1、Designation: C1605 04 (Reapproved 2014)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 monochr
7、oma-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 ar
8、e 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 28.0MgO 0.10 60.0CaO 0.02 60.0Na2O 0.15 30.0K2O 0.02 30.0TiO20.02 10.0P2O50.05 50.0MnO 0.01 15.0LOI (925C) 0.01 100.0
9、1.5 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 limitations prior to use.2. Referenced D
10、ocuments2.1 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, PhilipsPW1606 or equivalent.3.2 Pt-Au
11、 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.1These test methods are under the jurisdiction of ASTM Committe
12、e C21 onCeramic Whitewares and Related Productsand are the direct responsibility ofSubcommittee C21.03 on Methods for Whitewares and Environmental Concerns.Current edition approved Dec. 1, 2014. Published December 2014. Originallyapproved in 2004. Last previous edition approved in 2009 asC1605 04 (2
13、009). DOI: 10.1520/C1605-04R14.2The boldface numbers in parentheses refer to the list of references 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
14、, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14. Reagents4.1 Digest the samples in Johnson Matthey Spectroflux 1004or equivalent brand (lithium tetraborate). A blend
15、of lithiumtetraborate (Spectroflux 1004) and lithium metaborate (Spec-troflux 100A4) can be used if a lower fusion point is desired.The flux is ordered in powdered form, lot size as appropriate,and identified by number and date.4.2 Dry the minus 60-mesh material for the lot 2 days at300C and keep in
16、 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 tetraborateafter fusion.4.4 Weigh the charges of flux using a Zymark5robot to60.0035 g (60.04 % precision). If
17、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 of HCl, depending on the preference of thelaboratory.4.6 Prepare the LiBr used as a nonwetting agen
18、t 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 furnacemust be performed under a high velocity canopy hood. Boilingof the HCl cleaning solution is
19、 performed in a chemical fumehood with a safety sash. Safety glasses and specialnonflammable, nonasbestos, heat resistant gloves must be wornwhen removing the fluxer from the muffle furnace. Glass discsare sharp on the rear edge and should be handled with care.Dust from the flux must not be inhaled,
20、 so pouring of thepowdered flux must be done in a chemical hood. Preparation ofthe LiBr solution must be done by slowly adding LiCO3to theHBr so the generation of CO2does not cause the acid to spillover the edge of the beaker. The specific Chemical HygienePlan (CHP) for the laboratory, or laboratori
21、es if the corporationhas more than one, gives the first-aid treatment and disposalprocedures for chemical products used in this method.6. Procedure6.1 Ignite a 0.8000 g portion of minus 80-mesh sample in atared 95 percent Pt/5 percent Au crucible at 925C for 40minutes. Report the weight loss as perc
22、ent 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 thepowders.6.3 The combined weights of the sample and the flux willresult in an “infinitely thick” sample
23、 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 equipped to hold and the same number ofempty molds onto the fluxer.6.6 Following the instructions of th
24、e 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 and theblend of lithium tetraborate/lithium metaborate must be used.6.7 Remove the fluxer from the
25、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, Ni, Fe, Mnand high organic content require various special sample prepa-ration techniques, and, in s
26、ome 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 risk ofdamage of the Pt/Au crucibles.6.10 Using the wavelength dispersive X-ray spectrometer,the maj
27、or 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 Phillips PW1606 spectrometer. Theseconditions will be different for other models of x-ray spectro-photo
28、meters: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 required for the particular model of spectrophotometer beingused. The computerized recalibration is p
