# NBS SPECIAL PUBLICATION

# 260-110

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 ofCongress 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 for Materials Science and Engineering. 

## 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, industry, and commerce; provides advisory and research services to other Government agencies; conducts physical and chemical research; develops, 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: 

## The National Engineering Laboratory 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 ofthe following centers: 

## The Institutefor Computer Sciences and Technology Conducts research and provides scientific and technical services to aid Federal agencies in the selection, acquisition, application, and use of computer technology to improve effectiveness and economy in Government 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 ofthe 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 11

### R203 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



### ivPreface

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

vOTHERNBS PUBLICATIONSINTIDS SERIES
Seward, R. W., ed., NBS StandardReference Materials Catalog1988-89,NBS Spec.Publ.260(January 1988) Michaelis,R. E.,andWyman,L.L.,StandardReference 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., andMoore, G. A., Standard Reference Materials: Metallographic Characterization ofan NBS SpectrometricLow-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 SpectrometricAnalysisofCopper-BaseAlloys,NBS Misc. Publ. 260-5 (March 1965). PB168068** Shultz,J. I., StandardReferenceMaterials: Methods for the ChemicalAnalysisofWhiteCastIron Standards, NBS Misc. Publ. 260-6 (July 1965). COM74- 11068** Bell, R. K., StandardReferenceMaterials: Methods for the Chemical Analysis of NBS Copper-Base SpectrochermicalStandards,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 ReferenceMaterials: HalfLivesofMaterials Usedin the Preparation of Standard Reference Materials of NineteenRadioactiveNuclides IssuedbytheNational 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: HomogeneityCharacterizationofNBS Spectrometric Standards II: Cartridge Brass and Low-Alloy Steel, NBS Misc.Publ. 260-10 (December 1965). COM74- 11064** Napolitano,A., andHawkins,E.G.,StandardReference 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 CharacterizationofNBS SpectrometricStandardsIII:White CastIron and Stainless SteelPowderCompact,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 ofW20% Mo Alloy Fabricatedby PowderMetallurgical Methods, NBS Spec. Publ. 260-16 (January 1969). COM74-11062** Paule. R. C

.. and Mandel. J.• Standard Reference Materials: Analysis ofInterlaboratoryMeasurements on theVaporPressureofGold (CertificationofStandardReferenceMaterial745). NBS Spec. Publ. 260- 19 (January 1970).PB190071** Paule, R. C., and Mandel, J., Standard Reference Materials: Analysis ofInterlaboratoryMeasurements ontheVaporPressuresofCadmiumandSilver,NBS Spec.Publ.260-21(January 1971).COM74-11359** Yakowitz, 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., andHawkins,E. G.,StandardReference Materials: ViscosityofaStandardBorosilicateGlass, NBS Spec.Publ. 260-23 (December 1970). COM71- 00157** Sappenfield, K. M., Marinenko, G., and Hague, J. L., StandardReferenceMaterials: ComparisonofRedox 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., StandardReferenceMaterials:UraniumIsotopicStandard 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 andEvaluation 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.,StandardRelerenceMaterials: Calibration ofNBS 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.,andShaievitch,A. B. (translated by M. C. Selby), Standard Reference Materials: StandardSamples Issuedin the USSR (A Translationfrom theRussian),NBS Spec.Publ. 260- 30(June 1971).COM71-50283** Hust, J. G., and Sparks, L. L., Standard Reference Materials: ThermalConductivityofElectrolyticIron SRM734 from 4 to 300K,NBS Spec. Publ.260-31 (November 1971). COM71-50563** Mavrodineanu,R.,andLazar,J.W.,StandardReference Materials: Standard Quartz Cuvettes for High Accuracy Spectrophotometry, NBS Spec. Publ. 260-32 (December 1973). COM74-50018** Wagner, H. L., Standard Reference Materials: ComparisonofOriginalandSupplementalSRM705,Narrow Molecnlar Weight Distribution Polystyrene, NBS Spec. Publ. 260-33 (May 1972). COM72- 50526** Sparks, L. L., and Hust, J. G., Standard Reference Materials:ThermalConductivityofAusteniticStainlessSteel,SRM735from 5to280K,NBS Spec.PubI. 260-35 (April1972.)COM72-50368** Cali, J.P., Mandel, J., Moore, L. J., and Young, D. S., StandardReferenceMaterials: ARefereeMethod for the Determination ofCalcium 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., andPowell,R. L., StandardReference Materials: TheEddy 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 ofThermal 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 ofLinear Polyethylene, SRM 1475, NBS Spec. Publ. 260-42 (September 1972). COM72-50944**



