residue from Package 8 was 

complex, indicating the presence of short chain esters and amides. These are 

degradation products of the polymer and the "slip additive" which permits 

manipulation of Surlyn(TM) by high~speed machines. 

Table GS. 

Package 

Control 

3 

8 

Effect of Hot Environment 

Residue 

0.006% 

0.005 

0.020 

Packages of types 2 and 8 along with a glass vial of SRM 114n were subjected to 

the vibration and abrasion tests previously described. The external appearance 

of all three types of containers was unremarkable after the vibration test. 

Before testing, both the polyethylene and glass had very smooth surfaces 

showing only minor topography at moderate magnification. The Surlyn(TM) had a 

cratered appearance that turned out to be caused by the mirror-pocket casting 

rollers used in extruding this material. After testing and cleaning with 

alcohol the inner su~face of the polyethylene was deformed and cement particles 

remained on the surfaces of both the smooth glass and the cratered Surlyn(TM), 

but the plastic surface held many more particles than the glass surface. 

Packages that had an aluminum foil vapor barrier and a polyethylene heatsealable face performed well. The appearance of the Kraft paper substrates 

were slightly affected by the fog room exposures although the contents were 

preserved. The plastic substrates (Packages 4 and 6) gave the best external 

appearance after all tests. These plastic films (Mylar(TM) and Tyvek(TM)) also 

provide superior strength and external abrasion resistance; however, the Kraft 

paper substrates may accept and retain a printed label better than the plastic. 

The smoothness of the polyethylene inner surfaces allowed easy discharging of 

the samples, although some cement was difficult to remove from the seams. The 

rough surface of the Surlyn(TM) trapped some of the smaller particles, which 

could not be removed even with camel-hair brushes and swabbing. Coupled with 

the problem of the organic residue found in the cement, it is not recommended 

the Surlyn(TM) be used as a heat-sealable inner liner. 

87 
Conclusions and Recommendations 

Flexible packages made of laminated barrier materials containing pinhole-free 

aluminum foil and having polyethylene film as the sealing material were found 

to protect hygroscopic cement from hydration and carbonation. However, several 

factors mitigate against the use of these packages for cement: 

(1) Chemicals in or on the surfaces of the plastic films can contaminate the 

cement. 

(2) Sealing the packages is critical and should be performed with an automated 

sealing machine, which requires considerable capital investment. Cements 

may also interfere with proper sealing. 

(3) Cement sticks to the inner surtaces ot the flexible packages. Thus not all 

of the sample can be removed from its container and some segregation may 

occur. 

(4) Manufacturers of the packaging films generally agree that the filma will 

retain their initial properties for several years, but they will not 

guarantee them for as long as ten years. 

(5) It is concluded that at this time flexible packages are not reliable for 

cement SRMs that may be in storage for ten or more years before use. 

88