1、Designation: E439 10Standard 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 parenthese
2、s 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 ofberyllium having chemical compositions within the followinglimits:ConcentrationElement Range, %Aluminum 0.
3、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 thesections indicated below.SectionsChromium by th
4、e Diphenylcarbazide Photometric Test Method0.004 % to 0.04 % 10-19Iron by the 1,10-Phenanthroline Photometric Test Method0.05 % to 0.25 % 20-29Manganese by the Periodate Photometric Test Method0.008 % to 0.04 % 30-39Nickel by the Dimethylglyoxime Photometric Test Method0.001 % to 0.04 % 40-491.3 The
5、 values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This standard does not purport to address all of thesafety problems, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priat
6、e safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE50 Practices for Ap
7、paratus, Reagents, and Safety Consid-erations for Chemical Analysis of Metals, Ores, andRelated MaterialsE55 Practice for Sampling Wrought Nonferrous Metals andAlloys for Determination of Chemical CompositionE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption Spec
8、trometryE88 Practice for Sampling Nonferrous Metals and Alloys inCast Form for Determination of Chemical CompositionE135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE173 Practice for Conducting Interlaboratory Studies ofMethods for Chemical Analysis of Metals3E
9、1601 Practice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical Method3. Terminology3.1 For definitions of terms used in this test method, refer toTerminology E135.4. Significance and Use4.1 These test methods for the chemical analysis of beryl-lium metal are primar
10、ily intended as referee methods to testsuch materials for compliance with compositional specifica-tions. It is assumed that all who use these test methods will betrained analysts capable of performing common laboratoryprocedures skillfully and safely. It is expected that work will beperformed in a p
11、roperly equipped laboratory.1These test methods are under the jurisdiction of ASTM Committee E01 onAnalytical Chemistry for Metals, Ores, and Related Materials and are the directresponsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, their Alloys, andRelated Metals.Current edition approved
12、Jan. 15, 2010. Published February 2010. Originallypublished in 1971. Last previous edition approved in 2004 as E439 04a. DOI:10.1520/E0439-10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards vol
13、ume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Appara
14、tus, Reagents, and Photometric Practice5.1 Apparatus and reagents required for each determinationare listed in separate sections preceding the procedure unlessotherwise specified. The apparatus, standard solutions, andreagents shall conform to the requirements prescribed inPractices E50. Photometers
15、 shall conform to the requirementsprescribed in Practice E60.5.2 Photometric and spectrophotometric practice prescribedin these test methods shall conform to Practice E60.6. Hazards6.1 For precautions to be observed in these test methods,reference shall be made to Practices E50. Both beryllium metal
16、and its compounds may be toxic. Care should be exercised toprevent 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 be especially avoided. Beryllium-containing residues(especi
17、ally ignited oxide) should be carefully disposed of.7. Sampling7.1 Wrought products shall be sampled in accordance withPractice E55. Cast products shall be sampled in accordancewith Practice E88. However, these test methods do not super-sede any sampling requirements specified in a specific ASTMmate
18、rial specification.8. Rounding Calculated Values8.1 Calculated values shall be rounded to the desired num-ber of places as directed in Practice E29.9. Interlaboratory Studies9.1 These test methods have been evaluated in accordancewith Practice E173, unless otherwise noted under the precisionsection.
