1、Designation: E581 10Standard 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 number
2、 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 ofmanganese-copper alloys having chemical compositionswithin the following limits:Element Conc
3、entration 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 %11-20Manganese by the (Ethylenedinitri
4、lo)Tetraacetic Acid (EDTA)Back-Titrimetric Method 28 % to 32 %21-27Phosphorus by theMolybdivanadophosphoric AcidExtraction Photometric Method0.002 % to 0.014 %28-381.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 This sta
5、ndard 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 establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1
6、ASTM Standards:2D1193 Specification for Reagent WaterE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE50 Practices for Apparatus, Reagents, and Safety Consid-erations for Chemical Analysis of Metals, Ores, andRelated MaterialsE55 Practice for Samplin
7、g Wrought Nonferrous Metals andAlloys for Determination of Chemical CompositionE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption SpectrometryE88 Practice for Sampling Nonferrous Metals and Alloys inCast Form for Determination of Chemical CompositionE135 Terminol
8、ogy Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE173 Practice for Conducting Interlaboratory Studies ofMethods for Chemical Analysis of Metals3E1601 Practice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical Method3. Terminology3.1 Definit
9、ionsFor definitions of terms used in this testmethod, refer to Terminology E135.4. Significance and Use4.1 These test methods for the chemical analysis of metalsand alloys are primarily intended to test such materials forcompliance with compositional specifications. It is assumedthat all who use the
10、se test methods will be trained analystscapable of performing common laboratory procedures skill-fully and safely. It is expected that work will be performed ina properly equipped laboratory.5. Apparatus5.1 Photometers shall conform to the requirements pre-scribed in Practice E60.6. Reagents and Mat
11、erials6.1 Reagents required for each determination are listed inseparate sections of each test method. The standard solutionsand certain other reagents used in more than one procedureshall conform to the requirements prescribed in Practices E50.6.2 Purity of ReagentsReagent grade chemicals shall beu
12、sed in all tests. Unless otherwise indicated, it is intended that1These 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
13、Metals.Current edition approved Jan. 15, 2010. Published February 2010. Originallyapproved in 1976. Last previous edition approved in 2004 as E581 041. DOI:10.1520/E0581-10.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For A
14、nnual Book of ASTMStandards volume 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 1942
15、8-2959, United States.all reagents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use
16、without lessening the accuracy ofthe determination.6.3 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type I of Specification D1193.7. Hazards7.1 For precautions to be observed in this method, refer toPractices E50.7.2 A warning s
17、tatement is given in 24.7.8. Sampling8.1 For procedures for sampling the material, refer toPractices E55 and E88.9. Rounding Calculated Values9.1 Calculated values shall be rounded to the desired num-ber of places as directed in Practice E29 Rounding Method.10. Interlaboratory Studies10.1 These test
18、 methods have been evaluated in accordancewith Practice E173, unless otherwise noted in the precisionsection. The Reproducibility R2of Practice E173 correspondsto the Reproducibility Index R of Practice E1601. The Repeat-ability R1of Practice E173 corresponds to the RepeatabilityIndex r of Practice
19、E1601.IRON BY THE 1,10-PHENANTHROLINEPHOTOMETRIC METHOD11. Scope11.1 This test method covers the determination of iron inconcentrations from 0.003 % to 0.02 %.12. Summary of Test Method12.1 The sample is dissolved in HCl and hydrogen perox-ide, and the excess oxidant removed by evaporation. The iron
20、is extracted with methyl isobutyl ketone-benzene mixture. Theiron is extracted from the organic phase into a hydroxylaminehydrochloride solution and the red-colored 1,10-phenanthroline complex is formed. Photometric measurementis made at approximately 510 nm.13. Concentration Range13.1 The recommend
21、ed concentration range is from0.005 mg to 0.125 mg of iron per 50 mL of solution using a2-cm cell.NOTE 1This test method has been written for cells having a 2-cmlight path. Cells having other dimensions may be used, provided suitableadjustments can be made in the amounts of sample and reagents used.
