ASTM C1365-98(2004)
(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
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: aluminate (tricalcium aluminate, C3A), ferrite (tetracalcium aluminoferrite, C4AF), and periclase (magnesium oxide, M) (see Note 1).
Note 1—In the future, Subcommittee C01.23 plans to add additional phases: alite (tricalcium silicate, C3S), belite (dicalcium silicate, C2S), gypsum (CSH2), hemihydrate (CSH 1/2), and anhydrite (CS).
1.2 This test method specifies certain general aspects of the analytical procedure, but does not specify detailed aspects. A recommended procedure is described, but not specified. Regardless of the procedure selected, the user must demonstrate by analysis of reference materials (RM's) that the particular analytical procedure selected for this purpose qualifies (that is, provides acceptable precision and bias) (see Note 2). The recommended procedure is the one used in the round-robin analysis to determine the precision and bias levels of this test method.
Note 2—A similar approach was used in the performance requirements for alternative methods for chemical analysis in Test Methods C 114.
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:C 1365–98 (Reapproved 2004)
Standard Test Method for
Determination of Proportion of Phases in Portland Cement
and Portland-Cement Clinker Using X-Ray Powder
Diffraction Analysis
This standard is issued under the fixed designation C 1365; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) 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
aluminate (tricalcium aluminate, C A), ferrite (tetracalcium C183 Practice for Sampling and the Amount of Testing of
aluminoferrite, C AF), and periclase (magnesium oxide, M) Hydraulic Cement
(see Note 1). C219 Terminology Relating to Hydraulic Cement
C670 Practice for Preparing Precision and Bias Statements
NOTE 1—In the future, Subcommittee C01.23 plans to add additional
for Test Methods for Construction Materials
phases: alite (tricalcium silicate, C S), belite (dicalcium silicate, C S),
3 2
E29 Practice for Using Significant Digits in Test Data to
gypsum ~CSH ! , hemihydrate ~CSH½! , and anhydrite ~CS! .
Determine Conformance with Specifications
1.2 This test method specifies certain general aspects of the
E691 Practice for Conducting an Interlaboratory Study to
analytical procedure, but does not specify detailed aspects. A
Determine the Precision of a Test Method
recommended procedure is described, but not specified. Re-
gardless of the procedure selected, the user must demonstrate
3. Terminology
by analysis of reference materials (RM’s) that the particular
3.1 Definitions are in accordance with Terminology C 219.
analytical procedure selected for this purpose qualifies (that is,
3.2 Phases (1):
provides acceptable precision and bias) (see Note 2). The
3.2.1 alite, n—tricalcium silicate (C S) modified in compo-
recommended procedure is the one used in the round-robin
sition and crystal structure by incorporation of foreign ions;
analysis to determine the precision and bias levels of this test
occurstypicallybetween30to70%(bymass)oftheportland-
method.
cement clinker; and is normally either the M or M crystal
1 3
NOTE 2—Asimilarapproachwasusedintheperformancerequirements
polymorph, each of which is monoclinic.
for alternative methods for chemical analysis in Test Methods C114.
3.2.2 aluminate, n—tricalciumaluminate(C A)modifiedin
composition and sometimes in crystal structure by incorpora-
1.3 The values stated in SI units shall be regarded as the
tion of a substantial proportion of foreign ions; occurs as
standard.
2–15% (by mass) of the portland-cement clinker; is normally
1.4 This standard does not purport to address all of the
cubic when relatively pure and orthorhombic when in solid
safety concerns, if any, associated with its use. It is the
solutionwithsignificantamountsofsodium,thoughtetragonal
responsibility of the user of this standard to establish appro-
aluminate containing a substantial amount of potassium has
priate safety and health practices and determine the applica-
been reported (2).
bility of regulatory limitations prior to use. For specific
hazards, see Section 9.
1 3
ThistestmethodisunderthejurisdictionofASTMCommitteeC01onCement For referenced ASTM standards, visit the ASTM website, www.astm.org, or
andisthedirectresponsibilityofSubcommitteeC01.23onCompositionalAnalysis. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved August 1, 2004. Published August 2004. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1998. Last previous edition approved in 1998 as C1365-98. the ASTM website.
2 4
When expressing chemical formulae, C=CaO, S-SiO,A=Al O,F=Fe O , Theboldfacenumbersinparenthesesrefertothelistofreferencesattheendof
2 2 3 2 3
M=MgO, S =SO , and H=H O. this test method.
3 2
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
C 1365–98 (2004)
3.2.3 belite, n—dicalcium silicate (C S) modified in com- especially difficult due to the complex and variable nature of
position and crystal structure by incorporation of foreign ions; the individual clinker phases.
occurs typically as 15 to 45% (by mass) of the portland-
5. Summary
cement clinker as normally the b polymorph, which is mono-
clinic. In lesser amounts, other polymorphs can be present.
