1、Designation: C1605 04 (Reapproved 2009)Standard Test Methods forChemical Analysis of Ceramic Whiteware Materials UsingWavelength Dispersive X-Ray Fluorescence Spectrometry1This standard is issued under the fixed designation C1605; the number immediately following the designation indicates the year o
2、foriginal 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. Scope1.1 These test methods cover the determination of ten majorele
3、ments (SiO2,Al2O3,Fe2O3, MgO, CaO, Na2O, K2O, TiO2,P2O5, MnO, and LOI in ceramic whitewares clays and mineralsusing wavelength dispersive X-ray fluorescence spectrometry(WDXRF). The sample is first ignited, then fused with lithiumtetraborate and the resultant glass disc is introduced into awavelengt
4、h dispersive X-ray spectrometer. The disc is irradi-ated with X-rays from an X-ray tube. X-ray photons emitted bythe elements in the samples are counted and concentrationsdetermined using previously prepared calibration standards.(1)2In addition to 10 major elements, the method provides agravimetric
5、 loss-on-ignition.NOTE 1Much of the text of this test method is derived directly fromMajor element analysis by wavelength dispersive X-ray fluorescencespectrometry, included in Ref (1).1.2 Interferences, with analysis by WDXRF, may resultfrom mineralogical or other structural effects, line overlaps,
6、and matrix effects. The structure of the sample, mineralogicalor otherwise, is eliminated through fusion with a suitable flux.Fusion of the sample diminishes matrix effects and produces astable, flat, homogeneous sample for presentation to thespectrometer. Selecting certain types of crystal monochro
7、ma-tors eliminates many of the line overlaps and multiorder lineinterferences. A mathematical correction procedure (2) is usedto correct for the absorption and enhancement matrix effects.1.3 Concentrations of the elements in clays and minerals aredetermined independent of the oxidation state and are
8、 reportedin the oxidation state in which they most commonly occur inthe earths crust.1.4 Concentration ranges:ElementConcentration range(percent)SiO20.10 99.0Al2O30.10 58.0Fe2O30.04 28.0ElementConcentration range(percent)MgO 0.10 60.0CaO 0.02 60.0Na2O 0.15 30.0K2O 0.02 30.0TiO20.02 10.0P2O50.05 50.0
9、MnO 0.01 15.0LOI (925C) 0.01 100.01.5 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 limita
10、tions prior to use.2. Referenced Documents2.1 ASTM Standards:3C242 Terminology of Ceramic Whitewares and RelatedProductsC322 Practice for Sampling Ceramic Whiteware ClaysC323 Test Methods for Chemical Analysis of CeramicWhiteware Clays3. Apparatus3.1 Simultaneous X-ray Spectrometer, for example, Phi
11、lipsPW1606 or equivalent.3.2 Pt-Au Alloy Crucibles and Molds, (3).3.3 Fluxer,(4) or equivalent).3.4 Two Muffle Furnaces with Rocker AttachmentsAmuffle furnace is not required if the fluxer has automaticoperation with its own heat source.3.5 Hot Plate and Muffle Furnace.4. Reagents4.1 Digest the samp
12、les in Johnson Matthey Spectroflux 1004or equivalent brand (lithium tetraborate). A blend of lithiumtetraborate (Spectroflux 1004) and lithium metaborate (Spec-troflux 100A4) can be used if a lower fusion point is desired.1These test methods are under the jurisdiction of ASTM Committee C21 onCeramic
13、 Whitewares and Related Products and are the direct responsibility ofSubcommittee C21.03 on Methods for Whitewares and Environmental Concerns.Current edition approved Oct. 1, 2009. Published February 2010. DOI: 10.1520/C1605-04R09.2The boldface numbers in parentheses refer to the list of references
