1、Designation: E439 10E439 17Standard Test Methods forChemical Analysis of Beryllium1This standard is issued under the fixed designation E439; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in par
2、entheses 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 chemical analysis of beryllium having chemical compositions within the following limits:ConcentrationElement Range, %Al
3、uminum 0.05 to 0.30Beryllium 97.5 to 100Beryllium Oxide 0.3 to 3Carbon 0.05 to 0.30Copper 0.005 to 0.10Chromium 0.005 to 0.10Iron 0.05 to 0.30Magnesium 0.02 to 0.15Nickel 0.005 to 0.10Silicon 0.02 to 0.151.2 The test methods in this standard are contained in the sections indicated below.SectionsChro
4、mium by the Diphenylcarbazide Photometric Test Method0.004 % to 0.04 % 10 19Chromium by the Diphenylcarbazide Spectrophotometric TestMethod0.004 % to 0.04 % 10 19Iron by the 1,10-Phenanthroline Photometric Test Method0.05 % to 0.25 % 20 29Iron by the 1,10-Phenanthroline Spectrophotometric Test Metho
5、d0.05 % to 0.25 % 20 29Manganese by the Periodate Photometric Test Method0.008 % to 0.04 % 30 39Manganese by the Periodate Spectrophotometric Test Method0.008 % to 0.04 % 30 39Nickel by the Dimethylglyoxime Photometric Test Method0.001 % to 0.04 % 40 49Nickel by the Dimethylglyoxime Spectrophotometr
6、ic Test Method0.001 % to 0.04 % 40 491.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.4 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibilityof the
7、 user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use.1.5 This international standard was developed in accordance with internationally recognized principles on standardizationestablished in the Decision on Pr
8、inciples for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization Technical Barriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent Water1 These test methods are under the jurisdiction ofASTM
9、 Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and are the direct responsibilityof Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, Precious Metals, their Alloys, and Related Metals.Current edition approved Jan. 15, 2010May 1, 2017. Published February 2010July 2017. Ori
10、ginally published in 1971. Last previous edition approved in 20042010 asE439 04a.E439 10. DOI: 10.1520/E0439-10.10.1520/E0439-17.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume informatio
11、n, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict
12、all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-
13、2959. United States1E29 Practice for Using Significant Digits in Test Data to Determine Conformance with SpecificationsE50 Practices forApparatus, Reagents, and Safety Considerations for ChemicalAnalysis of Metals, Ores, and Related MaterialsE55 Practice for Sampling Wrought Nonferrous Metals and Al
14、loys for Determination of Chemical CompositionE60 Practice for Analysis of Metals, Ores, and Related Materials by SpectrophotometryE88 Practice for Sampling Nonferrous Metals and Alloys in Cast Form for Determination of Chemical CompositionE135 Terminology Relating to Analytical Chemistry for Metals
15、, Ores, and Related MaterialsE173 Practice for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals (Withdrawn 1998)3E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method3. Terminology3.1 For definitions of terms used in t
16、his test method, refer to Terminology E135.4. Significance and Use4.1 These test methods for the chemical analysis of beryllium metal are primarily intended as referee methods to test suchmaterials for compliance with compositional specifications. It is assumed that all who use these test methods wi
17、ll be trainedanalysts capable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed ina properly equipped laboratory.5. Apparatus, Reagents, and PhotometricSpectrophotometric Practice5.1 Apparatus and reagents required for each determination are
18、 listed in separate sections preceding the procedure unlessotherwise specified. The apparatus, standard solutions, and reagents shall conform to the requirements prescribed in Practices E50.PhotometersSpectrophotometers shall conform to the requirements prescribed in Practice E60.5.2 Photometric and
19、 spectrophotometric Spectrophotometric practice prescribed in these test methods shall conform to PracticeE60.6. Hazards6.1 For precautions to be observed in these test methods, reference shall be is made to Practices E50. Both beryllium metal andits compounds may be toxic. Care should be exercised