5.1 A QXRD test procedure includes some or all of the
3.2.4 ferrite, n—tetracalcium aluminoferrite solid solution
following:
of approximate composition C (A,F) modified in composition
5.1.1 Specimen preparation,
by variation in theAl/Fe ratio and by substantial incorporation
5.1.2 Standardization,
of foreign ions as C A F whereO
4 X 2-X
5.1.3 Use of an internal or external standard (to correct for
to 15% (by mass) of a portland-cement clinker; and is
various effects on intensity besides phase proportion),
orthorhombic.
5.1.4 Analysis of the sample (in which the intensity of
3.2.5 periclase, n—free magnesium oxide (M); cubic.
selected XRD peaks is measured), and
3.3 Definitions of Terms Specific to This Standard:
5.1.5 Calculation of the proportion of each phase.
3.3.1 standardization, n—process of determining the rela-
5.2 This test method does not specify details of the proce-
tionship between XRD intensity and phase proportion for one
dure. The user must demonstrate by analysis of reference
or more phases.
materials that the particular analytical procedure selected for
3.3.1.1 Discussion—In the literature of X-ray powder dif-
thispurposeprovidesacceptablelevelsofprecisionandbias.A
fraction analysis, this process has been commonly referred to
recommended procedure (the procedure used to determine the
as calibration; however, we have determined that standardiza-
acceptable levels of precision and bias) is given in Appendix
tion is a more accurate term.
X1.
3.3.2 diffractometer, n—the instrument, an X-ray powder
diffractometer, for determining the X-ray diffraction pattern of
6. Significance and Use
a crystalline powder.
6.1 This test method covers direct determination of the
3.3.3 phase, n—a homogeneous, physically distinct, and
proportion of some individual phases in portland cement or
mechanicallyseparableportionofamaterial,identifiablebyits
portland-cement clinker. Thus it provides an alternative to the
chemical composition and crystal structure.
indirect estimation of phase proportion using the equations in
3.3.3.1 Phases in portland-cement clinker that are included
Specification C150 (see Note C of Table1 and Note B of
inthistestmethodaretwomajorphases(aluminateandferrite)
Table2 of Specification C150).
and one minor phase (periclase).
6.2 Thistestmethodassumesthattheoperatorisqualifiedto
3.3.4 qualification, n—process by which a QXRD proce-
operate an X-ray diffractometer and to interpret X-ray diffrac-
dure is shown to be valid.
tion spectra.
3.3.5 Reference Material (RM) Clinkers, n—three cement
6.3 Thistestmethodmaybeusedaspartofaqualitycontrol
clinkerswithknownproportionsofeachmajorphase,available
program in cement manufacturing.
as RM’s, which shall be used in demonstrating qualification of
6.4 This test method may be used in predicting properties
a particular procedure for determination of the phases in
and performance of hydrated cement and concrete, to the
portland cement or portland-cement clinker.
extent that properties and performance are a function of phase
3.3.6 Standard Reference Material (SRM), n—a material
composition.
whose properties (in this case XRD peak position or intensity,
6.5 QXRD provides a bulk analysis (that is, the weighted
or both) are known and certified.
average composition of several grams of material). Results
3.3.7 X-ray diffraction (XRD), n—the process by which
maynotagreepreciselywithresultsofmicroscopicalmethods.
X-rays are coherently scattered by electrons in a crystalline
material.
7. Apparatus
4. Background 7.1 X-Ray Diffractometer—TheX-raydiffractometerallows
measurement of the X-ray diffraction pattern from which the
4.1 This test method assumes general knowledge concern-
crystalline phases within the sample may be qualitatively
ing the composition of portland cement and portland-cement
identified and the proportion of each phase may be quantita-
clinker. Necessary background information may be obtained
tively determined. X-ray diffractometers are manufactured
from a number of references (1,3).
commercially and a number of instruments are available. The
4.2 ThistestmethodalsoassumesgeneralexpertiseinXRD
suitability of the diffractometer for this test method shall be
and QXRD analysis. Important background information may
established using the qualification procedure outlined in this
be obtained from a number of references (4-7).
test method.
4.3 QXRD analysis is difficult and time-consuming and
QXRD of portland cement and portland-cement clinker is
8. Materials
8.1 Standardization Phases—The use of standardization
In this test method, RM clinkers refer specifically to RM8486, RM8487, and
phases is recommended.These phases must usually be synthe-
RM8488. These are available from the Standard Reference Material Program,
sized (8).
National Institute of Standards and Technology.
