1、Designation: E581 17E581 17aStandard 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.
2、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 These test methods cover the chemical analysis of manganese-copper alloys having chemical compositions within thefollowing limits:Ele
3、ment 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-PhenanthrolineSpectrophotometric Method0.003 % to 0.02 %11 20Manganese by the (Ethylenedinit
4、rilo)Tetraacetic Acid (EDTA)Back-Titrimetric Method 28 % to 32 %21 27Phosphorus by theMolybdivanadophosphoric 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
5、.4 This standard does not purport to address all of the safety concerns, if any, associated with its use. 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 internati
6、onal 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 Technical Barriers to Trade (TBT) Committe
7、e.2. Referenced Documents2.1 ASTM Standards:2D1193 Specification for Reagent WaterE29 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 Mater
8、ialsE55 Practice for Sampling Wrought 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 Compositi
9、onE135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related MaterialsE173 Practice for Conducting Interlaboratory Studies of Methods for Chemical Analysis of Metals (Withdrawn 1998)31 These methods are under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Met
10、als, 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 May 1, 2017Nov. 15, 2017. Published July 2017December 2017. Originally approved in 1976. Last previous editio
11、n approved in 20102017 asE581 10.E581 17. DOI: 10.1520/E0581-17.10.1520/E0581-17A.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
12、 on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.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 tec
13、hnically possible to adequately depict 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
14、 Box C700, West Conshohocken, PA 19428-2959. United States1E1601 Practice for Conducting an Interlaboratory Study to Evaluate the Performance of an Analytical Method3. Terminology3.1 DefinitionsFor definitions of terms used in this test method, refer to Terminology E135.4. Significance and Use4.1 Th
15、ese 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 these test methods will be trained analysts capableof performing common laboratory procedures skillfully and s
16、afely. It is expected that work will be performed in a properlyequipped laboratory.5. Apparatus5.1 Spectrophotometers shall conform to the requirements prescribed in Practice E60.6. Reagents and Materials6.1 Reagents required for each determination are listed in separate sections of each test method
17、. 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 grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that allreagents conform to the specif
18、ications 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 ascertained that the reagent is of sufficiently high purityto permit its use without lessening the accuracy of the determination.6
19、.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 precautions to be observed in this method, refer to Practices E50.7.2 A warning statement is given in 24.7.8. Sampling8.1 For proce
20、dures for sampling the material, refer to Practices E55 and E88.9. Rounding Calculated Values9.1 Rounding of test results obtained using this test method shall be performed as directed in Practice E29, Rounding Method,unless an alternative rounding method is specified by the customer or applicable m
21、aterial specification.10. Interlaboratory Studies10.1 These test methods have been evaluated in 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 of
22、Practice E173 corresponds to the Repeatability Index r of Practice E1601.IRON BY THE 1,10-PHENANTHROLINESPECTROPHOTOMETRIC METHOD11. Scope11.1 This test method covers the determination of iron from 0.003 % to 0.02 %.4 Reagent Chemicals, American Chemical Society Specifications, American Chemical Soc
23、iety, Washington, DC, www.chemistry.org. For suggestions on the testing ofreagents not listed by theAmerican Chemical Society, see the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD, http:/www.usp.org.TABLE 1 Statistical InformationTest Sa
24、mple LabsIron Found, % Repeatability(r, PracticeE1601)Reproducibility(R, PracticeE1601)ManganeseCopper7 0.0137 0.0013 0.0028E581 17a212. Summary of Test Method12.1 The sample is dissolved in HCl and hydrogen peroxide, and the excess oxidant removed by evaporation. The iron isextracted with methyl is
25、obutyl 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. Spectrophotometric absorbance measurementis made at 510 nm.13. Iron Range13.1 The recommended range is from 0.005 mg to 0.