14、at the end ofthis standard.3For 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.4Spectroflux is a registered tradm
15、ark of Johnson Matthey, Johnson Matthey Plc2-4 Cockspur Street, Trafalgar Square, London, SW1Y 5BQ, United Kingdom.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.The flux is ordered in powdered form, lot size as appropriate,and iden
16、tified by number and date.4.2 Dry the minus 60-mesh material for the lot 2 days at300C and keep in sealed Mason jars.4.3 After drying, perform a loss-on-fusion for each lot offlux from the manufacturer so that an appropriate amount offlux can be weighed out to yield 8.0000 g of lithium tetraborateaf
17、ter fusion.4.4 Weigh the charges of flux using a Zymark5robot to60.0035 g (60.04 % precision). If the Zymark5robot is notavailable the samples can be weighed by hand.4.5 Clean the platinum ware in 50 percent reagent gradeHCl, rinse in deionized water and dry at 140C. Other acidsmay be used instead o
18、f HCl, depending on the preference of thelaboratory.4.6 Prepare the LiBr used as a nonwetting agent by neutral-izing reagent grade concentrated HBr (48 %) with LiCO3.4.7 Filter the LiBr solution and dilute 1:1 with deionizedwater.5. Safety Precautions5.1 Fusions and ignitions of samples in a muffle
19、furnacemust be performed under a high velocity canopy hood. Boilingof the HCl cleaning solution is performed in a chemical fumehood with a safety sash. Safety glasses and special nonflam-mable, nonasbestos, heat resistant gloves must be worn whenremoving the fluxer from the muffle furnace. Glass dis
20、cs aresharp on the rear edge and should be handled with care. Dustfrom the flux must not be inhaled, so pouring of the powderedflux must be done in a chemical hood. Preparation of the LiBrsolution must be done by slowly adding LiCO3to the HBr sothe generation of CO2does not cause the acid to spill o
21、ver theedge of the beaker. The specific Chemical Hygiene Plan (CHP)for the laboratory, or laboratories if the corporation has morethan one, gives the first-aid treatment and disposal proceduresfor chemical products used in this method.6. Procedure6.1 Ignite a 0.8000 g portion of minus 80-mesh sample
22、 in atared 95 percent Pt/5 percent Au crucible at 925C for 40minutes. Report the weight loss as percent loss on ignition(LOI).6.2 Add a charge of lithium tetraborate (or a blend oflithium tetraborate/lithium metaborate) that will contribute8.0000 g after fusion to the sample and thoroughly mix thepo
23、wders.6.3 The combined weights of the sample and the flux willresult in an “infinitely thick” sample disc to the instrument.6.4 Add a 0.250 mL aliquot of the 1:1 LiBr solution, servingas a nonwetting agent, to the sample.6.5 Load whatever number of crucibles (with samples) andmolds the fluxer is equ
24、ipped to hold and the same number ofempty molds onto the fluxer.6.6 Following the instructions of the fluxer, allow it to reacha temperature of 1120C for ten minutes, and then rock for 5minutes to stir and homogenize the samples. If sulfur is to bedetermined, fusion temperature must be 1050C or less
25、 and theblend of lithium tetraborate/lithium metaborate must be used.6.7 Remove the fluxer from the furnace, pour the moltenmixtures into their respective molds, and cool to near roomtemperature. An essential feature of this mold is the molddesign (3).6.8 Samples with high concentrations of Cu, Cr,
26、Ni, Fe, Mnand high organic content require various special sample prepa-ration techniques, and, in some cases, cannot be prepared at all.6.9 Samples with arsenic or lead with concentrations inexcess of 2000 ppm, or with combined As/Pb concentration inexcess of 3000 ppm cannot be prepared because of