20、Exercise care to prevent contact of beryllium-containing materials with theskin. The inhalation of any beryllium-containing substance, either as a volatile compound or as finely divided powder, should beespecially avoided. Beryllium-containing residues (especially ignited oxide) should be carefully
21、disposed of.7. Sampling7.1 Wrought products shall be sampled in accordance with Practice E55. Cast products shall be sampled in accordance withPractice E88. However, these test methods do not supersede any sampling requirements specified in a specific ASTM materialspecification.8. Rounding Calculate
22、d Values8.1 Calculated values shall be rounded to the desired number of places Rounding of test results obtained using this test methodshall be performed as directed in Practice E29. , Rounding Method, unless an alternative rounding method is specified by thecustomer or applicable material specifica
23、tion.9. Interlaboratory Studies9.1 These test methods have been evaluated in accordance with Practice E173, unless otherwise noted under the precisionsection.CHROMIUM BY THE DIPHENYLCARBAZIDE(PHOTOMETRIC)(SPECTROPHOTOMETRIC) TEST METHOD10. Scope10.1 This test method covers the determination of chrom
24、ium in concentrations from 0.004 % to 0.04 %.10.2 This international standard was developed in accordance with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the Wor
25、ld Trade Organization Technical Barriers to Trade (TBT) Committee.3 The last approved version of this historical standard is referenced on www.astm.org.E439 17211. Summary of Test Method11.1 Chromium is oxidized by peroxydisulfate in the presence of silver nitrate, and the chromium diphenylcarbazide
26、 complexis then developed. PhotometricSpectrophotometric measurement is made at approximately 540 nm.12. ConcentrationChromium Range12.1 The recommended concentration range is from 0.02 mg to 0.10 mg of chromium per 250 mLof solution, using a 2-cm cell.NOTE 1This test method has been written for cel
27、ls having a 2-cm light path. Cells having other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.13. Stability of Color13.1 The color of the chromium complex develops almost immediately but starts to fade after about 10 min. PhotometricSpec-
28、trophotometric measurements should be made within 5 min after developing the color.14. Interferences14.1 The elements ordinarily present do not interfere if their concentrations mass fractions are under the maximum limits shownin 1.1.15. Reagents15.1 Acetone (CH3COCH3).15.2 Ammonium Peroxydisulfate
29、Solution (100 gL)Dissolve 10 g of ammonium peroxydisulfate (NH4)2S2O8) in water anddilute to 100 mL. Do not use a solution that has stood more than 12 h.15.3 Chromium, Standard Solution (1 mL = 0.005 mg Cr)Dissolve 0.2830 g of potassium dichromate (K2Cr2O7) in water ina 1-L volumetric flask, dilute
30、to volume, and mix. Using a pipet, transfer 5 mL to a 100-mL volumetric flask, dilute to volume,and mix.15.4 Diphenylcarbazide Solution (5 gL)Dissolve 0.50 g of diphenylcarbazide (1,5-diphenylcarbohydrazide) in 100 mL ofacetone. Do not use a solution that has stood for more than 1 h.15.5 Phosphoric
31、Acid (1 + 1)Mix one volume of concentrated phosphoric acid (H3PO4, sp gr 1.69) with one volume of water.15.5 Silver Nitrate Solution (2.5 gL)Dissolve 0.25 g of silver nitrate (AgNO3) in water and dilute to 100 mL.15.7 Sodium Hydroxide Solution (500 gL)Dissolve 50 g of sodium hydroxide (NaOH) in wate
32、r, and dilute to 100 mL.15.6 Sulfuric Acid (1 + 1)Mix carefully and with stirring one volume of concentrated H2SO4 (sp gr 1.84) into one volumeof water.15.7 Purity of WaterUnless otherwise indicated, reference to water shall be understood to mean reagent water as defined byType II of Specification D
33、1193.16. Preparation of Calibration Curve16.1 Calibration Solutions:16.1.1 Using pipets,pipet, transfer (5, 10, 15, and 20) mL of chromium solution (1 mL = 0.005 mg Cr) to 400-mL beakers. Add1 mL of H3PO4 (1 + 1) and dilute to approximately 250 mL with water.16.1.2 Adjust the pH to 0.95 6 0.05 with
34、NaOH solution or H2SO4 (1 + 1). Add 10 mL of AgNO3 solution, 10 mL of(NH4)2S2O8 solution, and a few glass beads. Cover the beaker with a ribbed cover glass, and boil for at least 25 min. During thisperiod, add water as required to maintain a volume not less than 150 mL. Cool, and transfer to a 250-m
35、L volumetric flask. Proceedas directed in 16.3.16.2 Reference SolutionAdd 1 mL of H3PO4 (1 + 1) to 250 mL of water in a 400-mL beaker. Proceed as directed in 16.1.2.16.3 Color DevelopmentAdd 2.0 mL of diphenylcarbazide solution. Dilute to volume, and mix.16.3.1 Prepare only that number of solutions