19、CHROMIUM BY THE DIPHENYLCARBAZIDE(PHOTOMETRIC) TEST METHOD10. Scope10.1 This test method covers the determination of chro-mium in concentrations from 0.004 % to 0.04 %.11. Summary of Test Method11.1 Chromium is oxidized by peroxydisulfate in the pres-ence of silver nitrate, and the chromium diphenyl
20、carbazidecomplex is then developed. Photometric measurement is madeat approximately 540 nm.12. Concentration Range12.1 The recommended concentration range is from0.02 mg to 0.10 mg of chromium per 250 mL of solution, usinga 2-cm cell.NOTE 1This test method has been written for cells having a 2-cmlig
21、ht 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 almostimmediately but starts to fade after about 10 min. Photometricmeasurements should be mad
22、e within 5 min after developingthe color.14. Interferences14.1 The elements ordinarily present do not interfere if theirconcentrations are under the maximum limits shown in 1.1.15. Reagents15.1 Acetone (CH3COCH3).15.2 Ammonium Peroxydisulfate Solution (100 g/L)Dissolve 10 g of ammonium peroxydisulfa
23、te (NH4)2S2O8)inwater and dilute to 100 mL. Do not use a solution that hasstood more than 12 h.15.3 Chromium, Standard Solution (1 mL = 0.005 mg Cr)Dissolve 0.2830 g of potassium dichromate (K2Cr2O7) in waterin a 1-L volumetric flask, dilute to volume, and mix. Using apipet, transfer 5 mL to a 100-m
24、L volumetric flask, dilute tovolume, and mix.15.4 Diphenylcarbazide Solution (5 g/L)Dissolve 0.50 gof diphenylcarbazide (1,5-diphenylcarbohydrazide) in 100 mLof acetone. Do not use a solution that has stood for more than1h.15.5 Phosphoric Acid (1 + 1)Mix one volume of concen-trated phosphoric acid (
25、H3PO4, sp gr 1.69) with one volume ofwater.15.6 Silver Nitrate Solution (2.5 g/L)Dissolve 0.25 g ofsilver nitrate (AgNO3) in water and dilute to 100 mL.15.7 Sodium Hydroxide Solution (500 g/L)Dissolve 50 gof sodium hydroxide (NaOH) in water, and dilute to 100 mL.15.8 Sulfuric Acid (1 + 1)Mix careful
26、ly and with stirringone volume of concentrated H2SO4(sp gr 1.84) into onevolume of water.15.9 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water as definedby Type II of Specification D1193.16. Preparation of Calibration Curve16.1 Calibration Soluti
27、ons:16.1.1 Using pipets, transfer (5, 10, 15, and 20) mL ofchromium solution (1 mL = 0.005 mg Cr) to 400-mL beakers.Add 1 mL of H3PO4(1 + 1) and dilute to approximately250 mL with water.16.1.2 Adjust the pH to 0.95 6 0.05 with NaOH solution orH2SO4(1 + 1). Add 10 mL of AgNO3solution, 10 mL of(NH4)2S
28、2O8solution, and a few glass beads. Cover the beakerwith a ribbed cover glass, and boil for at least 25 min. Duringthis period, add water as required to maintain a volume not lessthan 150 mL. Cool, and transfer to a 250-mL volumetric flask.Proceed as directed in 16.3.16.2 Reference SolutionAdd 1 mL
29、of H3PO4(1+1)to250 mL of water in a 400-mL beaker. Proceed as directed in16.1.2.16.3 Color DevelopmentAdd 2.0 mL of diphenylcarba-zide solution. Dilute to volume, and mix.16.3.1 Prepare only that number of solutions which can bemeasured 5 min after color development.E439 10216.4 Photometry:16.4.1 Mu
30、ltiple-Cell PhotometerMeasure the cell correc-tion, using absorption cells with a 2-cm light path and a lightband centered at approximately 540 nm. Using the test cell,take the photometric readings of the calibration solutions.16.4.2 Single-Cell PhotometerTransfer a suitable portionof the reference
31、solution to an absorption cell with a 2-cm lightpath and adjust the photometer to the initial setting using a lightband centered at approximately 540 nm. While maintainingthis adjustment, take the photometric readings of the calibra-tion solutions.16.5 Calibration CurvePlot the net photometric readi
32、ngsof the calibration solutions against milligrams of chromium per250 mL of solution.17. Procedure17.1 Test Solution:17.1.1 Transfer a 0.50-g sample, weighed to the nearest 0.1mg, to a 250-mL beaker (Note 2). Add 100 mL of water and, insmall increments, add 15 mL of H2SO4(1 + 1). When appar-ent reac
33、tion has ceased, warm until all action stops.NOTE 2If the chromium content of the sample is between 0.02 % and0.04 %, use a 0.25-g sample.17.1.2 Filter through an 11-cm fine filter paper into a400-mL beaker. Wash the paper five or six times with hotwater. Reserve the filtrate. Transfer the paper to
34、a platinumcrucible, 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 of HF.Evaporate to complete dryness, and ignite for 3 min to 4 min at900 C. Fuse the residue with about 1 g of potassium pyro-sulfate (K2S2O7). Cool
35、, leach in 25 mL of water, add thissolution to the reserved filtrate (17.1.2), and dilute to 250 mL.Proceed as directed in 16.1.2.17.2 Reference SolutionCarry a reagent blank through theentire procedure, using the same amounts of all reagents withthe sample omitted for use as the reference solution.
