1、Designation: E 2371 04Standard Test Method forAnalysis of Titanium and Titanium Alloys by AtomicEmission Plasma Spectrometry1This standard is issued under the fixed designation E 2371; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision
2、, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This method describes the analysis of titanium andtitanium alloys by ICP-AES (Inductively Coupled Plasm
3、a) andDCP-AES (Direct Current Plasma) for the following elements:ElementApplicationRange (wt.%)QuantitativeRange (wt.%)Aluminum 08 0.001 to 8.0Boron 00.04 0.0008 to 0.01Chromium 05 0.005 to 4.0Copper 00.6 0.002 to 0.5Iron 03 0.004 to 3.0Manganese 00.04 0.001 to 0.01Molybdenum 08 0.004 to 6.0Nickel 0
4、1 0.001 to 1.0Silicon 00.5 0.02 to 0.4Tin 04 0.02 to 3.0Vanadium 015 0.01 to 15.0Yttrium 00.04 0.001 to 0.004Zirconium 05 0.003 to 4.01.2 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 esta
5、blish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific safetyhazards statements are given in Section 9.2. Referenced Documents2.1 ASTM Standards:2D 1193 Specification for Reagent WaterE50 Practices for Apparatus, Reagents, and
6、 Safety Precau-tions for Chemical Analysis of MetalsE 135 Terminology Relating to Emission SpectroscopyE 882 Guide for Accountability and Quality Control in theChemical Analysis LaboratoryE 1479 Practice for Describing and Specifying Inductively-Coupled Plasma Atomic Emission SpectrometersE 1601 Pra
7、ctice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical MethodE 1763 Guide for Interpretation and Use of Results fromInterlaboratory Testing of Chemical Analysis MethodsE 1832 Practice for Describing and Specifying a Direct-Current-Plasma Atomic Emission Spectromete
8、rE 1914 Practice for the Use of Terms Relating to theDevelopment and Evaluation of Methods for ChemicalAnalysis3. Terminology3.1 For definitions of terms used in this method, refer toTerminology E 135 and Terminology section in E 1914.4. Summary of Test Method4.1 Amineral acid solution of the sample
9、 is aspirated into aninductively coupled plasma or a direct current plasma spec-trometer. The intensities of emission lines from the spectra ofthe analytes are measured and compared with calibrationcurves obtained from solutions containing known amounts ofpure elements.5. Significance and Use5.1 Thi
10、s method for the chemical analysis of titanium andtitanium alloys is primarily intended to test material forcompliance with specifications of chemical composition.5.2 It is assumed that all who use this method will be trainedanalysts capable of performing common laboratory proceduresskillfully and s
11、afely, and that the work will be performed in aproperly equipped laboratory.5.3 The method is designed to give the maximum flexibilityanalyzing elements in the titanium matrix. Thus options aregiven in calibration and analysis to accommodate the variety ofICP and DCP spectrometers and their auxiliar
12、y systems.6. Interferences6.1 Potential interferences for analytes (see 1.2) are listed inTable 1 for this methods analytical wavelengths. The analyti-cal wavelengths of Table 1 were selected for their freedomfrom interference by the elements included in this method andthe titanium base (see Note 1)
13、.1This 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.Current edition approved June 1, 2004. Published June 2004.2For referenced ASTM standar
14、ds, 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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA
15、19428-2959, United States.NOTE 1Elements outside the scope of this method may be present inproduction materials or experimental titanium alloys. These potentialinterferences must be tested for their effect as an interference on analytewavelengths and corrections made as necessary as a part of method
16、development according to manufacturers instructions.7. Apparatus7.1 Direct Current Plasma Atomic Emission Spectrometersused in this method may conform to the specifications given inPractice E 1832. A differently designed instrument may pro-vide equivalent measurements. Suitability for use is deter-m
17、ined by comparing the results obtained with the precision andbias statements contained in this method.7.2 Inductively Coupled Plasma Atomic Emission Spec-trometers used in this method may conform to the specifica-tions given in Practice E 1479. A differently designed instru-ment may provide equivale
18、nt measurements. Suitability for useis determined by comparing the results obtained with theprecision and bias statements contained in this method.7.3 The sample introduction system shall be constructed ofmaterials resistant to all mineral acids including HF.7.4 Each instrument shall be set up accor