### Vii Yakowitz, H., Ruff, A. W., and Michaelis, R. E., Standard Reference Materials: Preparation and HomogeneityCharacterizationofanAusteniticIronChromium-Nickel Alloy, NBS Spec. Publ. 260-43 (November 1972). COM73-50760** Schooley,J. F., Soulen;**R~:J.,** Jr., andEvans, G. A.,Jr., Standard Reference Materials: Preparation and Use ofSuperconductiveFixedPointDevices, SRM767, NBS Spec.Publ.260-44 (December 1972).COM73- 50037** Greifer,B.,Maienthal,E.J.,Rains,T. C.,andRasberry, S.D.,StandardReferenceMaterials:PowderedLeadBased 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 StandardReferenceMaterials: Austenitic Stainless Steel, SRM's735 and798,from 4 to 1200 K, NBS Spec. Publ. 260-46 (March 1975). COM75- 10339** Host, J. G., Standard Reference Materials: Electrical Resistivity ofElectrolytic Iron, SRM797, 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 ofPrecision Thermometers for theClinicalLaboratory, SRM933 and SRM 934, NBS Spec. Publ. 260-48 (May 1974). COM74-50533** Carpenter,B.S.,andReimer,G. M.,StandardReference 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: ElectrolyticIron,SRM's734and797from4to 1000K,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-SRM930NBS 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,from4to3000K,NBS Spec.Publ.260-52(September 1975). COM75-11193** Durst, R. A., Standard Reference Materials: Standardization ofpHMeasurements,NBS Spec.PubI. 260-**5~** (December 1975. Revised). PB248127**Burlce, R. W., and Mavrodineanu, R., Standard ReferenceMaterials: CertificationandUseofAcidic 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: PolyesterFilm for Oxygen Gas TransmissionMeasurementsSRM 1470,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 ofSodium 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 ReferenceMaterialQuinineSulfateDihydrate(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 ofNBS Stamlan.lReference Materials, NBS ResearchMaterials,andOtherRelatedSamples,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 DeterminationofChlorideinSerum,NBSSpec.Publ. 260-67 (November 1979).PB80-110117**



### viiiMavrodineanu. R.• and Baldwin. J. R.. Standard Reference Materials: Metal-On-Quartz Filters 

## as a StandardReference 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.,andRains,T. C., Standard Reference Materials: A Reference Method for the Determination ofLithium 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 StandardsIssuedbythe 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.,andMandel.J.• StandardReference**Materials~** SRM900.Antiepilepsy Drug Level Assay Standard, NBS Spec. Publ. 260-72 (June 1981).PB81-220758 Interrante, C. G., and Hicho, G. E., StandardReference Materials:AStandardReferenceMaterialContaining Nominally Fifteen Percent Austenite (SRM 486), NBS Spec. Publ. 260-73 (January 1982). PB82- 215559** Marinenko, R. B., Standard Reference Materials: PreparationandCharacterizationofK -411 andK-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 ofFirst 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:AStandardReferenceMaterialContaining NominallyFivePercentAustenite(SRM485a),NBS Spec. Publ. 260-76(August1982).PB83-115S68** Furukawa,G. T.,Riddle,

### J. L.,Bigge,W. G., andPfieffer,E.R., StandardReferenceMaterials: Application ofSomeMetalSRM'sasThennometricFixedPoints, NBS Spec. Publ. 260-77 (August 1982). PB83- 117325** Hicho, G. E., and Eaton, E. E., Standard Reference Materials: Standard Reference Material Containing NominallyThirtyPercentAustenite(SRM487),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., andHertz, H. S., Standard Reference**Ma~als:** Evaluation by an ID/MS Method ofthe AACC Reference Method forSerumGlucose,NBSSpec.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., StandardReference Materials: The Measurementof the Catalytic (Activity) Concentration ofSevenEnzymes inNBS Human Serum SRM909,NBS Spec. Publ. 260-83 (June 1983).PB83-239509** Gills,T.E.,Seward,R.W.,Collins,R.J., andWebster, W. C., Standard Reference Materials: Sampling, Materials Handling, Processing, and Packaging of NBS Sulfur in Coal Standard Reference Materials 2682,2683, 2684,and2685,NBS Spec.Publ.260-84 (August 1983).PB84-109552** Swyt, D. A., StandardReference Materials: A Look at TechniquesfortheDimensionalCalibrationofStandardMicroscopicParticles,NBS Spec. Publ. 260-85 (September 1983).PB84-112648** Hicho, G. E., and Eaton, E. E., Standard Reference Materials: A Standard Reference Material ContainingTwoandOne-HalfPercentAustenite, SRM488, NBS Spec. Publ. 260-86 (December 1983). PB84- 143296** Mangum, B. W., Standard Reference Materials: SRM 1969: Rubidium Triple-Point - A Temperature Reference StandardNear 39.30

# oc, NBS Spec.Publ. 260-87 (December 1983).PB84-149996** Gladney,E. S.,Burns,C.E.,Perrin,D.R.,Roelandts, I., andGills,T.E., StandardReferenceMaterials: 1982 Compilation of Elemental Concentration Data for NBS Biological, Geological, and Environmental StandardReferenceMaterials,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 5to 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 ElectricalResistivity ofEleetrolyticIron,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., andClark, A. F.; StandardReferenceMaterials: CriticalCurrentMeasurementsonanNbTiSuperconducting 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 (SupplementtoNBS 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 atthe National Bureau ofStandards to Certify Sulfurin Coal SRM'sforSulfurContent,CalorificValue,AshContent, 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: Developmentofa 1J.Ull DiameterParticle 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., andZook,A. C., StandardReference Materials: Unanium-235 Isotopic Abundance StandardReference Materials for Gamma Spectrometry Measurements,NBS Spec. Publ. 260-96 (September 1986).PB87-108544** Mavrodineanu,R., andGills,T.E.,StandardReference Materials: SummaryoftheCoal,Ore,Mineral,Rock, and Refactory Standards Issued by the National Bureau ofStandards,NBS Spec. Publ. 260-97 (September 1985). SN003-003-026HH-3• Hust,J. G., StandardReference Materials: Glass FiberboardSRMforThermalResistance,NBS Spec.PubI. 260-98 (August 1985). SN003-003-02674-3* Callanan,J. E.,Sullivan,S. A.,andVecchia,D. F.,Standard Reference Materials: Feasibility Study for the Development ofStandards Using Differential Scanning Calorimetry, NBS Spec. Publ. 260-99 (August 1985). SN003-003-02675-l*Taylor,