36、which can be measured 5 min after color development.16.4 Photometry:Spectrophotometry:16.4.1 Multiple-Cell PhotometerSpectrophotometerMeasure the cell correction, using absorption cells with a 2-cm lightpath and a light band centered at approximately 540 nm. Using the test cell, take the photometric
37、 spectrophotometric absorbancereadings of the calibration solutions.16.4.2 Single-Cell PhotometerSpectrophotometerTransfer a suitable portion of the reference solution to an absorption cellwith a 2-cm light path and adjust the photometerspectrophotometer to the initial setting using a light band cen
38、tered atapproximately 540 nm. While maintaining this adjustment, take the photometric spectrophotometric absorbance readings of thecalibration solutions.E439 17316.5 Calibration CurvePlot the net photometric spectrophotometric absorbance readings of the calibration solutions againstmilligrams of chr
39、omium per 250 mL of solution.17. Procedure17.1 Test Solution:17.1.1 Transfer a 0.50-g sample, weighed to the nearest 0.1 mg, to a 250-mLbeaker (beaker. Note 2).Add 100 mLof water and,in small increments, add 15 mLof H2SO4 (1 + 1). When apparent reaction has ceased, warm until all action stops. If th
40、e chromiumcontent of the sample is between 0.02 % and 0.04 %, use a 0.25-g sample.NOTE 2If the chromium content of the sample is between 0.02 % and 0.04 %, use a 0.25-g sample.17.1.2 Filter through an 11-cm fine filter paper into a 400-mL beaker. Wash the paper five times or six times with hot water
41、.Reserve the filtrate. Transfer the paper to a platinum crucible, dry, and ignite at 700 C.17.1.3 Treat the residue with one drop of H2SO4 (1 + 1), three drops or four drops of HNO3, and 3 mL or 4 mL 4 mL of HF.Evaporate to complete dryness, and ignite for 3 min to 4 min at 900 C. Fuse the residue w
42、ith about 1 g of potassium pyrosulfate(K2S2O7). Cool, leach in 25 mL of water, add this solution to the reserved filtrate (17.1.2), and dilute to 250 mL. Proceed asdirected in 16.1.2.17.2 Reference SolutionCarry a reagent blank through the entire procedure, using the same amounts of all reagents wit
43、h thesample omitted for use as the reference solution.omitted.17.3 Color DevelopmentProceed as directed in 16.3.17.4 PhotometrySpectophotometryTake the photometric spectrophotometric absorbance reading of the test solution asdirected in 16.4.18. Calculation18.1 Convert the net photometric spectropho
44、tometric absorbance reading of the test solution to milligrams of chromium bymeans of the calibration curve. Calculate the percentage of chromium as follows:Chromium,%5A/B 310! (1)where:A = chromium found in 250 mL of the final test solution, mg, andB = sample represented in 250 mL of the final test
45、 solution, g.19. Precision and Bias19.1 PrecisionEight cooperatorsanalysts from seven laboratories cooperated in testing this test method and obtained the datasummarized in Table 1.19.2 BiasNo certified reference materials suitable for testing this test method were available when this interlaborator
46、y testingprogram was conducted. The user of this standard is encouraged to employ accepted reference materials, if available, to determinethe bias of this test method as applied in a specific laboratory.19.3 Practice E173 has been replaced by Practice E1601. The Reproducibility Index R2 corresponds
47、to the ReproducibilityIndex R of Practice E1601. Likewise the The Repeatability Index R1 corresponds to the Repeatability Index r of Practice E1601.IRON BY THE 1,10-PHENANTHROLINEPHOTOMETRICSPECTROPHOTOMETRIC TEST METHOD20. Scope20.1 This test method covers the determination of iron in concentration
48、s from 0.05 % to 0.25 %.20.2 This international standard was developed in accordance with internationally recognized principles on standardizationestablished in the Decision on Principles for the Development of International Standards, Guides and Recommendations issuedby the World Trade Organization
49、 Technical Barriers to Trade (TBT) Committee.TABLE 1 Statistical InformationTest Material ChromiumFound, %Repeatability(R1, PracticeE173)Reproducibility(R2, PracticeE173)1 0.007 less than 0.001 0.0012 0.020 0.002 0.003E439 17421. Summary of Test Method21.1 The iron is reduced with hydroxylamine hydrochloride and converted to the 1,10-phenanthroline complex. Photometric-Spectrophotometric measurement is made at approximately 515 nm.22. ConcentrationIron Range22.1 The recommended concentration range is from 0.05 mg