26、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 having 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 devel
27、ops within 5 min and is stable for at least 4 h.15. Interferences15.1 Elements ordinarily present do not interfere if their percentages 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 (NH2OHHCl) in5
28、00 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 (purity: 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 vol
29、umetric flask, dilute to volume, and mix.16.3 Iron, Standard Solution B (1 mL = 0.00625 mg Fe)Using a pipet, transfer 50 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 is
30、obutyl ketone (MIBK) and 100 mL of benzene.16.5 1,10-Phenanthroline-Ammonium Acetate Buffer SolutionDissolve 1.0 g of 1,10-phenanthroline monohydrate in 5 mL ofHCl in a 600-mL beaker. Add 215 mL of acetic acid, and, while cooling, carefully add 265 mL of NH4OH. Cool to roomtemperature. Using a pH me
31、ter, check the pH; if it is not between 6.0 and 6.5, adjust it to that range by adding acetic acid orNH4OH as required. Dilute to 500 mL.17. Preparation of Calibration Curve17.1 Calibration Solutions:17.1.1 Using pipet, transfer (1, 2, 5, 10, 15, and 20) mL of iron solution B (1 mL = 0.00625 mg Fe)
32、to 50-mL volumetric flasks.Dilute to 20 mL.17.1.2 Add 20 mL of NH2OHHCl solution, mix, and allow to stand 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-phenanthrol
33、ine-ammonium acetate buffer solution, dilute to volume, and mix.Allow to stand at least 5 min but not more than 4 h.17.4 Spectrophotometry:17.4.1 Multiple-Cell SpectrophotometerMeasure the cell correction using absorption cells with a 2-cm light path and a lightband centered at 510 nm. Using the tes
34、t cell, take the spectrophotometric absorbance readings of the calibration solutions.17.4.2 Single-Cell SpectrophotometerTransfer a suitable portion of the reference solution to an absorption cell with a 2-cmlight path and adjust the spectrophotometer to the initial setting, using a light band cente
35、red at 510 nm. While maintaining thisadjustment, take the spectrophotometric absorbance readings of the calibration solutions.17.5 Calibration CurvePlot the net spectrophotometric absorbance readings of the calibration solutions against milligrams ofiron per 50 mL of solution.18. Procedure18.1 Test
36、Solution:18.1.1 Transfer a 2.0-g sample, weighed to the nearest 10 mg, to a 400-mL beaker.18.1.2 Process a reagent blank through the entire procedure, using the same amounts of all reagents but with the sample omitted.18.1.3 Add 25 mL of HCl (7 + 3) and then H2O2 as needed to dissolve the alloy comp
37、letely. When dissolution is complete, add20 mL of HCl and heat carefully to decompose excess H2O2. Cool to room temperature, transfer to a 125-mL conical separatoryfunnel. Add HCl (1 + 1), as required, to adjust the volume to 50 mL.E581 17a318.1.4 Add 20 mL of MIBK benzene mixture to the separatory
38、funnel 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.
39、Transferthe 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.
40、1.2.18.3 Color DevelopmentProceed as directed in 17.3.18.4 SpectrophotometryProceed as directed in 17.4.19. Calculation19.1 Convert the net spectrophotometric absorbance reading of the test solution to milligrams of iron by means of the calibrationcurve. Calculate the percentage of iron as follows:I
41、ron,%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 precision data shown in Tabl
42、e 1,which were calculated in accordance with Practice E1601. Although samples covered by this test method with iron percentagesnear the lower limit of the scope were not available for testing, the precision data obtained should apply.20.2 BiasThe accuracy of this test method could not be evaluated b
43、ecause 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.MANGANESE BY THE (ETHYLENEDINITRILO)TET
44、RAACETIC ACID (EDTA)BACK-TITRIMETRICMETHOD21. Scope21.1 This test method covers the determination of manganese from 28.0 % to 32.0 %.22. Summary of Test Method22.1 The sample is dissolved in HNO3. Manganese is chelated with disodium (ethylenedinitrilo) tetraacetate (EDTA), which isadded in excess. T
45、he 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 manganese solution.23. Interferences23.1 The elements ordinarily present do not interfere if their percentages are under the maximum limits shown in
46、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 of NH4OH, dilute to 1 L, and mix. Store in a polyethylene bottle.24.2 Copper Solution (25 g/L)Transfer 2.50 g of copper (purity: 99.9 % min) to a 250-mL beak
47、er. 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 wate
48、r, transfer to a 1-L volumetric flask, dilute to volume, and mix. Thesolution is stable for several months when stored in plastic or borosilicate glass bottles.24.3.1 Standardize the solution as follows: Using a pipet, transfer 25 mL of zinc solution (0.050 M) to a 400-mL beaker. Add25 mL of buffer
49、solution and dilute to about 250 mL. Add four drops to six drops of eriochrome black-T indicator solution andtitrate with EDTA standard solution to the color change from magenta to blue. Calculate the molarity of the EDTA solution asfollows:Molarity of EDTA solution,A 51.25B (2)where:A = molarity of EDTA solution, andE581 17a4B = milliliters of EDTA solution required to titrate 25 mL of zinc standard solution (0.050 M).24.4 Eriochrome Black-T Indicator Solution (8 gL)Dissolve 0.4 g of the sodium salt of eriochrome black-T in a mi