### J. K., StandardReference Materials: Handbook for SRMUsers, NBS Spec. Publ. 260-100 (September 1985).PB86-110897** Mangum, B. W., Standard Reference Materials: SRM 1970, Succinonitrile Triple-Point Standard: A TemperatureReferenceStandardNear58.08

# 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.,andAdams,B.,Standard Reference Materials: Holmium Oxide Solution Wavelength Standardfrom 240- 650nm, SRM2034, 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.,andAlvarez,R., StandardReference**Materials~** SummaryoftheBiological andBotanical 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 ReferenceMaterials: SummaryoftheEnvironmental Research,Analysis, andControlStandardsIssuedby the National Bureau ofStandards, NBS Spec. Publ. 260-105 (March 1986). SN003-003-02725-1* Koch, W. F., ed., Standard Reference Materials: MethodsandProceduresUsedattheNationalBureau ofStandards to Prepare, Analyze, and Certify SRM 2694, Simulated Rainwater, and Recommendations forUse,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 (InPreparation). Mavrodineanu, R., andGills,T. E., StandardReference Materials: SummaryofGasCylinderandPermeation TubeStandardReferenceMaterialsIssuedbytheNationalBureauofStandards,NBS Spec.Publ.260-108 (May 1987). Candela.G. A

..Chandler-Horowitz.D

..Novotny.D. B

.. Marchiando, 

### J. F., and Belzer, B. 

### J., Standard ReferenceMaterials:PreparationandCertificationof an Ellipsometrically DerivedThickness andRefractiveIndex Standardofa Silicon DioxideFilm (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, andTesting), NBS Spec.Publ. 260-110

X Gladney,E. S.,O'Malley,B.T.,Roelandts, 1.,andGills, T. E., StandardReferenceMaterials: Compilation of Elemental Concentration Data for NBS Clinical, Biological,Geological, andEnvironmental 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 onefourth of thepurchasepriceforpostage. **Maybeordered from: NationalTechnical Information Services {NTIS), Springfield,VA22161.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.

2SRM 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** 

# ·-·------·-·-·---------·----·

2O----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.

4Figure 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 Doubledehydration of thecement solution to precipitateout theSi02 • 

# J 

# I

PRECIPITATE of impure Si02 • Fll TRATE containsremaining cement elements. X-ray fluorescence (XRF) analysis used to**det~t** im· Colorimetric analysis used to determine unprecipi· puritiC$ in theprecipitate. tated (soluble) Si02 in filtrate. 

# I

.. HF" treatment of Si02 precipitate removes Si02 .(byevolution 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 NH40H (R20 3 ) group 

# J (AI:z03 , Fe20 3 , P20 5 , Ti02 , ZnO, Cr20 3 , and ZrOI. 

# I
PRECIPITATE ignited and weighed as R20 3 group. FILTRATE contains CaO,MgO, Mn20 3 , K 20, Na20, Sro, S03 , etc.I .X-ray fluorescence analysis used to detect ZnO, Atomic absorption analysis used to detect unprecipi· 0 20 3 , Zr and other impurities. tatedAl:z03 and Fe20 3 • 

# l Removal ofmanganese (by co-precipitation method of Peck) prior to thecalcium 

# J group determination. 

# I
PRECIPITATE of Mn02 discarded. FILTRATE (contains CaO, MgO, K 20, Na20, $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. FllTRATE (contains MgO, K 20, Na20, $03 , 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:!P20 7 • fll TRATE**(cont<~ins** K 20, Na20, 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 €ettifitattof 

# §nalpsts Standard Sampie 177 Portland Cement

ANALYST 

### SiOs 

### AJ,O, Fe,01 

### •TiOt 

### PtO, bCaO SrO 

### MgO 

# so, Mn,o, NatO K,O •Louon Ianldon 

## 1--------- 21.91 5.26 

## { d 2.4-3 

## 1 2.4.0 1,

_________ 21.88 5.28 ;2. 39 J

______ ID21.96 5.20 2. 38


# •------ 21.90 0 5.38 2.40 

## 5---------- 21.96**e~~5.SO** 2. 38 6

_________ 121.91 15.26 '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**~** tot,oooeC.for IS min. ina CDftrecl platiaaa crucible (ASTMSpec. Cll4-S3).

