1、Designation: E539 11Standard Test Method forAnalysis of Titanium Alloys by X-Ray FluorescenceSpectrometry1This standard is issued under the fixed designation E539; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last re
2、vision. 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 method2covers the X-ray fluorescence analysisof titanium alloys for the following elements in the rangesindicated:E
3、lement Mass Fraction Range, %Aluminum 0.041 to 8.00Chromium 0.013 to 4.00Copper 0.015 to 0.60Iron 0.023 to 2.00Manganese 0.003 to 9.50Molybdenum 0.005 to 4.00Nickel 0.005 to 0.80Niobium 0.004 to 7.50Palladium 0.014 to 0.200Ruthenium 0.019 to 0.050Silicon 0.014 to 0.15Tin 0.017 to 3.00Vanadium 0.017
4、to 15.50Yttrium 0.0011 to 0.0100Zirconium 0.007 to 4.001.2 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
5、 of regulatory limitations prior to use. Specific precau-tionary statements are given in Section 10.2. Referenced Documents2.1 ASTM Standards:3E135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE1172 Practice for Describing and Specifying aWavelength-Dispersive X
6、-Ray SpectrometerE1329 Practice for Verification and Use of Control Charts inSpectrochemical AnalysisE1361 Guide for Correction of Interelement Effects inX-Ray Spectrometric AnalysisE1621 Guide for X-Ray Emission Spectrometric AnalysisE1724 Guide for Testing and Certification of Metal, Ore,and Metal
7、-Related Reference Materials43. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this test method, referto Terminology E135.4. Summary of Test Method4.1 The specimen is finished to a clean, uniform surface andthen irradiated by high-energy X-ray photons. Secondary Xrays are produced
8、 and emitted from the sample. This radiationis diffracted by means of crystals and focused on a detector,which measures the count rates at specified wavelengths. Theoutput(s) of the detector(s) is integrated or counted for a fixedtime or until the counts reach a certain fixed number. Massfractions o
9、f the elements are determined by relating themeasured radiation of unknown samples to calibration curvesprepared using reference materials of known compositions.5. Significance and Use5.1 This method is suitable for providing data on thechemical composition of titanium alloys having compositionswith
10、in the scope of the standard. It is intended for routineproduction control and for determination of chemical compo-sition for the purpose of certifying material specificationcompliance. Additionally, the analytical performance dataincluded with this method may be used as a benchmark todetermine if s
11、imilar X-ray spectrometers provide equivalentprecision and accuracy.6. Interferences6.1 Line overlaps, interelement effects and matrix effectsmay exist for some of the elements in the scope. A list ofpotential line overlaps is provided in section 6.2. Modern X-rayspectrometers provide software for g
12、eneration of mathematical1This test method is under the jurisdiction of ASTM Committee E01 onAnalytical Chemistry for Metals, Ores, and Related Materials and is the directresponsibility of Subcommittee E01.06 on Ti, Zr, W, Mo, Ta, Nb, Hf, Re.Current edition approved May 1, 2011. Published July 2011.
