1、Designation: E581 10E581 17Standard Test Methods forChemical Analysis of Manganese-Copper Alloys1This standard is issued under the fixed designation E581; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A
2、 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 chemical analysis of manganese-copper alloys having chemical compositions within thefollowing limits:Elem
3、ent Concentration Range, %Element Range, %Copper 68.0 to 72.0Manganese 28.0 to 32.0Carbon 0.03 maxIron 0.01 maxPhosphorus 0.01 maxSilicon 0.05 maxSulfur 0.01 max1.2 The test methods appear in the following order:SectionsIron by the 1,10-PhenanthrolinePhotometric Method0.003 % to 0.02 %11 20Iron by t
4、he 1,10-PhenanthrolineSpectrophotometric Method0.003 % to 0.02 %11 20Manganese by the (Ethylenedinitrilo)Tetraacetic Acid (EDTA)Back-Titrimetric Method 28 % to 32 %21 27Phosphorus by theMolybdivanadophosphoric AcidExtraction Photometric Method0.002 % to 0.014 %28 38Phosphorus by theMolybdivanadophos
5、phoric AcidExtraction Spectrophotometric Method0.002 % to 0.014 %28 381.3 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 concerns, if any, associated with its us
6、e. It is the responsibilityof the 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 standardization
7、established in the Decision on Principles 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 WaterE29 Practice for Usin
8、g Significant Digits in Test Data to Determine Conformance with SpecificationsE50 Practices forApparatus, Reagents, and Safety Considerations for ChemicalAnalysis of Metals, Ores, and Related Materials1 These methods are under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals
9、, 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. Originally approved in 1976. Last previous edition a
10、pproved in 20042010 asE581 04E581 10.1. DOI: 10.1520/E0581-10.10.1520/E0581-17.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on
11、 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 all changes accurately, ASTM recommends that users
12、 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 19428-2959. United States1E55 Practice for Sampling Wrou
13、ght Nonferrous Metals and Alloys 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 Ana
14、lytical Chemistry for Metals, 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 Defini
15、tionsFor definitions of terms used in this test method, refer to Terminology E135.4. Significance and Use4.1 These test methods for the chemical analysis of metals and alloys are primarily intended to test such materials forcompliance with compositional specifications. It is assumed that all who use
16、 these test methods will be trained analysts capableof performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properlyequipped laboratory.5. Apparatus5.1 PhotometersSpectrophotometers shall conform to the requirements prescribed in Practice E60
17、.6. Reagents and Materials6.1 Reagents required for each determination are listed in separate sections of each test method. The standard solutions andcertain other reagents used in more than one procedure shall conform to the requirements prescribed in Practices E50.6.2 Purity of ReagentsReagent gra
18、de chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where suchspecifications are available.4 Other grades may be used, provided it is first ascertai
19、ned that the reagent is of sufficiently high purityto permit its use without lessening the accuracy of the determination.6.3 Purity of WaterUnless otherwise indicated, references to water shall be understood to mean reagent water as defined byType I of Specification D1193.7. Hazards7.1 For precautio
20、ns to be observed in this method, refer to Practices E50.7.2 A warning statement is given in 24.7.8. Sampling8.1 For procedures for sampling the material, refer to Practices E55 and E88.9. Rounding Calculated Values9.1 Calculated values shall be rounded to the desired number of places Rounding of te
21、st results obtained using this test methodshall be performed as directed in Practice E29 Rounding Method., Rounding Method, unless an alternative rounding method isspecified by the customer or applicable material specification.10. Interlaboratory Studies10.1 These test methods have been evaluated in