• NH.CNS-plaot.ometric. • Mob'bcla.....Waep.. a1 •rico t J11ame**~** S.AuLa.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
16l.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

......nlaeiudada

### no. orPJOa. • Flame plilotoawtric: (ASTMSpec. Cll4-S6T).**tkra~** clehTdratioo with HCO. with iaternniq
r Notiudacled iatbe •....._ 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, NationalBureau ofStandards. 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.**~'·** ,{alterH.Price,DivisionofEngineeringLaboratories, Bureau ofReclamation, 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
Fe2

## o 3

----------------------------- 2.01 0.25

.33 CaO (+SrO)

----------------------- 66.60 SrO

------------------------------ 0.11 

### MgO

------------------------------ 1.12 803

------------------------------ 1.75 Mn203

---------------------------- 0.03 Na2

## o ----------------------------- .08 K

2

## o ·-·--------------------------- .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
40U 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



### Si02 •••••••••••••••••••••••••••••••• 

### 24.1 7 

### Al 2

### 0 3 •••••••••••••••••**~** • • • • • • • • • • • • • 

### 3.30 

### Fe2

### 0 3 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 

### 3.07 

### Ti0 2 •••••••••••••••••••••••••••••• , • • 

### 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.·**~ 64~3** 

# 4 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 DivisionU. 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 Al2

### 0 3 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 

### 6.:38 Fe203

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . • . . . . . . . . . . 

### 2.5() Ti02 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 

### 0.25 p205

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 

### .32 CaO 

### <+SrO> ••••.••...•.•••••••••••••.••.••••.•• 63.36 

### SrO••••••••.••••••••••..•••••••••••••••••••**~**

# ~:::::::::::::::::::::::::::::~~ 270 Mn203

.........................**·o~\ ~** 

# .... 0.07 Na2

### 0 .......•...........

# ~**~-~** . . . . . •
. . . • • .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 0

--------------------------- 

### 2 3 Percent 20.65

5.04 3.27 

### 0.26
P205

--------------------------- .OS CaO (+ 

### SrO)

-------------------- 

### 61.48 

### SrO 0.11 MgO 4.25 

### 2.28


### Mn2

## o 3
--------------------------- 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
P2

# o5

------------------------ 

### .13 

### CaO (+SrO)-------------------

# 6~~ sro

# --------------------~~ 

# :::

# ~~~~~~~~~~~~--~**2::~ Mn203---~-~**  ---------- 0.04

# ~~~~~~~~~~~~~~~~~~~~~**~:: ~20**  ------------------------(.012) 

## Rb2 o 

## -----------------------*(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 44U.S.**~-:bf** Commerce**~o~driae**

## i~1 Nalional

### ~=:~f~

Ernest AID&ier', Director 

# Nattnnal fSurtau nf**~anbarbs** 

# Qttttifitatt nfAnalysts 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 ofinstrumental methods of analysis. The value listed for a constituent is the

### presentbestestimate ofthe "true" value based on the results ofa ·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 ofErlin, Hime Associates acting as consultant. The certified value for a constituent is not expected to deviate from the "true" value by more than ± 1

### inthe last significant figure reported; for a subscript figure, thedeviation is not expected tobe more than ± 

### S. Based ontheresults ofhomogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight 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 ofASTM C 114 are followed a smaU amountofCaOwill remain in the MgOprecipitate. Inthis casetheuncorrected 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 ofthe atomic weight ofoxygen to the molecular weight of fluorine (0.421). · The technical and support aspects involved in the preparation, certification, and issuance ofthis Standard Reference Material were coordinated through the Office ofStandard Reference Materials by B. E. Foster, R. E. Michaelis, and C. L. Stanley. Washington, D.C. 20234 December 15, 1983 (Revision ofcertificates dated 2-24-77 and 6-12-74) {Over) 45 Stanley D. Rasberry, Chief Office ofStandard Reference MaterialsHOMOGENEITY TESTING: Measurements were made at NBS on the portland cement supplied by the Lone Star Cement Corporationby 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 bymaking four independent measurements oneachbriquette. 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 majorconstituents CaO, Si02, AI2

## o3and MgO. (The methods were essentially those ofASTM Cll4using a 0.5-g sample.) Fe20 3was determinedbydichromate titration and S03byprecipitationin an acid solution after removal ofthe ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for ISO,**N~O,** SrO,**M~0 ,**  ZnOandCr20 3•Colorimetrictechniques were used todetermineTi02 and P 205 while_fluoride was determined by an ion selective electrode method. Loss on ignition was determined at**l000°C~** In each determination duplicatemeasurements were madeontwo to tenrandomly selected samples. Through theuse ofvarious techniques (colorimetric, gravimetric, potentiometric, opticalemissionelements 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:Toobtainthemostaccurateresults byx-ray fluorescent methods ofanalysis, theuser shouldcomparehis 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.