8.2 RM Clinkers—The use of RM clinkers is required to
SRM’s are available from the Standard Reference Material Program, National
Institute of Standards and Technology. qualify the QXRD procedure.
C 1365–98 (2004)
8.3 Internal Standard—The use of an internal standard is 11.1.5 Qualification shall consist of analyzing the three RM
recommended. Suitable materials include chemical reagents clinkers (see Note 3) for the proportions of C A (cubic and
(see 8.4) or SRM’s (see Appendix X1). orthorhombic), C AF, and M using the desired QXRD proce-
8.4 Reagent Chemicals—Reagent grade chemicals, if used dure (see Note 4).
either as an internal standard or during chemical extraction of
NOTE 3—Prior to qualification, it may be convenient to carry out a
the calcium silicate phases, shall meet the specifications of the
preliminaryassessmentinwhichoneormoremixturesofsyntheticphases
Committee onAnalytical Reagents of theAmerican Chemical
is analyzed. Such a preliminary assessment should produce no more than
Society where such specifications are available. Other grades the permissible variation described in 11.2.
NOTE 4—It is recommended that at least two replicate analyses be
may be used, provided it is first ascertained that the chemical
carried out.
is sufficiently pure to permit its use without lessening the
accuracy of the determination.
11.2 Permissible Variation:
11.2.1 The values of permissible variation were computed
9. Hazards
from the within-laboratory standard deviation values obtained
in the cooperative standardization and round robin analysis of
9.1 The need for careful and safe operation of an X-ray
mixtures of synthetic phases (see 14.2.1).
diffractometer cannot be overemphasized. X-rays are particu-
11.2.2 If replicate analyses are carried out, results should
larly hazardous. An X-ray diffractometer must be operated
differ from each other by no more than the value shown in
safelytoavoidseriousinjuryordeath.Furthermore,theX-rays
Table 1 for the particular number of replicates.
aregeneratedbyhighvoltages,perhapsashighas55kVpeak,
11.2.3 Themeanresultshalldifferfromtheknownvalueby
requiring care to avoid serious electric shock. Klug and
no more than the value shown in Table 2 for the particular
Alexander (5) (pp. 58–60) state, “The responsibility for safe
number of replicates.
operation rests directly on the individual operator” (italics are
11.2.4 Known Values—The known values of each phase in
theirs).
the RM clinkers provided by NIST were determined using
10. Sampling and Sample Preparation quantitative optical microscopy and differ somewhat from
those obtained using QXRD. For the purpose of this test
10.1 Take samples of portland cement in accordance with
method, the known values of the RM clinkers shall be the
the applicable provisions of Practice C183. Take samples of
values in the QXRD round robin analysis (see 14.2.2). These
portland-cement clinker so as to be representative of the
values are listed in Table 3.
material being tested.
11.3 Partial Results:
10.2 Prepare samples as required for the specific analytical
11.3.1 QXRDproceduresthatprovideacceptableresultsfor
procedure (see Appendix X1).
some phases but not for others shall be used only for those
phasesforwhichacceptableresultsareobtained.However,itis
11. Qualification and Assessment
notexpectedthataQXRDprocedurewouldprovideacceptable
11.1 Qualification of Test Procedure:
results for some phases and not for others, and such a result
11.1.1 When analytical data obtained in accordance with
may indicate that the procedure is not, in fact, valid.
this test method are required, any QXRD test procedure that
11.4 Assessing the Diffractometer:
meets the requirements described in this section may be used.
11.4.1 The procedures described in theAnnex shall be used
11.1.2 Prior to use for analysis of portland cement or
to assess the diffractometer. Note that assessment is different
portland-cement clinker, each QXRD test procedure must be
from qualification or requalification.
qualified for such analysis. The laboratory shall maintain
11.4.2 The diffractometer shall be assessed each day that
records that include a description of the QXRD procedure and
this test method is used.
the qualification data (or, if applicable, requalification data).
These records shall be made available to the purchaser if
TABLE 1 Permissible Maximum Difference Between Replicate
requested in the contract or order.
Values (percent of clinker)
11.1.3 If more than one X-ray diffractometer is used in a
A
Phase Number of Replicates Permissible Difference
specific laboratory for the same analysis, even if the instru-
ments are substantially identical, each shall be qualified sepa- Orthorhombic C A 2 1.06
3 1.25
rately.
4 1.37
11.1.4 If more than one procedure is used to mount speci-
5 1.48
mens for QXRD, the use of each procedure shall constitute a Cubic C A 2 1.04
3 1.22
separate test procedure and each procedure shall be qualified
4 1.33
separately.
5 1.44
C AF 2 1.68
3 1.98
4 2.16
5 2.34
Reagent Chemicals, American Chemical Society S
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