22、 accordance with Practice E173, unless otherwise noted in the precision section.The Reproducibility R2 of Practice E173 corresponds to the Reproducibility Index R of Practice E1601. The Repeatability R1 ofPractice E173 corresponds to the Repeatability Index r of Practice E1601.3 The last approved ve
23、rsion of this historical standard is referenced on www.astm.org.4 Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC, www.chemistry.org. For suggestions on the testing ofreagents not listed by theAmerican Chemical Society, see the United States Pha
24、rmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD, http:/www.usp.org.TABLE 1 Statistical InformationTest Sample LabsIron Found, % Repeatability(r, PracticeE1601)Reproducibility(R, PracticeE1601)ManganeseCopper7 0.0137 0.0013 0.0028E581 172IRON BY THE 1,10-PHE
25、NANTHROLINEPHOTOMETRICSPECTROPHOTOMETRIC METHOD11. Scope11.1 This test method covers the determination of iron in concentrations from 0.003 % to 0.02 %.11. Scope11.1 This test method covers the determination of iron from 0.003 % to 0.02 %.12. Summary of Test Method12.1 The sample is dissolved in HCl
26、 and hydrogen peroxide, and the excess oxidant removed by evaporation. The iron isextracted with methyl isobutyl ketone-benzene mixture. The iron is extracted from the organic phase into a hydroxylaminehydrochloride solution and the red-colored 1,10-phenanthroline complex is formed. Photometric Spec
27、trophotometric absorbancemeasurement is made at approximately 510 nm.13. ConcentrationIron Range13.1 The recommended concentration range is from 0.005 mg to 0.125 mg of iron per 50 mL of solution using a 2-cm cell.NOTE 1This test method has been written for cells having a 2-cm light path. Cells havi
28、ng other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.14. Stability of Color14.1 The color develops within 5 min and is stable for at least 4 h.15. Interferences15.1 Elements ordinarily present do not interfere if their concentrationsper
29、centages are under the maximum limits shown in 1.1.16. Reagents16.1 Hydroxylamine Hydrochloride Solution (10 g/L)Dissolve 5.0 g of hydroxylamine hydrochloride(NH2OH HCl)OHHCl) in 500 mL of water. Prepare fresh as needed.16.2 Iron, Standard Solution A (1 mL = 0.125 mg Fe)Transfer 0.1250 g of iron (pu
30、rity: 99.9 % min) to a 100-mLbeaker.Add10 mL of HCl (1 + 1) and 1 mL of bromine water. Boil gently until the excess bromine is removed. Add 20 mL of HCl, cool,transfer to a 1-L volumetric flask, dilute to volume, and mix.16.3 Iron, Standard Solution B (1 mL = 0.00625 mg Fe)Using a pipet, transfer 50
31、 mL of iron solution A (1 mL = 0.125 mgFe) to a 1-L volumetric flask, dilute to volume with HCl (1 + 49), and mix.16.4 Methyl Isobutyl Ketone-Benzene MixtureMix 200 mL of methyl isobutyl ketone (MIBK) and 100 mL of benzene.16.5 1,10-Phenanthroline-Ammonium Acetate Buffer SolutionDissolve 1.0 g of 1,
32、10-phenanthroline monohydrate in 5 mL ofHCl in a 600-mL beaker. Add 215 mL of CHacetic3COOH, acid, and, while cooling, carefully add 265 mL of NH4OH. Cool toroom temperature. Using a pH meter, check the pH; if it is not between 6.0 and 6.5, adjust it to that range by adding acetic acidor NH4OH as re
33、quired. Dilute to 500 mL.17. Preparation of Calibration Curve17.1 Calibration Solutions:17.1.1 Using pipets,pipet, transfer (1, 2, 5, 10, 15, and 20) mL of iron solution B (1 mL = 0.00625 mg Fe) to 50-mL volumetricflasks. Dilute to 20 mL.17.1.2 Add 20 mL of NH2OHHCl solution, mix, and allow to stand
34、 1 min. Proceed as directed in 17.3.17.2 Reference SolutionTransfer 20 mL of water to a 50-mL volumetric flask and proceed as directed in 17.1.2.17.3 Color DevelopmentAdd 5 mL of 1,10-phenanthroline-ammonium acetate buffer solution, dilute to volume, and mix.Allow to stand at least 5 min but not mor
35、e than 4 h.17.4 Photometry:Spectrophotometry:17.4.1 Multiple-Cell PhotometerSpectrophotometerMeasure the cell correction using absorption cells with a 2-cm lightpath and a light band centered at approximately 510 nm. Using the test cell, take the photometric spectrophotometric absorbancereadings of
36、the calibration solutions.17.4.2 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 centered atapproximately 510 nm. While maint