13、 Originally approvedin 1975. Last previous edition approved in 2007 as E539 07. DOI: 10.1520/E0539-11.2Supporting data for this test method as determined by cooperative testing hasbeen filed at ASTM International Headquarters as three separate research reportsRR:E02-1010, RR:E01-1061, RR:E01-1114.3F
14、or 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.4Withdrawn. The last approved version of this historical standa
15、rd is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.corrections to model the effects of line overlaps, interelementand matrix interferences. The user of this method may chooseto use these mathematical corr
16、ections for analysis. GuideE1621 provides a more extensive overview of mathematicalinterference correction methods.6.2 Potential line overlaps may occur directly on the analyteline or may create problems with the background. Some listedinterfering elements may not be present in significant massfract
17、ions in the particular alloy being tested, but are listed forconsideration. The magnitude of the overlap will be a functionof the collimation on the analyte line. Line overlaps toconsider:Analyte Interfering Element(s)V Ti (direct overlap)Cr V (direct overlap)Cr Mn (background overlap)Ni Nb, Cu (bac
18、kground overlaps)Mo Nb, Zr (background overlaps)Pd Mo (background overlap)Ru Mo, Nb (background overlap)Y Zr (background overlap)Zr Cu (background overlap)7. Apparatus7.1 Specimen Preparation Equipment:7.1.1 Surface Grinder, with 60 to 600-grit silicon carbidebelts or disks capable of providing test
19、 specimens with auniform flat finish. For silicon determinations 60600 gritaluminum oxide or aluminum zirconium oxide belts or diskscapable of providing test specimens with a uniform flat finishshould be used. A wet belt or wet disk grinder is preferred toprevent work hardening of the sample.7.1.2 L
20、athe, as an alternative to abrasive surfacing of testspecimens a lathe may be used to produce a uniform surface.7.2 X-ray Spectrometer:7.2.1 Practice E1172 describes the essential components ofa wavelength-dispersive spectrometer and should be used as areference source for considerations in selectio
21、n of a suitablespectrometer for testing to this method.8. Reagents and Materials8.1 Detector GasAs specified by the spectrometer manu-facturer for use with flow proportional detectors.9. Reference Materials9.1 Certified reference materials are commercially availablefrom both domestic and internation
22、al sources. These should beused for the development of calibration curves.9.2 It may be necessary to produce additional referencematerials to supplement the certified reference materials usedin the development of calibration curves. Refer to Guide E1724for guidance in developing these reference mate
23、rials.9.3 The reference materials shall cover the mass fractionranges of the elements being determined. A minimum of threereference materials shall be used to develop the calibrationcurve for each element. A greater number of calibrationmaterials may be required to calculate mathematical correc-tion
24、s for interferences, especially when interference correc-tions are estimated using only empirical data. See GuideE1361.10. Hazards10.1 X-ray spectrometers produce ionizing radiation. Thismethod does not purport to address all safety considerationsrelating to the installation and use of an X-ray spec
25、trometer toperform this method. In general, however, OSHA guidelinesfor use of ionizing radiation producing equipment must be met,as well as state and local regulations relating to radiationhygiene must be followed. Additionally, the safety guidelinesestablished by the instrument manufacturer should
26、 be fol-lowed. Appropriate safety practices should be used withsample preparation equipment. Refer to Guide E1621 foradditional information on hazards.11. Preparation of Reference Materials and TestSpecimens11.1 The reference materials and test specimens must be ofan appropriate size for fabrication
27、 into a flat surfaced piece thatwill fit into the cup utilized to perform the test with the flatsurface completely covering the aperture of the cup. Grind orlathe/mill the reference materials/specimens to provide a flat,clean area for testing. All reference materials and test speci-mens must receive
28、 the same surface preparation. Care must beused in selecting the grinding media, in order to minimize thepotential for surface contamination from the media. For in-stance, aluminum oxide and aluminum zirconium oxide grind-ing belts/disks may introduce aluminum and/or zirconiumcontamination and silic
29、on carbide belts/disks may introducesilicon contamination. The 2010 ILS study indicated thatgrinding using an aluminum based media may be an unsuitablepreparation method for aluminum determination of mass frac-tions of less than 1.0 % as statistically significant aluminumpickup was observed for labs
30、 using grinding for preparation ofCP type materials.12. Preparation of Apparatus12.1 Install and operate the spectrometer in accordance withthe manufacturers instructions. Also refer to Guide E1621 foradditional considerations for preparing the spectrometer.12.2 The tube power supply conditions (kV/
31、mA) should beoptimized according to the manufacturers recommendations.Once established the optimized current and voltage settingsshall be used for generation of calibration curves and for allsubsequent specimen measurements.12.3 Check pulse height discrimination for each detector perthe manufacturer
32、s recommendations to verify that the limitvoltages are properly established for each element beingdetermined.12.4 The crystals and X-ray lines specified in Table 1 havebeen found to provide acceptable performance. Set up theinstrument in accordance with manufacturers recommenda-tions to analyze usin
33、g these X-ray lines. Other lines may beused provided performance criteria using the alternative linescompare favorably to the precision and bias stated for thismethod.12.5 Choose a sample cup size that is suitable for theexpected specimen sizes.12.6 Use the spinner if available on the spectrometer.