29、erformed using discsfrom the original calibration which are used to set the slope of4Spectroflux is a registered tradmark of Johnson Matthey, Johnson Matthey Plc2-4 Cockspur Street, Trafalgar Square, London, SW1Y 5BQ, United Kingdom.5Zymark is a registered trademark of Zymark Corporation, Hopkinton
30、Massa-chusetts.TABLE 1 Operating Conditions for Determination of Elements byWDXRFElement Line Crystal Detector Gas WindowNa K PX-1 Flow, P-10 2 m, polypropyleneMg K TLAP Flow, P-10 2 m, polypropyleneAl K PET Sealed neon 25 m, berylliumSi K InSb Sealed neon 25 m, berylliumPK Ge Sealed neon 50 m, bery
31、lliumKK LiF 200 Sealed krypton 100 m, berylliumCa K LiF 200 Sealed krypton 100 m, berylliumTi K LiF 200 Sealed krypton 100 m, berylliumMn K LiF 200 Sealed krypton 100 m, berylliumFe K LiF 200 Sealed krypton 100 m, berylliumPX-1 = Tungsten carbide layered; TLAP = thallium hydrogen phthalate; PET =pen
32、taerythritol 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 (2014)2the calibration curve. The U.S. Geographical Survey referencematerials used include AGV-2
33、(Andesite), DTS-1 (Dunite),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. Thisallows the original
34、calibration to be maintained while compen-sating for minor changes in the reagents, 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 instr
35、ument drift by using drift moni-tor analyses. Compare monitor intensity values obtained 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 ch
36、anges in the operating parameters.7.4 In order to keep track of instrumental short-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 d
37、isc exceeds three times thestandard deviation of the counting statistics, halt the 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, p
38、repare a samplepreparation check standard, TB-16for every 20 samples whichis produced 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, t
39、hen halt thesample preparation and locate the problem. Instrument recali-bration 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
40、and LOI by their percentage inthe sample.9. Precision and Bias9.1 PrecisionThe WDXRF 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 in
41、cludes the principal elements in a sample, then thetotal of their determinations 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 101pe
42、rcent, then it is automatically repeated. Precision in theWDXRF method depends on 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
43、 National Institute of Standards and Technology,is available to determine bias.APPENDIX(Nonmandatory Information)X1. TABLES6Refer to the U. S. Geological Survey listing of their reference materials,(HTTP:/minerals.cr.USGS.govgeo_chem_stand) or contact U.S. GeologicalSurvey, Box 25046, MS 973 Denver,
44、 CO 80225 for complete details of the referencematerials used in this procedure.C1605 04 (2014)3TABLE 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
45、 Tl2O31.1174As2O5 1.5339 Eu2O31.1579 MnO21.5825 RhO 1.5555 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 V2O51.7852Bi2O51.191
46、4 GeO21.4408 Nd2O31.1664 SeO31.6079 WO31.2610CO23.6644 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 Ta
47、2O51.2211CoO 1.2715 K2O 1.2046 PdO 1.1504 Tb2O31.1510Cr2O31.4615 La2O31.718 Pr2O31.1703 Tb4O71.1762Ca2O 1.0602 Li2O 2.1527 Pr6O111.2082 TeO31.3762TABLE X1.2 Weight-to-ppm-to-ppb EquivalentsWeight Percent ppm ppb ppt1.0 100000.1 10000.01 1000.001 100.0001 1 1000 1 g/g or 1 mg/L0.00001 0.1 1000.000001
48、 0.01 100.0000001 0.001 1 1000 1 ng/g or 1 g/L0.00000001 0.0001 0.1 1000.000000001 0.00001 0.01 100.0000000001 0.000001 0.001 1 1 pg/g or 1 ng/LTABLE X1.3 Grain Size and Sieve EquivalentsMesh OpeningU.S. StandardMesh No.TylerMeshEquivalentMicrometers Inches850 0.0331 20 20710 0.0278 25 24600 0.0234
49、30 28500 0.0197 35 32425 0.0165 40 35355 0.0139 45 42300 0.0117 50 48250 0.0098 60 60212 0.0083 70 65180 0.0070 80 80150 0.0059 100 100125 0.0049 120 115106 0.0041 140 15090 0.0035 170 17075 0.0029 200 20063 0.0025 230 25053 0.0021 270 27045 0.0017 325 32538 0.0015 400 400C1605 04 (2014)4REFERENCES(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, January 11, 2002(2) deJongh, W. K., X-ray Fluorescence Analysis Apply