19、ding to the manu-facturers instructions.8. Reagents and Materials8.1 Purity of reagents utilized in this procedure shall con-form to the requirements prescribed in Practice E50.8.2 The purity of water used shall conform to the require-ments in Specification D 1193 for reagent water, Type II.8.3 The
20、argon supply for the ICP or DCP plasma shall be of99.998 % minimum purity; for purging the ICP Optical path,99.999 % minimum purity.8.4 The nitrogen supply for purging the ICP Optical pathshall be 99.995 % minimum purity.8.5 Reference solutions are available for purchase as analternative to the prep
21、aration of solutions from pure metals orcompounds.8.5.1 Single element reference solutions in the form ofCertified Reference Materials are available from the NationalInstitute of Standards and Technology (NIST) and a number ofcommercial suppliers. The NIST Standard Reference Materials(SRM) 31003seri
22、es are available as 10 mg/g (5 mg/g for someelements) solutions. See Notes 2 and 3.8.5.2 Reference solutions from other sources may be used ifthey have a documented link of traceability to primary refer-ence materials or CRMs from a national metrology instituteand the concentrations of impurities ar
23、e known or determined(see Note 4).NOTE 2To use solution standards of concentration less than theoriginal concentration, prepare the solution by dilution of the concentratedreference solution. Maintain the acid concentration as recommended in theNIST or other certificate. NIST certificates provide in
24、structions fordilution by mass or by volume. Dilution by mass may be preferable topipetting, especially for solutions containing HF.NOTE 3The user should establish internal laboratory procedures thatspecify a maximum shelf life for a working standard solution. It has beenobserved that polytetrafluor
25、oethylene (PTFE) bottles preserve the integrityof the solutions stored in them for a long period of time.NOTE 4If single element solutions are not provided with values fortrace impurities, it is necessary to either determine the concentrations ofelements that are in the scope of this method or, if t
26、hey cannot be detected,ensure that the method detection limit is sufficiently low that theimpurities cannot be detected in solutions prepared for calibration of thismethod.8.5.3 Calibrants Prepared from Pure Metals or their Salts(see Notes 5 and 6):NOTE 5Elemental solutions of 10.0 mg/mL or 1.00 mg/
27、mL can bestored in HDPE or polytetrafluoroethylene (PTFE) for one (1) year. The0.100 mg/mL solutions must be made fresh before each use.NOTE 6Elements and compounds for the solutions below are usuallysupplied on a “metals basis” assay. The concentration of the elementsought, as percent in the presen
28、t usage, is the total metallic content of thecompound less the assayed metallic impurities (including B, Si, Y).8.5.3.1 Aluminum Standard Solution A (1 mL = 10.0 mgAl)Dissolve 10.000 g aluminum wire (purity 99.99 %, min)in 200 mL of HCl (1+1) with gentle heating. Cool, transfer toa 1 L volumetric fl
29、ask, dilute to the mark and mix. (A smallcrystal of mercuric nitrate may be added to catalyze thedissolution reaction.)8.5.3.2 Boron Standard Solution A (1 mL = 1.00 mgB)Dissolve 5.720 g of boric acid, H3BO3(purity 99.99 %,min) in 500 mL of water. Transfer toa1Lvolumetric flask,dilute to the mark an
30、d mix. Store in a plastic bottle.8.5.3.3 Chromium Standard Solution A (1 mL = 10.0 mgCr)Dissolve 10.00 g of chromium (purity 99.99 %, min.)chips in 200 mL of HCl (1+1) with gentle heating. Cool,transfer to a 1 L volumetric flask, dilute to the mark and mix.8.5.3.4 Copper Standard Solution A (1 ML =
31、10.0 MGCU)Dissolve 10.00 g of copper wire (purity 99.99 %, min.)in 100 mL of HNO3(1+1) with gentle heating. Continueheating until brown fumes cease to evolve. Cool, transfer to a1 L volumetric flask, and add 50 mL of HNO3, dilute to themark and mix.8.5.3.5 Copper Standard Solution B (1 mL = 1.00 mgC
32、u)Pipet 10 mL of Copper Standard Solution A into a 100mL volumetric flask, add 10 mL of HNO3, dilute to the markand mix.3Available from National Institute of Standards and Technology, 100 BureauDrive, Gaithersburg, MD 20899, USA.TABLE 1 Analytical Lines and Potential InterferencesElementWavelength(n
33、m)PotentialInterferencesNotesAl 394.401B 249.678Cr 267.716Cu 327.396Fe 259.940Mn 257.610Mo 202.030Ni 231.604Si 288.160 CrSn 175.790 2242.949 Mo, Fe 3V 292.402 Mo, FeY 360.073 MoZr 343.823NoteSn 175.790 Low UV CapableSn 242.949 DCP; non-Low UV capable alternativeE23710428.5.3.6 Iron Standard Solution
34、 A (1 mL = 10.0 mg Fe)Dissolve 10.00 g of iron rod (purity 99.99 %, min, that hasbeen cleaned to remove oxidation) in 100 mL of HNO3byheating to boiling. Continue gentle boiling until brown fumescease to evolve. Cool, transfer toa1Lvolumetric flask, diluteto the mark and mix.8.5.3.7 Manganese Standa
