1、Designation: C1365 06 (Reapproved 2011)Standard Test Method forDetermination of the Proportion of Phases in PortlandCement and Portland-Cement Clinker Using X-Ray PowderDiffraction Analysis1This standard is issued under the fixed designation C1365; the number immediately following the designation in
2、dicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers direct determin
3、ation of theproportion by mass of individual phases in portland cement orportland-cement clinker using quantitative X-ray (QXRD)analysis. The following phases are covered by this standard:alite (tricalcium silicate), belite (dicalcium silicate), aluminate(tricalcium aluminate), ferrite (tetracalcium
4、 aluminoferrite),periclase (magnesium oxide), gypsum (calcium sulfate dihy-drate), bassanite (calcium sulfate hemihydrate), anhydrite (cal-cium sulfate), and calcite (calcium carbonate).1.2 This test method specifies certain general aspects of theanalytical procedure, but does not specify detailed a
5、spects.Recommended procedures are described, but not specified.Regardless of the procedure selected, the user shall demon-strate by analysis of certified reference materials (CRMs) thatthe particular analytical procedure selected for this purposequalifies (that is, provides acceptable precision and
6、bias) (seeNote 1). The recommended procedures are ones used in theround-robin analyses to determine the precision levels of thistest method.NOTE 1Asimilar approach was used in the performance requirementsfor alternative methods for chemical analysis in Test Methods C114.1.3 The values stated in SI u
7、nits shall be regarded as thestandard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory li
8、mitations prior to use. For specifichazards, see Section 9.2. Referenced Documents2.1 ASTM Standards:2C114 Test Methods for Chemical Analysis of HydraulicCementC150 Specification for Portland CementC183 Practice for Sampling and the Amount of Testing ofHydraulic CementC219 Terminology Relating to Hy
9、draulic CementC670 Practice for Preparing Precision and Bias Statementsfor Test Methods for Construction MaterialsE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Tes
10、t Method3. Terminology3.1 Definitions are in accordance with Terminology C219.3.2 Phases (1):33.2.1 alite, ntricalcium silicate (C3S)4modified in com-position and crystal structure by incorporation of foreign ions;occurs typically between 30 to 70 % (by mass) of the portland-cement clinker; and is n
11、ormally either the M1or M3crystalpolymorph, each of which is monoclinic.3.2.2 alkali sulfates, narcanite (K2SO4) may accommo-date Na+, Ca2+, and CO3in solid solution, aphthitalite (K4-x,Nax)SO4with x usually 1 but up to 3), calcium langbeinite(K2Ca2SO43) may occur in clinkers high in K2O, andthenard
12、ite (Na2SO4) in clinkers with high Na/K ratios (1).1This test method is under the jurisdiction of ASTM Committee C01 on Cementand is the direct responsibility of Subcommittee C01.23 on CompositionalAnalysis.Current edition approved Dec. 1, 2011. Published May 2012. Originallyapproved in 1998. Last p
13、revious edition approved in 2006 as C1365 - 98 (2006).DOI: 10.1520/C1365-06R11.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page o
14、nthe ASTM website.3The boldface numbers in parentheses refer to the list of references at the end ofthis standard.4When expressing chemical formulae,C=CaO,S=SiO2,A=Al2O3,F=Fe2O3,M = MgO, S =SO3,andH=H2O.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International,
15、100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.2.3 aluminate, ntricalcium aluminate (C3A) modified incomposition and sometimes in crystal structure by incorpora-tion of a substantial proportion of foreign ions; occurs as 2 to15 % (by mass) of the portland-cemen
16、t clinker; is normallycubic when relatively pure and orthorhombic or monoclinicwhen in solid solution with significant amounts of sodium (2).3.2.4 anhydrite, ncalcium sulfate CS! and is orthorhom-bic (see Note 2).NOTE 2Calcium sulfate is added to the clinker during grinding tocontrol setting time, s
17、trength development, and volume stability. Severalphases may form as a result of dehydration of gypsum. The first 1.5molecules of water are lost between 0 and 65 C with minor changes instructure; and, above 95 C, the remaining 0.5 molecules of water are losttransforming the structure to the metastab
18、le g polymorph of anhydrite(sometimes referred to as soluble anhydrite) and subsequently theorthorhombic form (3).3.2.5 bassanite, ncalcium sulfate hemihydrate CSH1/2!and is monoclinic.3.2.6 belite, ndicalcium silicate (C2S) modified in com-position and crystal structure by incorporation of foreign
