ASTM C1365-06(2011)
(Test Method)Standard Test Method for Determination of the Proportion of Phases in Portland Cement and Portland-Cement Clinker Using X-Ray Powder Diffraction Analysis
Standard Test Method for Determination of the Proportion of Phases in Portland Cement and Portland-Cement Clinker Using X-Ray Powder Diffraction Analysis
SIGNIFICANCE AND USE
This test method allows direct determination of the proportion of some individual phases in cement or portland-cement clinker. Thus it provides an alternative to the indirect estimation of phase proportion using the equations in Specification C150 (Annex A1).
This test method assumes that the operator is qualified to operate an X-ray diffractometer and to interpret X-ray diffraction spectra.
This test method may be used as part of a quality control program in cement manufacturing.
This test method may be used in predicting properties and performance of hydrated cement and concrete that are a function of phase composition.
QXRD provides a bulk analysis (that is, the weighted average composition of several grams of material). Therefore, results may not agree precisely with results of microscopical methods.
SCOPE
1.1 This test method covers direct determination of the proportion by mass of individual phases in portland cement or portland-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 aluminoferrite), periclase (magnesium oxide), gypsum (calcium sulfate dihydrate), bassanite (calcium sulfate hemihydrate), anhydrite (calcium sulfate), and calcite (calcium carbonate).
1.2 This test method specifies certain general aspects of the analytical procedure, but does not specify detailed aspects. Recommended procedures are described, but not specified. Regardless of the procedure selected, the user shall demonstrate by analysis of certified reference materials (CRM's) that the particular analytical procedure selected for this purpose qualifies (that is, provides acceptable precision and bias) (see Note 1). The recommended procedures are ones used in the round-robin analyses to determine the precision levels of this test method.
Note 1—A similar approach was used in the performance requirements for alternative methods for chemical analysis in Test Methods C114.
1.3 The values stated in SI units shall be regarded as the standard.
1.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazards, see Section 9.
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Designation: C1365 − 06 (Reapproved 2011)
Standard Test Method for
Determination of the Proportion of Phases in Portland
Cement and Portland-Cement Clinker Using X-Ray Powder
Diffraction Analysis
This standard is issued under the fixed designation C1365; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 2. Referenced Documents
1.1 This test method covers direct determination of the 2.1 ASTM Standards:
proportion by mass of individual phases in portland cement or C114 Test Methods for Chemical Analysis of Hydraulic
portland-cement clinker using quantitative X-ray (QXRD) Cement
analysis. The following phases are covered by this standard: C150 Specification for Portland Cement
alite (tricalcium silicate), belite (dicalcium silicate), aluminate C183 Practice for Sampling and the Amount of Testing of
(tricalcium aluminate), ferrite (tetracalcium aluminoferrite), Hydraulic Cement
periclase (magnesium oxide), gypsum (calcium sulfate C219 Terminology Relating to Hydraulic Cement
dihydrate), bassanite (calcium sulfate hemihydrate), anhydrite C670 Practice for Preparing Precision and Bias Statements
(calcium sulfate), and calcite (calcium carbonate). for Test Methods for Construction Materials
E29 Practice for Using Significant Digits in Test Data to
1.2 This test method specifies certain general aspects of the
Determine Conformance with Specifications
analytical procedure, but does not specify detailed aspects.
E691 Practice for Conducting an Interlaboratory Study to
Recommended procedures are described, but not specified.
Determine the Precision of a Test Method
Regardless of the procedure selected, the user shall demon-
strate by analysis of certified reference materials (CRM’s) that
3. Terminology
the particular analytical procedure selected for this purpose
3.1 Definitions: Definitions are in accordance with Termi-
qualifies (that is, provides acceptable precision and bias) (see
nology C219.