46U.S. Departi\\tm.OfCommerce**M~~~'B.ald,rige :~~~~**  ;-···;................... Nauonal'U,urcau of-Standards

Ernest A'mbti:r.**Dir~tor** 

# National Jlureau nf!;tanbarbs <tterttftcattnfAnalusis 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 ofinstrumental methods of analysis. The value listed for a constituent is the

### presentbestestimate ofthe "true" value based on the results ofa 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 ofErlin, Hime Associates acting as consultant. The certified value for a constituent is not expected to deviate from the "true" value bymore than 

### ± 1inthelast significant figure reported; for a subscript figure, the deviation is notexpected tobemorethan 

### ±5. Based ontheresults ofhomogeneitytesting, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight

caoa**~2.58** Na2 0 0.15 Si02 20.73 SrO .12 Al20 3 5.21 

### P2

### 0, .10 Fe20 3 2.84 Mn203 .28 503 2.21 

### F .08 MgOa 3.30 ZnO .02 K

20 0.42 Cr2 0 3 .08 Ti02 .29 lgn. loss 1.62 Totalb 100.00


### •uthe procedures ofASTM CI14are followed asmall amountofCaOwillremain inthe MgOprecipitate. Inthis casetheuncorrectedvalues given below for CaO and MgO should beused. CaO 62.54 MgO 3.33
bAcorrection has been made for the amount offluoride present. This correction, which was subtracted from the gross total, was determined by multiplying the percent fluoride by the ratio ofthe atomic weight ofoxygen to the molecular weight offluorine (0.421).
The Lcchnkal and support aspects involved in the preparation, certification, and issuance ofthis Standard Reference Material were coordinated through the Office ofStandard Reference Materials by B. E. Foster, R. E. Michaelis, and C. L. Stanley. Washington, D.C. 

### 20234 December 15, 1983 {Revision ofcertificates dated 

### 2-24-77 and 

### 6-12-74) (Over) 47 Stanley D. Rasberry, Chief OfficeofStandard Reference MaterialsHOMOGENEITY 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 ofthese data indicated the homogeneity was satisfactory. Following these measurements the cement was thoroughly blended and packaged in hermetically sealed glass vials by personnel ofthe 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 majorconstituents CaO, Si02, Al20 3and MgO. (The methods were essentially thoseofASTM C114using a 0.5-g sample.)Fe20 3was determinedbydichromatetitrationand S03byprecipitationin an acid solution after removal ofthe ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K 2 0,Na2 0,SrO, Mn2 0 3, ZnOandCr2

# o3•Colorimetrictechniques were used todetermineTi02 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 weremadeontwototen randomly selected samples.Through theuse ofvarioustechniques (colorimetric, gravimetric, potentiometric, opticalemissionelements were determinedto be less than 0.01 

### wtOfo: Cl, 

### Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of 

### 100.0007o ofthe certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. CAUTION: To obtain themost accurateresults by x-ray fluorescent methodsofanalysis, the user should comparehis 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.



### 48U.S. 

### DepartiMm·:i>rCommerce**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 ofinstrumental methods of analysis.
The value listed for a constituentis thepresent best estimate ofthe ''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 ofErlin, Hime Associates acting as consultant. The certified value for a constituent is not exJ'eeted to deviate from the "true" value bymore than ± 1in the last significant figure reported: for a subscript figure, the deviationis notexpected to be morethan ±

### 5. Based onthe results ofhomogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight

caoa 59.83**N~O** 0.07 Si02 18.41 SrO .21 Al203 6.29 P20s .17 Fe2 0 3 2.61 Mn2 0 3 

### .09 

## so3 7.07 F 

### .04 MgOa 1.23 ZnO .01 

### K

2 0 0.45 Cr2 0 3 .01 Ti02 .32 Ign. loss 3.24 Totalb 100.03

1 1ftheprocedures ofASTM C114arefollowed asmallamountofCaOwillremainintheMgOprecipitate. Inthiscasetheuncorrectedvalues given below for CaO and MgO should be used. CaO 59.79 MgO 1.26 bA correction has been made for the amount offluoride present. This correction, which was subtracted from the gross total, was determined by multiplying the percent fluoride by the ratio ofthe atomic weight ofoxygen to the molecular weight offluorine (0.421). The technical and support aspects involved in the preparation, certification, and issuance ofthis Standard Reference Material were coordinated through the Office ofStandard Reference Materials by B. E. Foster, R. E. Michaelis, and C. L. Stanley. Washington, D.C. 20234 December 15, 1983 (Revision ofcertificates dated 2-24-77 and 6-12-74) (Over)



### 49 Stanley D. Rasberry, Chief Office ofStandard Reference MaterialsHOMOGENEITY 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 byx-ray fluorescence analysis. Thecement 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 majorconstituents CaO, Si02, AI20 3 and MgO. (The methods were essentially thoseofASTM C114using a 0.5-g sample.) Fe20 3was determinedbydichromate titrationand S03byprecipitationin an acid solution after removal ofthe ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K2 0,**N~O,** SrO, Mn2 

### o3, ZnOandCr2 0 3. Colorimetrictechniques wereusedtodetermineTi02 and P205 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 1000°C. In each determination duplicatemeasurements were madeontwo to ten randomly selected samples. Through theuse ofvarious techniques (colorimetric. gravimetric. potentiometric. opticalemission**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: Toobtainthe most accurateresults byx-ray fluorescent methods ofanalysis, the user should comparehis 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.



