1、Designation: D5380 93 (Reapproved 2014)Standard Test Method forIdentification of Crystalline Pigments and Extenders in Paintby X-Ray Diffraction Analysis1This standard is issued under the fixed designation D5380; the number immediately following the designation indicates the year oforiginal adoption
2、 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. Scope1.1 This test method covers the identification of crystallinepigments and extend
3、ers in liquid paint and dry paint film. It isapplicable to both water-reducible and solvent-reducible paint.It also may be used to identify pigment and extender in grindpaste or alone as dry powder. It is not applicable to amorphouscomponents such as carbon black, amorphous silica, or highlyprocesse
4、d clay.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 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 establi
5、sh appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardstatements are given in Section 6.2. Referenced Documents2.1 ASTM Standards:2D3925 Practice for Sampling Liquid Paints and RelatedPigmented Coatings3. Summary of Test M
6、ethod3.1 Every crystalline substance, in this case pigment orextender, has a characteristic X-ray diffraction pattern.Whether the substance is present alone or in a mixture, itproduces its pattern independently and can be identified by it.An X-ray diffraction pattern of a sample is recorded. Eachcry
7、stalline substance in the sample is identified by theHanawalt or Fink method or other systematic procedure basedon comparison of the diffraction pattern of the sample withreference patterns of standards.3,4,54. Significance and Use4.1 The choice of pigments and extenders influences theappearance, du
8、rability, cost, and other properties of paint. Thistest method is a convenient way, and probably the mostreliable, to identify pigments in paint.5. Apparatus5.1 X-ray Diffractometer, suitable for collecting intensityversus two theta (20) angle diffraction patterns in the rangefrom 5 to 65 20. It is
9、preferred that the diffractometer beequipped with a copper target X-ray tube and a monochromatorthat passes only copper K-alpha radiation. If a monochromatoris not available, then a suitable filter may be used to removecopper K-beta radiation from the diffracted X-ray beam. Anickel filter may be use
10、d for this purpose when a copper targettube is employed.NOTE 1Follow the recommendations of the manufacturer of thediffractometer used.5.2 Liquid Paint or Grind Paste:5.2.1 Paint Shaker.5.2.2 Film Applicator, that will produce a 3- to 10-mil (75-to 250 m) wet film thickness.5.2.3 Plastic Sheet, such
11、 as polyester film, that contains nocrystalline components that would produce interfering X-raydiffraction peaks and is not attacked by paint solvent.5.2.4 Perforated Suction Plate or other flat surface.5.3 Paint Chips or Pigment Powder:5.3.1 Miniature Reciprocating Ball Mill.5.3.2 Stainless Steel V
12、ials, with agitator for ball mill.5.3.3 Powder Specimen Holders, for X-ray diffractometer.6. Hazards6.1 PrecautionAs exposure to excessive quantities ofX-radiation is injurious to health, X-ray producing equipment1This test method is under the jurisdiction of ASTM Committee D01 on Paintand Related C
13、oatings, Materials, andApplications and is the direct responsibility ofSubcommittee D01.21 on Chemical Analysis of Paints and Paint Materials.Current edition approved July 1, 2014. Published July 2014. Originally approvedin 1993. Last previous edition approved in 2009 as D5280 93 (2009). DOI:10.1520
14、/D5380-93R0914.2For 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 onthe ASTM website.3Search Manual, (Hanawalt), “Inorganic Phases,
15、” International Centre forDiffraction Data, (ICDD), Catalog No. HA 42, Newtown Square Corporate Campus,12 Campus Blvd., Newtown Square, PA 19073-3273.4Search Manual, (Fink), “Inorganic Phases,” ICDD.5“Powder Diffraction File, Inorganic,” ICDD.Copyright ASTM International, 100 Barr Harbor Drive, PO B
16、ox C700, West Conshohocken, PA 19428-2959. United States1can be dangerous to both the operator and persons in theimmediate vicinity unless safety precautions are strictly ob-served. Therefore, users should avoid exposing any parts oftheir bodies, not only to the direct beam, but also to secondaryor
17、scattered radiation that occurs when an X-ray beam strikesor passes through any material. It is strongly recommended thatusers check the degree of exposure by film carried on them orby the use of dosimeters and that blood counts be madeperiodically. Before utilizing the equipment, all persons desig-
18、nated or authorized to operate X-ray instrumentation or super-vise its operation, should have a full understanding of its natureand should also become familiar with established safe exposurefactors by a careful study of the NIST handbook,6“X-rayRecommendations of the International Roentgen Ray Commi