Note 1). The recommended procedures are ones used in the
3.2 Phases (1):
round-robin analyses to determine the precision levels of this
3.2.1 alite, n—tricalcium silicate (C S) modified in com-
test method.
position and crystal structure by incorporation of foreign ions;
NOTE 1—Asimilar approach was used in the performance requirements
occurs typically between 30 to 70 % (by mass) of the portland-
for alternative methods for chemical analysis in Test Methods C114.
cement clinker; and is normally either the M or M crystal
1 3
1.3 The values stated in SI units shall be regarded as the
polymorph, each of which is monoclinic.
standard.
3.2.2 alkali sulfates, n—arcanite (K SO ) may accommo-
2 4
+ +
1.4 This standard does not purport to address all of the
date Na , Ca2 , and CO in solid solution, aphthitalite (K ,
3 4-x
safety concerns, if any, associated with its use. It is the Na )SO with x usually 1 but up to 3), calcium langbeinite
x 4
responsibility of the user of this standard to establish appro-
(K Ca [SO ] ) may occur in clinkers high in K O, and
2 2 4 3 2
priate safety and health practices and determine the applica- thenardite (Na SO ) in clinkers with high Na/K ratios (1).
2 4
bility of regulatory limitations prior to use. For specific
hazards, see Section 9.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
1 the ASTM website.
This test method is under the jurisdiction ofASTM Committee C01 on Cement
The boldface numbers in parentheses refer to the list of references at the end of
and is the direct responsibility of Subcommittee C01.23 on CompositionalAnalysis.
this standard.
Current edition approved Dec. 1, 2011. Published May 2012. Originally
Whenexpressingchemicalformulae,C=CaO,S=SiO ,A=Al O ,F=Fe O ,
2 2 3 2 3
approved in 1998. Last previous edition approved in 2006 as C1365 - 98 (2006).
¯
DOI: 10.1520/C1365-06R11. M = MgO, S =SO,andH=H O.
3 2
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
C1365 − 06 (2011)
3.2.3 aluminate, n—tricalcium aluminate (C A) modified in 3.3.3 phase, n—a homogeneous, physically distinct, and
composition and sometimes in crystal structure by incorpora- mechanically separable portion of a material, identifiable by its
tion of a substantial proportion of foreign ions; occurs as 2 to chemical composition and crystal structure.
15 % (by mass) of the portland-cement clinker; is normally
3.3.3.1 Discussion—Phases in portland-cement clinker and
cubic when relatively pure and orthorhombic or monoclinic
cements that are included in this test method are four major
when in solid solution with significant amounts of sodium (2).
phases (alite, belite, aluminate, and ferrite) and one minor
¯ phase (periclase).
3.2.4 anhydrite, n—calcium sulfate ~CS! and is orthorhom-
3.3.3.2 Discussion—Precision values are provided for addi-
bic (see Note 2).
tional phases (gypsum, bassanite, anhydrite, arcanite, and
NOTE 2—Calcium sulfate is added to the clinker during grinding to
control setting time, strength development, and volume stability. Several
calcite). Values for these constituents may be provided using
phases may form as a result of dehydration of gypsum. The first 1.5
this method but are considered informational until suitable
molecules of water are lost between 0 and 65 °C with minor changes in
certified reference materials for qualification are available.
structure; and, above 95 °C, the remaining 0.5 molecules of water are lost
transforming the structure to the metastable γ polymorph of anhydrite
3.3.4 qualification,n—processbywhichaQXRDprocedure
(sometimes referred to as ‘soluble anhydrite’) and subsequently the
is shown to be valid.
orthorhombic form (3).
3.3.5 Rietveld analysis, n—process of refining crystallo-
¯
~ !