### 50U.S. [)epartri1CnfofCommerce**Mal~laLBildri&e ~·** 

### :.~>:!!

### ..

### ! National**~**otStalldards

Ernest**~;riuector** 

# Nntinnnl Jiurtnu nf.&tunbnrbs C!ttrtificntt nfAnulgsis 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 ofinstrumental methods of analysis. The value listed for a constituent is the

### presentbestestimate ofthe "true" value based on the results ofa 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 ofErlin, Hime Associates acting as consultant. The certified value for a constituent is not expected to deviate from the**"true~'** value by more than 

### ± 1inthe last significant figure reported; for a subscript figure, the deviation is not expected to be more than 

### ±5. Based onthe results ofhomogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight CaQii 63.54 Na2 0 0.11 

### Si02 23.; 

### SrO .04 Al2 0 3 3.02 P20s .08 Fe2 o 3 1.61 Mn2 0 3 .12 

## so3 2.3. F .06 Mgo• 

### 3.95 ZnO .03 

### K

2 0 0.59 Cr2 0 3 .01 Ti02 .18 lgn. loss 1.16 Totcilb 100.00


## autheprocedures ofASTM Cll4are followed asmallamountofCaOwillremainintheMgOprecipitate. Inthiscasetheuncorrectedvalues given below for CaO and MgO should be used. CaO 63.49 MgO 3.98

bA correction has been made for the amount offluoride present. This correction, which was subtracted from the gross total, was determined by multiplying the percent fluoride by the ratio ofthe atomic weight ofoxygen to the molecular weight offluorine (0.421). The technical and support aspects involved in the preparation. certification. and issuance ofthis 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 ofcertificates do.ted 2-24-77 and 6-12-74) (Over)


### 51 Stanley D. Rasberry, Chief OfficeofStandard Reference MaterialsHOMOGENEITY 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 checkinginhomogeneity, were determined bymaking four independent measurements oneach 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 themajorconstituents CaO, Si02, AI20 3andMgO. (The methods were essentially those ofASTM Cll4using a 0.5-g sample.)Fe20 3was determinedbydichromatetitrationandS03byprecipitationin an acid solution after removal ofthe ammonium hydroxide group and silica. Atomic absorption spectroscopy tech**nique~** wereused for JSO,**N~O,** SrO,**M~0 ,**  ZnO andCr2 

### o3•Colorimetrictechniques wereusedtodetermineTi02 and P20 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 1000°C. In each determination duplicatemeasurements were madeontwo totenrandomly selected samples. Through theuse ofvarioustechniques (colorimetric. gravimetric. potentiometric. opticalemissionelements were determinedto be less than 0.01 wtOJo: Cl, Ba, Zr, B, V, Ni, Mo, Sn, Pb, Cu, and Ag. The total of lOO.OOOJo ofthe certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. CAUTION:To obtainthe most accurateresults by x-ray fluorescent methods ofanalysis, theuser shouldcomparehis 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.



### 52U.S.**Depart~i-~f** Commerce

### Ma'~e!fge i ··..,..·,.-.·. ! National**~ea11** of$taadards

ErnatAmttler-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

### presentbestestimate ofthe "true" value based on the results ofa 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 ofErlin, Hime Associates acting as consultant. The certified value for a constituent is not expected to deviate from the ''true'' value by more than 

### ± 1in the last significant figure reported; for a subscript figure, the deviation is notexpected tobemorethan 

### ±S. Based on the results ofhomogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight

caoa 66.04 N"lO 

### 0.1S Si02 

### 23.07 SrO .09 Al20 3 

### .3.28 P20s .24 Fe20 3 1.80 Mn2

## o3 .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


### autheprocedures ofASTM C 114are followed a small amountofCaOwill remain in theMgOprecipitate. In this casetheuncorrectedvalues 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 ofthe atomic weight ofoxygen to the molecular weight of fluorine (0.421). The technical and support aspects involved in the preparation, certification, and issuance ofthis 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 ofcertificates dated 2-24-77 and 6-12-74) (Over)


### 53 Stanley D. Rasberry, Chief OfficeofStandard ReferenceMaterialsHOMOGENEITY 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 byx-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 oneach 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, AI2

### o3 and MgO. (The methods were essentially those ofASTM Cll4using a 0.5-g sample.) Fe2

## o3was determinedbydichromatetitrationand S03byprecipitationin an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K 20,Na20, SrO, Mn20 3, ZnOand Cr20 3•Colorimetrictechniques were used todetermineTi02 and P2 o 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 1000°C. In each determination duplicatemeasurements were madeon two to ten randomly selected samples. Through theuse ofvarious techniques (colorimetric, gravimetric, potentiometric, opticalemission 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 accurateresults byx-ray fluorescent methods ofanalysis, the user should comparehis 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.