19、ions;occurs typically as 15 to 45 % (by mass) of the portland-cement clinker as normally the b polymorph, which is mono-clinic. In lesser amounts, other polymorphs can be present.3.2.7 calcite, ncalcium carbonate is trigonal and may bepresent in a cement as an addition or from carbonation of freelim
20、e.3.2.8 ferrite, ntetracalcium aluminoferrite solid solutionof approximate composition C2(A,F) modified in compositionby variation in the Al/Fe ratio and by substantial incorporationof foreign ions as C4AXF2-Xwhere0x1.4; constituting 5to 15 % (by mass) of a portland-cement clinker; and isorthorhombi
21、c.3.2.9 free lime, nfree calcium oxide (C); cubic (see Note3).NOTE 3Free lime (CaO) may be present in clinker and cement butreadily hydrates to form portlandite (Ca(OH)2). Portlandite may carbonateto form calcium carbonate, generally as calcite. Heat-treating a freshly-ground sample to 600 C is usef
22、ul to convert any portlandite back to freelime but will also dehydrate the hydrous calcium sulfate phases (gypsumand bassanite) to anhydrite.3.2.10 gypsum, ncalcium sulfate dihydrate CSH2! and ismonoclinic .3.2.11 periclase, nfree magnesium oxide (M); cubic.3.3 Definitions of Terms Specific to This
23、Standard:3.3.1 Certified Reference Material (CRM), na materialwhose properties (in this case phase abundance, XRD peakposition or intensity, or both) are known and certified (see Note4).NOTE 4NIST Standard Reference Material (SRMt) Clinkers 2686,2687, and 2688 are suitable CRMs for qualification.53.
24、3.2 diffractometer, nthe instrument, an X-ray powderdiffractometer, for determining the X-ray diffraction pattern ofa crystalline powder.3.3.3 phase, na homogeneous, physically distinct, andmechanically separable portion of a material, identifiable by itschemical composition and crystal structure.3.
25、3.3.1 DiscussionPhases in portland-cement clinker andcements that are included in this test method are four majorphases (alite, belite, aluminate, and ferrite) and one minorphase (periclase).3.3.3.2 DiscussionPrecision values are provided for addi-tional phases (gypsum, bassanite, anhydrite, arcanit
26、e, andcalcite). Values for these constituents may be provided usingthis method but are considered informational until suitablecertified reference materials for qualification are available.3.3.4 qualification, nprocess by which a QXRD proce-dure is shown to be valid.3.3.5 Rietveld analysis, nprocess
27、of refining crystallo-graphic and instrument variables to minimize differencesbetween observed and calculated X-ray powder diffractionpatterns for one or more phases, estimating their relativeabundance.3.3.6 standardization, nprocess of determining the rela-tionship between XRD intensity and phase p
28、roportion for oneor more phases (see Note 5).NOTE 5In the literature of X-ray powder diffraction analysis, thestandardization process has been commonly referred to as calibration;however, we have determined that standardization is a more accurate term.3.3.6.1 DiscussionRietveld analysis uses crystal
29、 structuremodels to calculate powder diffraction patterns of phases thatserve as the reference patterns. The pattern-fitting step seeksthe best-fit combination of selected pattern intensities to theraw data. The relative pattern intensities along with thecrystallographic attributes of each phase are
30、 used to calculaterelative abundance. The standardization approach uses pow-dered samples of pure phases to assess the relationship betweendiffraction intensity ratios and mass fraction ratios of two ormore constituents; and is referred to here as the traditionalmethod.3.3.7 X-ray diffraction (XRD),
31、 nthe process by whichX-rays are coherently scattered by electrons in a crystallinematerial.4. Background4.1 This test method assumes general knowledge concern-ing the composition of cement and portland-cement clinker.Necessary background information may be obtained from anumber of references (1, 4)
32、.4.2 This test method also assumes general expertise in XRDand QXRD analysis. Important background information maybe obtained from a number of references (5-10).5. Summary5.1 This test method covers direct determination of theproportion by mass of individual phases in cement or portland-cement clink
33、er using quantitative X-ray powder diffractionanalysis. The following phases are covered by this standard:alite (tricalcium silicate, C3S), belite (dicalcium silicate C2S),aluminate (tricalcium aluminate, C3A), ferrite (tetracalcium5Portland cement clinker SRMst from the Standard Reference MaterialP
34、rogram, National Institute of Standards and Technology.C1365 06 (2011)2aluminoferrite, C4AF), periclase (magnesium oxide, M), arcan-ite (potassium sulfate, KS!, gypsum (calcium sulfate dihy-drate, CSH2!, bassanite (calcium sulfate hemihydrate,CSH1/2!, anhydrite (calcium sulfate CS!, and calcite (cal