34、Theorientation of the grinding striations on the reference materialsE539 112must be situated the same as the striation pattern on thespecimens if a sample spinner is not employed.12.7 Determine and specify background correction, if avail-able and necessary, by following the manufacturers recom-menda
35、tions.12.8 Optimize counting times to obtain adequate precisionfor the determinations being made. A minimum of 10 000counts is required for one percent precision in the countingstatistics, 40 000 for one-half percent.13. Calibration and Standardization13.1 Calibration (Preparation of Analytical Curv
36、es)Using the conditions given in Section 12, measure a series ofreference materials that cover the required mass fractionranges. Use at least three reference materials for each element.Prepare a calibration curve for each element being determinedusing the instrument manufacturers recommendations. It
37、 willbe necessary to analyze more than three reference materials togenerate mathematical interference corrections from the em-pirical data. It is acceptable to use matrix corrections generatedfrom fundamental parameter calculations such as those pro-vided in some instrument manufacturers software (N
38、ote 1).Because the number of calibration materials available forgeneration of titanium alloy calibrations for some elements isvery limited, it may be preferable to use matrix correctionsgenerated from fundamental parameters. Refer to PracticesE1361 and E1621 for more detailed information on X-raycal
39、ibration curve generation and corrections.NOTE 1Two approaches may be taken for the use of fundamentalparameters. In one case, fundamental parameters calculations are used tocreate a set of influence coefficients that are used in a specific mathemati-cal model to fit the measured calibration data. T
40、he second approach is fullfundamental parameters software in which all calculations are based ontheory and internal to the software. The analyst is not required to choosean algorithm and no coefficients are reported.13.2 As X-ray tubes and detectors age, it is normal for countrates to change and sta
41、ndardization (drift correction) or reca-libration will be necessary to maintain analytical quality.Control charting per Practice E1329 may be used to verifycontinuing calibration curve performance and to establish theneed for recalibration or standardization (drift correction). Ifstandardization (dr
42、ift correction) is to be used, establish aprotocol at the time that the calibration curves are established.13.3 Calibration VerificationThe performance of a cali-bration curve must be verified after establishment. This isaccomplished by re-analyzing enough reference materials toestablish that the ca
43、libration curve is performing as desired.NOTE 2The user of this method is strongly cautioned to use calibra-tion reference materials that fully cover the mass fraction ranges expectedto be analyzed.14. Procedure14.1 Specimen LoadingIf the spectrometer is equippedwith a sample spinner, it shall be us
44、ed. If a sample spinner isnot available, the grinding striation orientation on all speci-mens and reference materials must be the same when they areplaced in the spectrometer.14.2 ExcitationExpose the specimens to X radiation inaccordance with the conditions specified in Section 12 byfollowing the i
45、nstrument manufacturers recommendations.14.3 Radiation MeasurementsRefer to Guide E1621 forguidance on obtaining enough counts to be statistically mean-ingful.15. Calculation of Results15.1 Using the count rates measured in 14.3 and thecalibration curves generated in 13.1, determine the massfraction
46、s of the elements in the specimen.16. Precision and Bias16.1 The data presented in Tables 2-14 were determined inprior studies made to demonstrate method performance for themethod as historically scoped for Titanium 6Al-4V analysisonly. The data in Table 2 and Table 14 are supported by theresearch r
47、eport RR:E02-1010. The data in Tables 3-13 aresupported by the research report RR:E01-1061.16.2 A new study was performed in 2010 in order todemonstrate method precision and bias for an expanded scopeof alloys. Six laboratories participated in this interlaboratorystudy. Two of the six laboratories s
48、ubmitted datasets from twoinstruments. Up to eight total datasets per analyte werecollected from the laboratories for twelve different materials.The twelve different materials were selected to represent arange of titanium alloys, as well as a range of concentrationsfor the elements that may be deter
49、mined using this method.Precision and bias were calculated in accordance with E1601and are presented for each material tested in Tables 15-29. Thesupporting data is found in RR:E01-1114.17. Keywords17.1 fluorescence; titanium; X-rayTABLE 1 Suggested X-Ray LinesElementLineDesignationA2u Angle,degBWavelength,(nm)CrystalAluminum Ka 144.67 0.8339 PETAluminum Ka 142.57 0.8339 EDDTChromium Kb 62.36 0.2085 LiF 200Chromium Ka 69.36 0.2291 LiF 200Copper Ka 45.03 0.1542 LiF 200Iron Ka 57.52 0.1937 LiF 200Manganese Ka 62.97 0.2103 LiF 200Molybdenum Ka 20.33 0.0710 LiF 200Nicke