54U.S. Department ofCommerce**~ae**

# ~~~ NatioDal**~** ofStudards**Emal·~..-** 1>irector 

# Nntinnul iiur.euu nf**~unburbs** 

# Q!ertificatt nfAnuluuts 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

### presentbestestimate ofthe "true" value based on the results ofa 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 ofErlin, Hime Associates acting as consultant. Thecertified value for a constituent is not expected to deviate from the "true"value

### by morethan ± 1inthelast significant figure reported; for a subscript figure, the deviation is notexpected tobemorethan 

### ±5. Based ontheresults ofhomogeneitytesting, maximum variations within and among samples are estimated to be less than those uncertainty figures. Constituent PercentbyWeight Constituent PercentbyWeight

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 K

20 0.59 Cr20 3 .01 Ti02 .25 Ign. loss .9s Totalb 99.97
•Ifthe proceduresofASTM Cll4arefoliowed a small amountofCaOwill remain in theMgOprecipitate. Inthis case theuncorrectedvalues given below for CaO and MgO should be used.
CaO 62.05 MgO 3.86
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 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 ofthis Standard Reference Material were coordinated through the Office ofStandard Reference Materials by B. E. Foster, R. E. Michaelis, and C. L. Stanley. Washington, D.C. 20234 December 15, 1983 (Revision ofcertificates dated 2-24-77 and 6-12-74) (Over) 55 Stanley D. Rasberry, Chief OfficeofStandard Reference MaterialsHOMOGENEITY 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 majorconstituents CaO, Si02, AI20 3andMgO. (The methods were essentially those ofASTM Cll4using a0.5-g sample.)Fe20 3was determinedbydichromatetitration and S03byprecipitationin an acid solution after removal ofthe ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques wereused for

### K 20,**N~O,** SrO, Mn2

## o3, ZnOandCr2

## o3. Colorimetrictechniques wereusedtodetermineTi02 and P2 0 5 while fluoride was determined by an ion selective electrode method. Loss on ignition was determined at 1000°C. In each determinationduplicatemeasurements were madeontwo to tenrandomly selected samples. Through the use ofvarioustechniques (colorimetric, gravimetric, potentiometric, opticalemissionelements were deteoninedto 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: Toobtain themostaccurateresults byx-ray fluorescent methods ofanalysis, theuser should comparehis 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.



### 56U.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 thepresent best estimate ofthe "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 bymorethan ± 1

### in the last significant figure reponed; for a subscript figure, the deviation is not expected tobe morethel!l ±5. Based on theresUlts ofhomogeneity testing, maximum variations within and among samples are estimated to be less than those uncertainty figures.
Constituent PercentbyWeight Constituent PercentbyWeight

caoa 

### 65.76**N~O** 

### 0.65 Si02 

### 21.61 SrO 

### .15 Al203 

### 4.28 P205 .08 Fe2

### o3 

### 2.40**M~0**

### 3 .08 

## so3 2.4g F .02 

### Mgoa 1.26 ZnO .01 

### K..,O



# .. 0.06 Cr2 

### 0 3 

### .01 Ti02 

### .32 lgn. loss l.Oo Totalb 

### 100.16

1 Ifthe procedures ofASTM Cll4are followed a small amountofCaOwill remain intheMgOprecipitate. Inthis case theuncorrected values given below for CaO and MgO should be used.
CaO 65.73 MgO 1.28
bA 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 ofthis Standard Reference Material were coordinated through the Office ofStandard 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 ofStandard Reference MaterialsHOMOGENEITY 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'IALYSIS PROGR

. .L\1\1 OF THE PORTLAND CEMENT CORPORATION: "Wet" chemical gravimetric methods were used for the major**~onstituents** CaO, Si02, Al20 3and ;vtgO. (The methods were essentially those of**AST~l** C 114 using a 0.5-g sample.) Fe20 3was determinedby dichromatetitration and S03by precipitationin an acid solution after removal of the ammonium hydroxide group and silica. Atomic absorption spectroscopy techniques were used for K 20, 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 ofvarious 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 accurateresults by x-ray fluorescent methods ofanalysis, 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 calibrationofinstrumental methods ofanalysis. SRM 1880consistsofthreesealedvialsoftype 1Portlandcement,each containing approximately 5 grams. The certified value listed for a constituent is the present best estimate ofthe "true'" value based on the results of a definitive analysis programcarried outin thelaboratories ofthePortland CementAssociation. Thecertifiedvaluefora constituent is not expected to deviate from the "true'" value by morethan

### ± 1in thelast significant figure reported; fora 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 PercentbyWeight Constituent PercentbyWeight 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 •Ifthe procedures ofASTM Cll4arefollowed, a small amount ofCaOwill remain in the MgOprecipitate. Inthiscase the uncorrected values given below for CaO and MgO should be used: CaO 63.0s MgO 2.7s bA correction has been made for the amount offluoride present. Thiscorrection. which was subtracted from the gross total, was determined by multiplyingthepercentfluoridebytheratio .Jftheatomicweight ofoxygentotwicethea.tomic weight of fluorine (0.421). Correction ofthe total for the small amount of chloride was negligible (<0.0I%). The technical and support aspects involved in the preparation, certification, and issuance ofthis 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 ofStandard Reference MaterialsAcknowledgements 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 cementwas 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 ofType I Portland cement supplied by the St. Mary's Cement Company in Canada and theTexas Cement Company. Before blending, each cementwas ground in an impact mill untilall particles were between 0.5 and 45 .urn as selected with an air classifier. The size distributions ofthe 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 Followingthe packaging ofthe cement in hermetically sealed glass vials the homogeneity was determined by measuring 36 samples selected in a stratified random process. X-rayfluorescence analysis was used to determinethedifferences in calcium, sulfur, and iron by four replicate measurements on each briquette.
Definitive Analysis "Wet" chemical gravimetric methods were used for the majorconstituents CaO, Si02, Ah03 and MgO. (The methods were essentially those ofASTM Cll4using a 0.5-g sample.) Fe203 was determined bydichromatetitrationand S03by precipitation in an acid solution. Atomic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn203 and ZnO.,Colorimetrictechniques were used todetermineTi02 and P20s. Fluoridewasdeterminedbyanionselective electrode method and chloride wasdeterminedbya potentiometrictitrationmethod. Lossonignitionwasdeterminedat ·1000 °C. In eachdeterminationduplicatemeasurementsweremadeonthreetotenrandomlyselected samples. Through the use of various techniques (colorimetric, gravimetric, and AAS) the presence ofthe following trace elements were determined to be less than0.0