27、risk ofdamage of the Pt/Au crucibles.6.10 Using the wavelength dispersive X-ray spectrometer,the major element concentrations are determined by comparingthe intensities obtained from standards with those obtainedfrom the sample (5,6). For example, the following instrumentalconditions are for the Phi
28、llips PW1606 spectrometer. Theseconditions will be different for other models of x-ray spectro-photometers:Tube Rhodium, end windowPower 35 Kv and 60 maTime 100 sAtmosphere Vacuum7. Operating Conditions for Determination of Elementsby WDXRF7.1 Recalibrate the spectrophotometer every two weeks oras r
29、equired for the particular model of spectrophotometer beingused. The computerized recalibration is performed using discsfrom the original calibration which are used to set the slope ofthe calibration curve. The U.S. Geographical Survey referencematerials used include AGV-2 (Andesite), DTS-1 (Dunite)
30、,BHVO-1 (Basalt), STM-1 (Syenite), NOD-P-1(ManganeseNodule), MRG-1, BX-N, FK-N, GS-N, MICA-FE, NIM-D,NIM-P, GSR-4, GFS-401, and NBS-120C.67.2 Prepare six blanks from the current batch of flux andLiBr to use for recalibration of the curves intercept. This5Zymark is a registered trademark of Zymark Co
31、rporation, Hopkinton Massa-chusetts.6Refer to the U. S. Geological Survey listing of their reference materials,(HTTP:/minerals.cr.USGS.govgeo_chem_stand) or contact U.S. Geological Sur-vey, Box 25046, MS 973 Denver, CO 80225 for complete details of the referencematerials used in this procedure.TABLE
32、 1 Operating Conditions for Determination of Elements byWDXRFElement Line Crystal Detector Gas WindowNa Ka PX-1 Flow, P-10 2 m, polypropyleneMg Ka TLAP Flow, P-10 2 m, polypropyleneAl Ka PET Sealed neon 25 m, berylliumSi Ka InSb Sealed neon 25 m, berylliumPKa Ge Sealed neon 50 m, berylliumKKa LiF 20
33、0 Sealed krypton 100 m, berylliumCa Ka LiF 200 Sealed krypton 100 m, berylliumTi Ka LiF 200 Sealed krypton 100 m, berylliumMn Ka LiF 200 Sealed krypton 100 m, berylliumFe Ka LiF 200 Sealed krypton 100 m, berylliumPX-1 = Tungsten carbide layered; TLAP = thallium hydrogen phthalate; PET =pentaerythrit
34、ol tetrakis (hydroxymethyl) methane; InSb = indium antimonide; GE =Germanium 111; LiF 200 = lithium fluoride (200 lattice orientation); P-10 gas = 90percent argon + 10 percent methane.C1605 04 (2009)2allows the original calibration to be maintained while compen-sating for minor changes in the reagen
35、ts, P-106gas, orinstrument parameters due to equipment maintenance. Follow-ing a recalibration, prepare and count a new disc of the qualitycontrol check standard TB-16to verify the calibration.7.3 Correct long-term instrument drift by using drift moni-tor analyses. Compare monitor intensity values o
36、btained duringthe analyses with monitor intensity values from the originalcalibration. Calculate the corrections using the spectrometerssoftware. Long-term drift monitoring cannot correct for short-term or significant changes in the operating parameters.7.4 In order to keep track of instrumental sho
37、rt-term drift,use every twelfth disc as an instrument check standard: AGV-2(Andesite), DTS-1 (Dunite), BCS 381 , or BX-N6. Thesestandards represent the average, high and low for the 10analyzed elements. If the analyzed disc exceeds three times thestandard deviation of the counting statistics, halt t
38、he analysisand check the instrument using other discs. If the disc iscorrupt, remove it and make another one. Perform a recalibra-tion if the instrument shows signs of drift.7.5 In addition to the instrument standards, prepare a samplepreparation check standard, TB-16for every 20 samples whichis pro