35、rd Solution A (1 mL = 1.00 mgMn)Dissolve 1.000 g of manganese (purity 99.98 %, min) in100 mL of HNO3(1+1) with gentle heating. Boil gently toexpel brown fumes and cool. Transfer toa1Lvolumetric flask,add 50 mL of HNO3, dilute to the mark and mix.8.5.3.8 Molybdenum Standard Solution A (1 mL = 10.0 mg
36、Mo)Transfer 5.00 g of molybdenum rod (purity 99.98 %,min) to a 600 mL beaker. Add 200 mL of an acid mixture ofHCl, HNO3and water (3+2+1) and heat gently to dissolve.Cool, transfer to a 500 mL volumetric flask, dilute to the markand mix.8.5.3.9 Nickel Standard Solution A (1 mL = 10.0 mgNi)Dissolve 10
37、.00 g of nickel wire (purity 99.99 %, min) in100 mL of HNO3with gentle heating. Continue heating untilbrown fumes are no longer evolved. Cool, transfer toa1Lvolumetric flask, dilute to the mark and mix.8.5.3.10 Nickel Standard Solution B (1 mL = 1.00 mgNi)Pipet 10 mL of Nickel Standard SolutionAinto
38、 a 100 mLvolumetric flask, add 10 mL of HNO3, dilute to the mark andmix.8.5.3.11 Silicon Standard Solution A (1 mL = 1.00 mgSi)Fuse 0.2139 g of silicon dioxide (purity 99.99 %, min)with 2.00 g of sodium carbonate (purity 99.995 %, min) in aplatinum crucible. Dissolve the melt in water, transfer to a
39、 100mL flask, dilute to the mark and mix. Store in a plastic bottle.8.5.3.12 Tin Standard Solution A (1 mL = 10.0 mg Sn)Dissolve 10.00 g of tin wire (purity 99.99 %, min) in 100 mLof HCl with gentle heating. Cool, transfer toa1Lvolumetricflask, and add 400 mL of HCl, dilute to the mark and mix.8.5.3
40、.13 Vanadium Standard Solution A (1 mL = 10.0 mgV)Dissolve 17.852 g of vanadium (V) oxide (V2O5) (purity99.99 %, min) ina1Lvolumetric flask by adding 300 mL ofHCl and warm (# 75C) to complete dissolution. Cool, diluteto the mark and mix.8.5.3.14 Yttrium Standard Solution A (1 mL = 1.00 mgY)Dissolve
41、1.270 g of yttrium oxide (Y2O3) (purity 99.99 %,min) in 30 mL of HCl (1+1). Transfer toalLvolumetric flask,dilute to the mark and mix.8.5.3.15 Zirconium Standard Solution A (1 mL = 10.0 mgZr)Transfer 35.326 g of ZrOCl28H2O (purity 99.99 %, min)toa1Lvolumetric flask, add approximately 500 mL of water
42、,and swirl until dissolved.Add 50 mL of HCl, cool, dilute to themark and mix.8.6 Titanium base metal for the production of all calibrationstandards shall be of 99.99 % minimum purity on a metalsbasis. See Notes 6 and 7.NOTE 7Impurities of this titanium base material shall be determinedby Glow Discha
43、rge Mass Spectrometry (GDMS) or suitable technique thathas detection limits for each respective analyte that is less than that of theICP or DCP in the titanium matrix.8.7 An internal standard may be used to control drift. If aninternal standard is used, it shall not interfere with the analytesof thi
44、s method.8.8 A surfactant may be used to control droplet formation inthe spray chamber and sample tubes of the DCP spectrometer.A maximum 0.1 % Vol/Vol of a surfactant such asPolyoxyethyene(10)isooctylphenyl ether is recommended.8.9 Calibration Solutions:8.9.1 Standard Solution A:8.9.1.1 Add 5.00 g
45、(ICP system) or 10.00 g (DCP system) oftitanium (purity 99.99 %, min) toa1Lplastic volumetric flask(see Note 8).NOTE 8The ICP procedure and DCP procedure require differingsample sizes. This is maintained consistently throughout the method interms of sample weights and analyte additions for samples,
46、calibrationsolutions and quality control solutions.8.9.1.2 Add 150 mL of HCl, then 20 mL of HF (see warningnote below in 8.9.1.4).8.9.1.3 After all titanium has dissolved, add 10 mL ofHNO3(ICP) or 15 mL of HNO3(DCP) to oxidize.8.9.1.4 Cool, add internal standard solution and/or surfac-tant if desire
47、d, dilute to the mark and mix. (WarningHFcauses burns that require immediate medical attention eventhough they are not immediately painful; refer to the paragraphabout HF in the Safety Precautions of Practice E50.)8.9.1.5 Store in a polytetrafluoroethylene (PTFE) bottle.Label the bottle and mark wit
48、h the date of preparation. Thissolutions shelf life is six (6) months.8.9.1.6 Adjust the “0” values of Standard A to reflect theactual concentration of the analytes in the titanium basematerial before calibration.8.9.2 Standard Solutions B-G:8.9.2.1 Weigh quantities of titanium (purity 99.99 % min)i
49、nto 1 L plastic volumetric flasks in accordance with AppendixX1 for ICP and Appendix X2 for DCP.8.9.2.2 To each, add the specified volumes of HCl and HF(see warning in 8.9.1.4) in accordance with Appendix X1 forICP and Appendix X2 for DCP.8.9.2.3 After the titanium dissolves completely, add thespecified volumes of HNO3in accordance with Appendix X1for ICP and Appendix X2 for DCP.8.9.2.4 Cool, add volumes of standard solutions in accor-dance with Appendix X1 for ICP and Appendix X2 for DCP.8.9.2.5 Add internal standard solution and/or surfa