19、t-tee on X-ray Protection,” the manufacturers instructionmanual, and other standard publications on the subject. Inqui-ries should be made of state agencies as to existing require-ments.7. Specimen Preparation7.1 Prepare a specimen from the sample using one of thefollowing methods:7.1.1 Liquid Paint
20、 or Pigment PasteThoroughly mix andsample the paint or paste in accordance with Practice D3925.Place a plastic sheet on the perforated suction plate. On thesheet make a drawdown of the sample. A wet film thickness of3.0 to 10.0 mil (75 to 250 m) is suggested. Cut from thedrawdown on the plastic shee
21、t a specimen of shape and sizesuitable for the mounting in the specimen holder of thediffractometer.7.1.2 Paint ChipUsing a ball mill, grind to a powder thepaint chip or, if it contains more than one layer, the part of thechip of interest. Prepare sufficient specimen to fill the specimenholder or to
22、 satisfy the requirements of the preparation tech-nique to be used. In cases where the chip has a planar surfaceand uniform thickness, it may be possible to cut the chip to therequired dimensions and mount it directly in the specimenholder with no preparation.NOTE 2X-ray diffraction patterns collect
23、ed for specimens consistingof whole chips will reveal the composition of all paint layers probed by theX-rays. The depth probed will depend upon the wavelength of X-ray used,the composition of the paint layer or layers through which the X-rays pass,the composition of the deepest layer probed, the tw
24、o-theta angle, and otherfactors. When a copper X-ray tube is used, the depth probed may rangefrom as little as approximately 2 mils (75 m) in the case of very highdensity coatings to as much as 197 mils (0.5 cm) in the case ofunpigmented resin.7.1.3 Paint Film on PanelCut from the panel a specimenof
25、 dimensions suitable for mounting in the specimen holder.Asan alternative, it may be convenient to cut a piece of specimento the same dimensions as the specimen holder and use thespecimen without the holder.NOTE 3An X-ray diffraction pattern collected for coating on a panelwill be a superposition of
26、 the diffraction patterns of the crystallinecomponents in the coating on the panel and, to the extent that X-raysdiffracted from the substrate reach the detector, the diffraction pattern ofthe substrate.7.2 Mount the specimen in the specimen holder, taking careto insure that the surface of the speci
27、men is flush with theoptical plane of the holder.NOTE 4Failure to place the specimen surface in the optical planeilluminated by the X-ray source and viewed by the detector will result ina systematic shift from the correct position of peaks in the observeddiffractogram. The greater the shift, the gre
28、ater the difficulty in using theobserved diffractogram to identify components in the specimen.8. Procedure8.1 Experimental:8.1.1 Turn on the diffractometer and allow it to stabilizethoroughly before beginning collection of results. With the aidof the manufacturers literature, select instrument opera
29、tionconditions that permit collection of X-ray diffractogramsspanning the two-theta range from 5 to 65. The conditionschosen must be suitable for qualitative analysis of a multicom-ponent mixture assuming the presence of a minor componentpresent at approximately one percent by weight. Resultscollect
30、ed must be available as the d-spacing and intensity,preferably the integrated intensity, of each peak. In the case ofdiffractometers not equipped with a computer, the two-thetaand intensity data must be measured manually from plotteddiffraction patterns and the d-spacings then calculated from thetwo
31、-theta angles of the peaks. In the latter case, the diffractionpatterns must be plotted with two-theta scale expansion thatpermits the angle of each peak to be measured to the nearest0.01 for peaks in the range above 3.5 and to the nearest0.001 for peaks below approximately 3.5 .NOTE 5If not already
32、 established, then make sure that the two-thetacalibration of the goniometer of the diffractometer is verified at two ormore angles in accordance with recommendations of the manufacturer andcorrected as needed. The procedure will entail comparison of the observedand expected d-spacing of diffraction
33、 peaks of highly crystalline referencematerials at least at one high and one low two-theta angle.8.1.2 For each sample correct the diffraction pattern span-ning at least from 5 to 65 two-theta.9. Identification9.1 Prepare a list of all diffraction peaks exhibited by thesample including both the d-sp
34、acing and intensity (preferablyintegrated intensity) of each peak, listed in decreasing order ofd-spacing. The d-spacing of each peak should be stated at thenearest hundredth of an angstrom for d-spacings greater than3.5 and stated to the nearest thousandth of an angstrom ford-values of less than ab