22、14. Stability of Color14.1 The color develops within 5 min and is stable for atleast 4 h.15. Interferences15.1 Elements ordinarily present do not interfere if theirconcentrations are under the maximum limits shown in 1.1.16. Reagents16.1 Hydroxylamine Hydrochloride Solution (10 g/L)Dissolve 5.0 g of
23、 hydroxylamine hydrochloride(NH2OH HCl) 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 (purity: 99.9 % min) to a 100-mLbeaker. Add 10 mL of HCl (1 + 1) and 1 mL of bromine water.Boil gently until the excess bromine is removed.
24、 Add 20 mL ofHCl, 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 mL of iron solution A(1 mL = 0.125 mg Fe) to a 1-L volumetric flask, dilute tovolume with HCl (1 + 49), and mix.16.4 Methyl Isobutyl Ke
25、tone-Benzene MixtureMix200 mL of methyl isobutyl ketone (MIBK) and 100 mL ofbenzene.16.5 1,10-Phenanthroline-Ammonium Acetate BufferSolutionDissolve 1.0 g of 1,10-phenanthroline monohydratein 5 mL of HCl in a 600-mL beaker. Add 215 mL ofCH3COOH, and, while cooling, carefully add 265 mL ofNH4OH. Cool
26、 to room temperature. Using a pH meter, checkthe pH; if it is not between 6.0 and 6.5, adjust it to that rangeby adding acetic acid or NH4OH as required. Dilute to 500 mL.17. Preparation of Calibration Curve17.1 Calibration Solutions:17.1.1 Using pipets, transfer (1, 2, 5, 10, 15, and 20) mL ofiron
27、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 allowto stand 1 min. Proceed as directed in 17.3.17.2 Reference SolutionTransfer 20 mL of water to a50-mL volumetric flask and proceed as directed in 17.1.2.17.3 Color Develop
28、mentAdd 5 mL of 1,10-phenanthroline-ammonium acetate buffer solution, dilute tovolume, and mix. Allow to stand at least 5 min but not morethan 4 h.4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC, www.chemistry.org. For suggestions on thetesting
29、of reagents not listed by the American Chemical Society, see the UnitedStates Pharmacopeia 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
30、, PracticeE1601)ManganeseCopper7 0.0137 0.0013 0.0028E581 10217.4 Photometry:17.4.1 Multiple-Cell PhotometerMeasure the cell correc-tion using absorption cells with a 2-cm light path and a lightband centered at approximately 510 nm. Using the test cell,take the photometric readings of the calibratio
31、n solutions.17.4.2 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 510 nm. While maintain-ing this adjustment, take the photometric rea
32、dings of thecalibration solutions.17.5 Calibration CurvePlot the net photometric readingsof the calibration solutions against milligrams of iron per50 mL of solution.18. Procedure18.1 Test Solution:18.1.1 Transfer a 2.0-g sample, weighed to the nearest10 mg, to a 400-mL beaker.18.1.2 Carry a reagent
33、 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 H2O2as neededto dissolve the alloy completely. When dissolution is complete,add 20 mL of HCl and heat carefully to decompose excessperoxide. Cool to room tem
34、perature, transfer to a 125-mLconical separatory funnel. Add HCl (1 + 1), as required, toadjust the volume to 50 mL.18.1.4 Add 20 mL of MIBK benzene mixture to theseparatory funnel and shake 1 min. Allow the phases toseparate, discard the aqueous phase, wash the organic phasethree times with 3-mL to
35、 5-mL portions of HCl (1 + 1) toremove copper, and discard the washings. Extract the iron fromthe organic phase by shaking vigorously 30 s with 10 mL ofNH2OHHCl solution. Transfer the aqueous phase to a 50-mLvolumetric flask. Repeat the extraction with a second 10-mLportion of NH2OHHCl solution, and
36、 transfer the extract to the50-mL flask. Dilute to 40 mL and proceed as directed in 18.3.18.2 Reference SolutionUse the reagent blank solutionprepared as directed in 18.1.2.18.3 Color DevelopmentProceed as directed in 17.3.18.4 PhotometryProceed as directed in 17.4.19. Calculation19.1 Convert the ne