36、17.3 Color DevelopmentProceed as directed in 16.3.17.4 PhotometryTake the photometric reading of the testsolution as directed in 16.4.18. Calculation18.1 Convert the net photometric reading of the test solutionto milligrams of chromium by means of the calibration curve.Calculate the percentage of ch
37、romium as follows:Chromium, % 5 A/B 3 10! (1)where:A = chromium found in 250 mL of the final test solution,mg, andB = sample represented in 250 mL of the final test solution,g.19. Precision and Bias19.1 PrecisionEight cooperators from seven laboratoriescooperated in testing this test method and obta
38、ined the datasummarized in Table 1.19.2 BiasNo certified reference materials suitable fortesting this test method were available when this interlabora-tory testing program was conducted. The user of this standardis encouraged to employ accepted reference materials, ifavailable, to determine the bias
39、 of this test method as appliedin a specific laboratory.19.3 Practice E173 has been replaced by Practice E1601.The Reproducibility Index R2corresponds to the Reproduc-ibility Index R of Practice E1601. Likewise the RepeatabilityIndex R1corresponds to the Repeatability Index r of PracticeE1601.IRON B
40、Y THE 1,10-PHENANTHROLINEPHOTOMETRIC TEST METHOD20. Scope20.1 This test method covers the determination of iron inconcentrations from 0.05 % to 0.25 %.21. Summary of Test Method21.1 The iron is reduced with hydroxylamine hydrochlorideand converted to the 1,10-phenanthroline complex. Photomet-ric mea
41、surement is made at approximately 515 nm.22. Concentration Range22.1 The recommended concentration range is from0.05 mg to 0.250 mg of iron per 100 mL of solution using a2-cm cell.NOTE 3This test method has been written for cells having a 2-cmlight path. Cells having other dimensions may be used, pr
42、ovided suitableadjustments can be made in the amounts of sample and reagents used.23. Stability of Color23.1 The color develops within 10 min and is stable for atleast 2 h.24. Interferences24.1 Nickel forms a complex with and consumes 1,10-phenanthroline. However, an amount of nickel equivalent tofo
43、ur times the amount of iron does not affect the irondetermination. Other elements ordinarily present in berylliumdo not interfere if their concentrations are under the maximumlimits shown in 1.1.25. Reagents25.1 Ammonium Acetate Solution (230 g/L)Dissolve115 g of ammonium acetate in water and dilute
44、 to 500 mL.25.2 Hydroxylamine Hydrochloride Solution (100 g/L)Dissolve 5.0 g of hydroxylamine hydrochloride (NH2OH HCl) in 50 mL of water. Prepare fresh as needed.25.3 Iron, Standard Solution (1 mL = 0.01 mg Fe)Dissolve 0.7020 g of ferrous ammonium sulfateTABLE 1 Statistical InformationTest Material
45、ChromiumFound, %Repeatability(R1, PracticeE173)Reproducibility(R2, PracticeE173)1 0.007 less than 0.001 0.0012 0.020 0.002 0.003E439 103(Fe(NH4)2(SO4)26H2O) in 10 mL of water, and add 1 mL ofH2SO4(1 + 1). Transfer to a 100-mL volumetric flask, diluteto volume, and mix.25.4 1,10-Phenanthroline Soluti
46、on (1 g/L)Dissolve 0.1 gof 1,10-phenanthroline monohydrate in 100 mL of water.25.5 Purity of WaterUnless otherwise indicated, referenceto water shall be understood to mean reagent water as definedby Type II of Specification D1193.26. Preparation of Calibration Curve26.1 Calibration SolutionsUsing pi
47、pets, transfer (5, 10,15, 20, and 25) mL of iron solution (1 mL = 0.01 mg Fe) to100-mL volumetric flasks. Add 1 mL of H2SO4(1 + 1) anddilute to 50 mL. Proceed as directed in 26.3.26.2 Reference SolutionTransfer 50 mL of water and1mLofH2SO4(1 + 1) to a 100-mL volumetric flask. Proceedas directed in 2
48、6.3.26.3 Color DevelopmentAdd 3 mL of NH2OH HCl so-lution, and 20 mLof ammonium acetate solution, and mix.Add10 mL of 1,10-phenanthroline solution, and mix. Check the pHof the solution with indicator paper and, if required, addammonium acetate solution to adjust the pH to between 4.0 and4.5. Dilute
49、to volume, and mix.26.4 Photometry:26.4.1 Multiple-Cell PhotometerDetermine the cell cor-rection using absorption cells with a 2-cm light path and a lightband centered at approximately 515 nm. Using the test cell,take the photometric readings of the calibration solutions.26.4.2 Single-Cell PhotometerTransfer a suitable portionof the reference solution to an absorption cell with a 2-cm lightpath and adjust the photometer to the initial setting, using alight band centered at approximately 515 nm. While maintain-ing this adjustment, take