35、out 3.5 .9.2 Identify the crystalline phase or phases that account forall peaks in the diffraction pattern of the sample under analysis,using the Hanawalt Method, Fink Method, or other systematicprocedure. Full identification of the crystalline componentsmay be speeded by use of information about co
36、mponentsknown to be or suspected of being in the sample (that is,preconceived composition) or by use of the list of commonpigments and extenders appended (see Table 1).9.2.1 Verification of Preconceived Components:9.2.1.1 Prepare a list of components known to be present orsuspected of being present
37、on the basis of other information, if6NIST Handbook, X-Ray Recommendations for the International Roentgen RayCommittee on X-Ray Protection, NIST, Gaithersburg, MD, 20899.D5380 93 (2014)2any, available to the user. Use the ICDDAlphabetical Index7orother compilation of diffraction peak data to determi
38、ne thed-values of the three strongest peaks of a suspected component.Compare the three peaks for the suspected component listed inthe Alphabetical Index with the set of diffraction peaksobserved for the sample under analysis. If any one of the threepeaks is absent from the diffraction pattern of the
39、 sample, thenthe suspected component is not present in the sample. (Excep-tion: If a component has one or more peaks with relativeintensity much greater than its other peaks and is present at lowconcentration, then it may not be possible to observe its weakerpeaks.) If all three peaks are present, t
40、hen make sure that thefile number beside the listed d-values is noted and the full setof diffraction data for the suspected component is inspected inthe Powder Data File.59.2.1.2 Confirmation of the presence of the suspected com-ponent requires that all peaks listed for the suspect in thePowder Diff
41、raction File, or other reference source, must bepresent in the diffraction pattern of the sample. Furthermore,the relative intensity of the peaks in the diffraction pattern mustbe similar to the relative intensity of the peaks in the referencepattern when experimental error and possible overlap by p
42、eaksof other components are taken into account. Once a componentin the sample is identified, make sure that the corresponding setof peaks is either labeled or crossed off the list of peakobserved for the sample. However, a peak may be left on thelist for further consideration if the observed intensi
43、ty signifi-cantly exceeds the intensity cited in the reference file, thussuggesting that a peak of another component overlaps the onein question. Repeat the procedure stated in 9.2.1 until allpreconceived components are confirmed or rejected. Unas-signed peaks, if any, remaining on the list prepared
44、 in 9.1represent unidentified components in the sample. Identify thesecomponents using one or more of the following methods:NOTE 6When comparing the d-values of observed peaks withd-values of peaks listed in references, allow for reasonable experimentalerror. As a general rule allow for a margin of
45、error of 6 0.02 for peakswith d-values greater than 3.5 and 60.005 for peaks with d-valuesless than about 3.5 . The set of relative intensities observed for thesample under analysis may differ from the values listed in the referencepattern, even when the phase has been correctly identified, because
46、of7Alphabetical IndexInorganic Phases, Catalog No. Al42, ICDD.TABLE 1 Common Pigments and Extenders for Paintd-Value and IntensityAName FormulaICDD FileNumber17.6x9.054.4983.5841.5046bentoniteBNa0.3(AlMg)2Si4O1012-219(OH)2H2O10.1x4.4993.6663.36x2.5659micaBKal2Si3AlO10(OH)27-259.34x4.6693.116x2.47671
47、.8704talcBMg3Si4O10(OH)213-5587.63x4.283x3.06582.87352.6854gypsum CaSO42H2O 33-3117.36x4.5653.6682.45171.5317chrysotile-20rcl Mg3Si2O5(OH)425-6457.31x4.5753.6572.2731.5355chrysotile-2Mcl Mg3Si2O5(OH)431-8087.17x4.36664.18653.57982.4955kaoliniteBAl2Si2O5(OH)414-1644.568x9.1264.41023.46032.8537zinc ph
48、osphateBZn3(PO4)2H2O 37-4654.18x2.6942.4552.1921.722yellow iron oxide FeO(OH) 29-7134.040x3.13612.84112.48712.4860crystobalite SiO239-14253.52x2.37021.89241.70021.6672anatase TiO221-12723.445x3.31973.103x2.12182.1068barium sulfate BaSO424-10353.39x6.3222.98682.84042.2692chrome orange Pb2(OH)2CrO48-4
49、373.38x2.90352.78752.63231.7553red lead Pb3O48-193.342x4.25722.45781.81811.5429quartz SiO233-11613.310x3.12982.92691.910381.76425zinc sulfide ZnS 36-14503.28x4.9634.3833.4863.037lead chromate PbCrO48-2093.260x9.7965.77124.25123.1305lead oxide sulfatehydratePb4O3SO4H2O 29-7813.260x3.45283.00662.54362.3085strontium chromate SrCrO415-3563.247x2.48752.18831.68761.6242rutile TiO221-12763.22x4.8934.7233.12x2.6682moly orange Pb(Cr19Mo11)O419-6853.160x3.58383.36762.06861.7615cadmium yellow CdS 6-3143.142x4.57123.49433.17423.1188antimony oxide Sb2O311