39、duced and analyzed long with the samples. If this discshows a deviation of 3 standard deviations or more, and theinstrument standards show no deviation, then prepare anothersample of TB-16. If it again shows deviation, then halt thesample preparation and locate the problem. Instrument recali-bration
40、 is performed if both the sample preparation standardand the instrument standard exceed controls.8. Report8.1 Report the following information:8.1.1 Identification of the material tested, and8.1.2 A table listing oxides and LOI by their percentage inthe sample.9. Precision and Bias9.1 PrecisionThe W
41、DXRF method for major elementanalysis is unique among analytical method packages in that ittakes advantage of the summation of the determined elements.This summation acts as a measure of quality control. If ananalysis includes the principal elements in a sample, then thetotal of their determinations
42、 should approach 100 percent. Thischeck is the main reason that a LOI was initially incorporatedin the package. If an analysis yields a total major element oxidedetermination of less than 97 percent or greater than 101percent, then it is automatically repeated. Precision in theWDXRF method depends o
43、n the stability of the instrument, theorientation of this sample disc as it is presented to theinstrument, and the homogeneity of the sample preparation.9.2 BiasNo data, regarding the reference samples, assupplied by the National Institute of Standards and Technology,is available to determine bias.A
44、PPENDIX(Nonmandatory Information)X1. TABLESTABLE X1.1 Element to Oxide Conversion FactorsAg2O 1.0741 CuO 1.2518 Lu2O31.1371 PtO 1.0820 ThO21.1379Al2O31.8895 Dy2O31.1477 MgO 1.6582 Rb2O 1.0936 TiO21.6681As2O31.3203 Er2O31.1435 MnO 1.2912 ReO 1.0859 Tl2O31.1174As2O5 1.5339 Eu2O31.1579 MnO21.5825 RhO 1
45、.5555 Tm2O31.1421Au2O 1.0406 FeO 1.2865 MoO31.5003 RuO 1.1583 UO21.1344B2O33.2202 Fe2O31.4197 NO34.4267 SO32.4972 UO31.2017BaO 1.1165 Ga2O31.3442 Na2O 1.4305 Sb2O51.3284 U3O81.1792BeO 2.7758 Gd2O31.1526 Nb2O51.4305 Sc2O31.5338 V2O51.7852Bi2O51.1914 GeO21.4408 Nd2O31.1664 SeO31.6079 WO31.2610CO23.664
46、4 HfO21.1793 NiO 1.2725 SiO22.1392 Y2O31.2699CaO 1.3992 HgO 1.0798 OsO 1.0841 Sm2O31.1596 Yb2O31.1387CdO 1.1423 Ho2O31.1455 P2O52.2916 SnO21.2696 ZnO 1.2448Ce2O31.1713 In2O31.2091 PbO 1.0772 SrO 1.1826 ZrO21.3508CeO21.2284 IrO 1.0832 PbO21.1544 Ta2O51.2211CoO 1.2715 K2O 1.2046 PdO 1.1504 Tb2O31.1510
47、Cr2O31.4615 La2O31.718 Pr2O31.1703 Tb4O71.1762Ca2O 1.0602 Li2O 2.1527 Pr6O111.2082 TeO31.3762C1605 04 (2009)3REFERENCES(1) Taggart, Joseph E., Jr., and Siems, David F., Analytical Methods forthe Chemical Analysis of Geologic and Other Materials, U.S. Geo-logical Survey Open File Report 02-223-T, Jan
48、uary 11, 2002(2) deJongh, W. K., X-ray Fluorescence Analysis Applying TheoreticalMatrix CorrectionStainless Steel, X-ray Spectroscopy, Vol 2, 1973,pp. 151-158(3) Taggart, J. E. and Wahlberg, J. S., New Mold Design for Casting FusedSamples, Advances in X-ray Analysis, Vol 23, 1980a, pp. 257-261(4) Ta
49、ggart, J. E. and Wahlberg, J. S., A New In-Muffle Automatic FluxerDesign for Casting Glass Discs for X-Ray Fluorescence Analysis,Federation of Analytical Chemists and Spectroscopy Society, abstract327a, 1980b(5) Taggart, Joseph E., Jr., Lichte, F. E., and Wahlberg, J. S., Methods ofAnalysis of Samples Using X-Ray Fluorescence and InductionCoupled Plasma Spectroscopy, in Lipman, P. W., and Mullineaux, D.R., The 1980 Eruption of Mount St. Helens, Washington, U.S.Geological Survey, Professional Paper 1250, 1981, pp. 683-687(6) Taggart, Joseph E., Jr., Lindse