37、aining this adjustment, take the photometric spectrophotometric absorbance readings of thecalibration solutions.E581 17317.5 Calibration CurvePlot the net photometricspectrophotometric readings of the calibration solutions against milligrams ofiron per 50 mL of solution.18. Procedure18.1 Test Soluti
38、on:18.1.1 Transfer a 2.0-g sample, weighed to the nearest 10 mg, to a 400-mL beaker.18.1.2 CarryProcess a reagent blank through the entire procedure, using the same amounts of all reagents but with the sampleomitted.18.1.3 Add 25 mL of HCl (7 + 3) and then H2O2 as needed to dissolve the alloy comple
39、tely. When dissolution is complete, add20 mL of HCl and heat carefully to decompose excess peroxide.H2O2. Cool to room temperature, transfer to a 125-mL conicalseparatory funnel. Add HCl (1 + 1), as required, to adjust the volume to 50 mL.18.1.4 Add 20 mL of MIBK benzene mixture to the separatory fu
40、nnel and shake 1 min. Allow the phases to separate, discardthe aqueous phase, wash the organic phase three times with 3-mL to 5-mL portions of HCl (1 + 1) to remove copper, and discardthe washings. Extract the iron from the organic phase by shaking vigorously 30 s with 10 mL of NH2OHHCl solution. Tr
41、ansferthe aqueous phase to a 50-mL volumetric flask. Repeat the extraction with a second 10-mL portion of NH2OHHCl solution, andtransfer the extract to the 50-mL flask. Dilute to 40 mL and proceed as directed in 18.3.18.2 Reference SolutionUse the reagent blank solution prepared as directed in 18.1.
42、2.18.3 Color DevelopmentProceed as directed in 17.3.18.4 PhotometrySpectrophotometryProceed as directed in 17.4.19. Calculation19.1 Convert the net photometric spectrophotometric absorbance reading of the test solution to milligrams of iron by means ofthe calibration curve. Calculate the percentage
43、of iron as follows:Iron,%5A/B 310! (1)where:A = milligrams of iron found in 50 mL of the final test solution, andB = grams of sample represented in 50 mL of the final test solution.20. Precision and Bias20.1 PrecisionSeven laboratories cooperated in testing this test method and obtained the precisio
44、n data shown in Table 1,which were calculated in accordance with Practice E1601. Although samples covered by this test method with ironconcentrationspercentages near the lower limit of the scope were not available for testing, the precision data obtained should apply.20.2 BiasThe accuracy of this te
45、st method could not be evaluated because adequate certified standard reference materials wereunavailable at the time of testing. The user is encouraged to verify by the use of certified reference materials, if available, that theaccuracy of this test method is adequate for the contemplated use.MANGA
46、NESE BY THE (ETHYLENEDINITRILO)TETRAACETIC ACID (EDTA)BACK-TITRIMETRICMETHOD21. Scope21.1 This test method covers the determination of manganese in concentrations from 28.0 % to 32.0 %.21. Scope21.1 This test method covers the determination of manganese from 28.0 % to 32.0 %.22. Summary of Test Meth
47、od22.1 The sample is dissolved in HNO3. Manganese is chelated with disodium (ethylenedinitrilo) tetraacetate (EDTA), which isadded in excess. The pH of the solution is adjusted to 10 and sodium cyanide is added to complex copper. The manganese is thendetermined by back-titration with standard mangan
48、ese solution.23. Interferences23.1 The elements ordinarily present do not interfere if their concentrationspercentages are under the maximum limits shownin 1.1.24. Reagents24.1 Buffer Solution (pH 10)Transfer 54 g of ammonium chloride (NH4Cl) to a 1-L beaker, dissolve in 500 mL of water, add350 mL o
49、f NH4OH, dilute to 1 L, and mix. Store in a polyethylene bottle.E581 17424.2 Copper Solution (25 g/L)Transfer 2.50 g of copper (purity: 99.9 % min) to a 250-mL beaker. Add 20 mL of HNO3(1 + 1). When dissolution is complete, boil to expel oxides of nitrogen. Cool, dilute to 100 mL, and mix.24.3 Disodium (Ethylenedinitrilo)tetraacetic Acid Dihydrate (EDTA), Standard Solution (0.05 M)Dissolve 18.6127 g ofdisodium (ethylenedinitrilo) tetraacetate dihydrate in water, transfer to a 1-L volumetric flask, dilute to volume, an