35、-cium carbonate, CaCO3.A QXRD test procedure includes some or all of the follow-ing: (a) specimen preparation; (b) data collection and phaseidentification; (c) standardization (for the standardization ap-proach); (d) collecting a set of crystal structure models forrefinement (for the Rietveld approa
36、ch); (e) use of an internal orexternal standard (to correct for various effects on intensitybesides phase proportion); (f) analysis of the sample (in whichthe powder diffraction pattern is measured and/or the intensityof selected XRD peaks or patterns are measured); and (g)calculation of the proport
37、ion of each phase.5.2 This test method does not specify details of the QXRDtest procedure. The user must demonstrate by analysis ofcertified reference materials that the particular analytical pro-cedure selected for this purpose provides acceptable levels ofprecision and bias. Two recommended proced
38、ures (the Riet-veld approach and the traditional approach used to determinethe acceptable levels of precision and bias) are given inAppendix X1 and Appendix X2.6. Significance and Use6.1 This test method allows direct determination of theproportion of some individual phases in cement or portland-cem
39、ent clinker. Thus it provides an alternative to the indirectestimation of phase proportion using the equations in Specifi-cation C150 (Annex A1).6.2 This test method assumes that the operator is qualified tooperate an X-ray diffractometer and to interpret X-ray diffrac-tion spectra.6.3 This test met
40、hod may be used as part of a quality controlprogram in cement manufacturing.6.4 This test method may be used in predicting propertiesand performance of hydrated cement and concrete that are afunction of phase composition.6.5 QXRD provides a bulk analysis (that is, the weightedaverage composition of
41、several grams of material). Therefore,results may not agree precisely with results of microscopicalmethods.7. Apparatus7.1 X-Ray DiffractometerThe X-ray diffractometer allowsmeasurement of the X-ray diffraction pattern from which thecrystalline phases within the sample may be qualitativelyidentified
42、 and the proportion of each phase may be quantita-tively determined. X-ray diffractometers are manufacturedcommercially and a number of instruments are available. Thesuitability of the diffractometer for this test method shall beestablished using the qualification procedure outlined in thistest meth
43、od.8. Materials8.1 Standardization PhasesThe use of standardizationphases is recommended for establishing the intensity ratio/mass ratio relationships when using the traditional quantitativemethod. These phases must usually be synthesized (12, 13).8.2 CRM ClinkerThe use of three CRM clinkers isrequi
44、red to qualify the QXRD procedure.8.3 Internal StandardThe use of an internal standard isrecommended for the standardization approach. Suitable ma-terials include chemical reagents (see 8.4) or CRMs (seeAppendix X1).8.4 Reagent ChemicalsReagent grade chemicals, if usedeither as an internal standard
45、or during chemical extraction ofcertain phases, shall meet the specifications of the Committeeon Analytical Reagents of the American Chemical Societywhere such specifications are available.6Other grades may beused, provided it is first ascertained that the chemical issufficiently pure to permit its
46、use without lessening the accu-racy of the determination.9. Hazards9.1 The importance of careful and safe operation of anX-ray diffractometer cannot be overemphasized. X-rays areparticularly hazardous. An X-ray diffractometer must be oper-ated safely to avoid serious injury or death. The X-rays areg
47、enerated by high voltages, perhaps as high as 55 kV peak,requiring care to avoid serious electric shock. Klug andAlexander (6) (pp. 5860) state, “The responsibility for safeoperation rests directly on the individual operator” (italics aretheirs).10. Sampling and Sample Preparation10.1 Take samples o
48、f cement in accordance with the appli-cable provisions of Practice C183. Take samples of portland-cement clinker so as to be representative of the material beingtested.10.2 Prepare samples as required for the specific analyticalprocedure (see Appendix X2).11. Qualification and Assessment11.1 Qualifi
49、cation of Test Procedure:11.1.1 When analytical data obtained in accordance withthis test method are required, any QXRD test procedure thatmeets the requirements described in this section may be used.11.1.2 Prior to use for analysis of cement or portland-cement clinker, qualify the QXRD test procedure for theanalysis. Maintain records that include a description of theQXRD procedure and the qualification data (or, if applicable,re-qualification data). Make these records available to thepurchaser if requested in the contract or order.