3.2.5 bassanite, n—calcium sulfate hemihydrate CSH
1/2
graphic and instrument variables to minimize differences
and is monoclinic.
between observed and calculated X-ray powder diffraction
3.2.6 belite, n—dicalcium silicate (C S) modified in com-
patterns for one or more phases, estimating their relative
position and crystal structure by incorporation of foreign ions;
abundance.
occurs typically as 15 to 45 % (by mass) of the portland-
3.3.6 standardization, n—process of determining the rela-
cement clinker as normally the β polymorph, which is mono-
tionship between XRD intensity and phase proportion for one
clinic. In lesser amounts, other polymorphs can be present.
or more phases (see Note 5).
3.2.7 calcite, n—calcium carbonate is trigonal and may be
NOTE 5—In the literature of X-ray powder diffraction analysis, the
present in a cement as an addition or from carbonation of free
standardization process has been commonly referred to as calibration;
lime.
however,wehavedeterminedthatstandardizationisamoreaccurateterm.
3.2.8 ferrite, n—tetracalcium aluminoferrite solid solution
3.3.6.1 Discussion—Rietveld analysis uses crystal structure
of approximate composition C (A,F) modified in composition
models to calculate powder diffraction patterns of phases that
by variation in theAl/Fe ratio and by substantial incorporation
serve as the reference patterns. The pattern-fitting step seeks
of foreign ions as C A F where0
4 X 2-X
the best-fit combination of selected pattern intensities to the
to 15 % (by mass) of a portland-cement clinker; and is
raw data. The relative pattern intensities along with the
orthorhombic.
crystallographic attributes of each phase are used to calculate
3.2.9 free lime, n—free calcium oxide (C); cubic (see Note
relative abundance. The standardization approach uses pow-
3).
deredsamplesofpurephasestoassesstherelationshipbetween
NOTE 3—Free lime (CaO) may be present in clinker and cement but diffraction intensity ratios and mass fraction ratios of two or
readilyhydratestoformportlandite(Ca(OH) ).Portlanditemaycarbonate
2 more constituents; and is referred to here as the traditional
to form calcium carbonate, generally as calcite. Heat-treating a freshly-
method.
ground sample to 600 °C is useful to convert any portlandite back to free
lime but will also dehydrate the hydrous calcium sulfate phases (gypsum
3.3.7 X-ray diffraction (XRD), n—the process by which
and bassanite) to anhydrite.
X-rays are coherently scattered by electrons in a crystalline
¯
3.2.10 gypsum, n—calcium sulfate dihydrate ~CSH ! and is material.
monoclinic .
4. Background
3.2.11 periclase, n—free magnesium oxide (M); cubic.
4.1 This test method assumes general knowledge concern-
3.3 Definitions of Terms Specific to This Standard:
ing the composition of cement and portland-cement clinker.
3.3.1 Certified Reference Material (CRM), n—a material
Necessary background information may be obtained from a
whose properties (in this case phase abundance, XRD peak
number of references (1, 4).
positionorintensity,orboth)areknownandcertified(seeNote
4).
4.2 This test method also assumes general expertise in XRD
and QXRD analysis. Important background information may
NOTE 4—NIST Standard Reference Material (SRM®) Clinkers 2686,
be obtained from a number of references (5-10).
2687, and 2688 are suitable CRMs for qualification.
3.3.2 diffractometer, n—the instrument, an X-ray powder
5. Summary
diffractometer, for determining the X-ray diffraction pattern of
a crystalline powder.
5.1 This test method covers direct determination of the
proportion by mass of individual phases in cement or portland-
cement clinker using quantitative X-ray powder diffraction
analysis. The following phases are covered by this standard:
Portland cement clinker SRM’s® from the Standard Reference Material
Program, National Institute of Standards and Technology. alite (tricalcium silicate, C S), belite (dicalcium silicate, C S),
3 2
C1365 − 06 (2011)
aluminate (tricalcium aluminate, C A), ferrite (tetracalcium 8. Materials
aluminoferrite,C AF),periclase(magnesiumoxide,M),arcan-
8.1 Standardization Phases—The use of standardization
¯
ite (potassium sulfate, KS), gypsum (calcium sulfate dihydrate,
phases is recommended for establishing the intensity ratio/
¯ ¯
CSH ), bassanite (calcium sulfate hemihydrate, CSH1), anhy-
2 mass ratio relationships when using the traditional quantitative
¯
drite (calcium sulfate, CS), and calcite (calcium carbonate, method. These phases must usually be synthesized (11, 12).