### t wt. 

### %: Ba, Zr, B, and Cr. Thetotal of 100.28%ofthecertifiedconstituentsinthecement corroborates the evaluation and indicates that significant biases have not been introduced.
Caution To obtainthemostaccurateresultsbyx-rayfluorescence methodsofanalysis,theusershouldcomparehis samplestothe particular SRM'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 ColorisWhite)

This StandardReferenceMaterial (SRM) is intendedfor use in evaluatingchemicalmethodsofanalysis andinthe calibration ofinstrumentalmethods ofanalysis. SRM 1881 consistsofthree sealedvials oftype I Portland Cement, eachcontaining approximately5 grams. The certifiedvalue listedfor a constitutentis the presentbestestimate ofthe "true" value based on the results ofa definitive analysis programcarriedoutinthelaboratories ofthePortlandCementAssociation. Thecertified 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 homogeneitytesting, maximumvariations withinandamong samples areestimatedtobeless thanthoseuncertainty figures. Constituent PercentbyWeidtt Constituent PercentbyWeiiht 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 Ifthe proceduresofASI'M C114 are followed, a small amount ofCaOwill remain in the MgO precipitate. In this case the uncorrectedvalues

given belowfor CaO andMgO should be used: CaO 58.65 MgO 2.70 b '\ correction has been made for the amount offluoride present. This correction,which was subtracted from the gross total, was determinedby

multiplying the percent fluoride by the ratio ofthe atomicweight ofoxygen to twice the atomicweight offluorine (0.421). Thetechnicalandsupportaspectsinvolvedin thepreparation,certification,andissuanceofthisStandardReference Material were coordinatedthrough the Office ofStandard Reference Materials by R.L. McKenzie.

Gaithersburg, MD 20899 December 7, 1987 (Revision ofcertificate dated 2-10-84) (over)


### 61 Stanley D. Rasberry, Chief Office ofStandard Reference MaterialsAcknowledgements 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. Homogeneitytestingwas 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 PortlandCementAssociationand5wt.%ofTerraAlba gypsum. Before blending, the ..-:cmcnt was ground in an impact milluntil allparticleswere smallerthan4Q**~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 Followingthe packaging ofthe cement inhermetically 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 ofASTM Cl14 using a 0.5-g sample.) Fe203 was determined by dichromate titrationand SOJby precipitation in an acid solution.

### At~ic absorption spectroscopy techniques were used for K20, Na20, SrO, Mn203 and ZnO. Colorimetrictechniques were used to determineTi02 and P20s. Fluoridewasdeterminedbyanionselective electrode method. Loss on ignition was determined at 1000 °C. In each determination duplicate measurements were made on threeto ten randomly selected samples. Through the use ofvarious techniques (colorimetric, gravimetric, and AAS) the presence ofthe following trace elements were determined to be lessthan0.01 wt

..%: Ba,Zr, B, Cl, andCr. The total of I00.04% of the certified constituents in the cement corroborates the evaluation and indicates that significant biases have not been introduced. ·Caution To obtain the mostaccurateresults by x-rayfluorescence methodsofanalysis,theusershouldcomparehis samplestothe 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.



### 62Appendix 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 11duplicates", 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)

70A 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 

# t2[**~**

# 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 

### 0.0 0.1 

## w +0.10 0.08 

## w 0.0 0.4 

## w 0.00 0.02 

## w +0.04 0.04 

## w 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 0.24Table 

### 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 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 w 

### 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 0.05U. S. Department of Commerce Frederick B. Dent Secretary National Bureau of Standards

# ~ational 

# lJlureau 

# nf**~tandards** Richard W. Roberta, Director 

# <!Iertifitate 

# nf**~nalt!sis** Standard Reference Materials 633-639 Portland Cements These SRM's are fine powders and are intended for use both in checkingchemical 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 3.74 

### 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 Mn

### 2

### 03 .04 

### .28 .09 

### .12 .06 

### .05 .08

K

2

### 0 .165 .43 .45 .57 .245 .59 .05 Na

### 2 

### 0 .64 .14 .07 .10 .13 .12**.6~** 

### SrO .31 

### .12 .22 .04 .10 .07 .15 Fe

### 20 

### 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 99.81a 

### 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 ofStandard 

### Rcferencc \laterials

### 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 0.130 (\"')

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.

82The 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