CaCO ).
8.2 CRM Clinker—The use of three CRM clinkers is re-
quired to qualify the QXRD procedure.
A QXRD test procedure includes some or all of the follow-
ing: (a) specimen preparation; (b) data collection and phase
8.3 Internal Standard—The use of an internal standard is
identification; (c) standardization (for the standardization ap-
recommended for the standardization approach. Suitable ma-
proach); (d) collecting a set of crystal structure models for
terials include chemical reagents (see 8.4) or CRM’s (see
refinement (for the Rietveld approach); (e) use of an internal or
Appendix X1).
external standard (to correct for various effects on intensity
8.4 Reagent Chemicals—Reagent grade chemicals, if used
besides phase proportion); (f) analysis of the sample (in which
either as an internal standard or during chemical extraction of
the powder diffraction pattern is measured and/or the intensity
certain phases, shall meet the specifications of the Committee
of selected XRD peaks or patterns are measured); and (g)
on Analytical Reagents of the American Chemical Society
calculation of the proportion of each phase.
where such specifications are available. Other grades may be
5.2 This test method does not specify details of the QXRD used, provided it is first ascertained that the chemical is
sufficiently pure to permit its use without lessening the accu-
test procedure. The user must demonstrate by analysis of
certified reference materials that the particular analytical pro- racy of the determination.
cedure selected for this purpose provides acceptable levels of
9. Hazards
precision and bias. Two recommended procedures (the Riet-
veld approach and the traditional approach used to determine
9.1 The importance of careful and safe operation of an
the acceptable levels of precision and bias) are given in
X-ray diffractometer cannot be overemphasized. X-rays are
Appendix X1 and Appendix X2.
particularly hazardous. An X-ray diffractometer must be oper-
ated safely to avoid serious injury or death. The X-rays are
6. Significance and Use generated by high voltages, perhaps as high as 55 kV peak,
requiring care to avoid serious electric shock. Klug and
6.1 This test method allows direct determination of the
Alexander (6) (pp. 58–60) state, “The responsibility for safe
proportion of some individual phases in cement or portland-
operation rests directly on the individual operator” (italics are
cement clinker. Thus it provides an alternative to the indirect
theirs).
estimation of phase proportion using the equations in Specifi-
cation C150 (Annex A1).
10. Sampling and Sample Preparation
6.2 Thistestmethodassumesthattheoperatorisqualifiedto
10.1 Take samples of cement in accordance with the appli-
operate an X-ray diffractometer and to interpret X-ray diffrac-
cable provisions of Practice C183. Take samples of portland-
tion spectra.
cement clinker so as to be representative of the material being
tested.
6.3 Thistestmethodmaybeusedaspartofaqualitycontrol
10.2 Prepare samples as required for the specific analytical
program in cement manufacturing.
procedure (see Appendix X2).
6.4 This test method may be used in predicting properties
and performance of hydrated cement and concrete that are a
11. Qualification and Assessment
function of phase composition.
11.1 Qualification of Test Procedure:
6.5 QXRD provides a bulk analysis (that is, the weighted 11.1.1 When analytical data obtained in accordance with
average composition of several grams of material). Therefore, this test method are required, any QXRD test procedure that
meets the requirements described in this section may be used.
results may not agree precisely with results of microscopical
methods. 11.1.2 Prior to use for analysis of cement or portland-
cement clinker, qualify the QXRD test procedure for the
analysis. Maintain records that include a description of the
7. Apparatus
QXRD procedure and the qualification data (or, if applicable,
7.1 X-Ray Diffract
...
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