37、t photometric reading of the test solutionto milligrams of iron by means of the calibration curve.Calculate the percentage of iron as follows:Iron, % 5 A/B 3 10! (1)where:A = milligrams of iron found in 50 mL of the final testsolution, andB = grams of sample represented in 50 mL of the final testsol
38、ution.20. Precision and Bias20.1 PrecisionSeven laboratories cooperated in testingthis test method and obtained the precision data shown in Table1, which were calculated in accordance with Practice E1601.Although samples covered by this test method with ironconcentrations near the lower limit of the
39、 scope were notavailable for testing, the precision data obtained should apply.20.2 BiasThe accuracy of this test method could not beevaluated because adequate certified standard reference mate-rials were unavailable at the time of testing. The user isencouraged to verify by the use of certified ref
40、erence materials,if available, that the accuracy of this test method is adequatefor the contemplated use.MANGANESE BY THE(ETHYLENEDINITRILO)TETRAACETIC ACID(EDTA)BACK-TITRIMETRIC METHOD21. Scope21.1 This test method covers the determination of manga-nese in concentrations from 28.0 % to 32.0 %.22. S
41、ummary of Test Method22.1 The sample is dissolved in HNO3. Manganese ischelated with disodium (ethylenedinitrilo) tetraacetate(EDTA), which is added in excess. The pH of the solution isadjusted to 10 and sodium cyanide is added to complex copper.The manganese is then determined by back-titration wit
42、hstandard manganese solution.23. Interferences23.1 The elements ordinarily present do not interfere if theirconcentrations are under the maximum limits shown in 1.1.24. Reagents24.1 Buffer Solution (pH 10)Transfer 54 g of ammoniumchloride (NH4Cl) to a 1-L beaker, dissolve in 500 mL of water,add 350
43、mL of NH4OH, dilute to 1 L, and mix. Store in apolyethylene bottle.24.2 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 ofnitrogen. Cool, dilute to 100 mL, and mix.24.3 Disodium (Eth
44、ylenedinitrilo)tetraacetic Acid Dihy-drate (EDTA), Standard Solution (0.05 M)Dissolve18.6127 g of disodium (ethylenedinitrilo) tetraacetate dihy-drate in water, transfer to a 1-L volumetric flask, dilute tovolume, and mix. The solution is stable for several monthswhen stored in plastic or borosilica
45、te 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.Add 25 mL of buffer solution and dilute to about 250 mL. Addfour drops to six drops of eriochrome black-T indicatorsolution and titrate with EDTA standard solution
46、to the colorchange from magenta to blue. Calculate the molarity of theEDTA solution as follows:Molarity of EDTA solution, A 51.25B(2)where:A = molarity of EDTA solution, andE581 103B = millilitres of EDTA solution required to titrate 25 mLof zinc standard solution (0.050 M).24.4 Eriochrome Black-T I
47、ndicator Solution (8 g/L)Dissolve 0.4 g of the sodium salt of eriochrome black-T in amixture of 20 mL of ethanol and 30 mL of triethanolamine.This solution is stable for at least three months when kept in atightly closed plastic dropping bottle.24.5 Hydroxylamine Hydrochloride Solution (100 g/L)Diss
48、olve 5.0 g of hydroxylamine hydrochloride (NH2OH HCl) in 50 mL of water. Prepare fresh as needed.24.6 Manganese, Standard Solution (0.05 M)Pretreatmanganese metal (purity, 99.8% min) (Note 2) as follows:Wash in H2SO3, rinse with water, and dry. Store in a coveredglass beaker in a desiccator. Transfe
49、r 2.7470 g, weighed to thenearest 0.1 mg (do not use small particles of metal) to a150-mL beaker, and cover. Add 10 mL of HNO3(1 + 1). Heatgently until dissolution is complete and brown fumes areexpelled. Cool, transfer to a 1-L volumetric flask, dilute tovolume, and mix.NOTE 2For the analysis of high-manganese materials, the manganesemetal must be assayed. This would include the determination of oxygen aswell as all metallics.24.6.1 Standardize as follows: Using a pipet, transfer 25 mLof the manganese solution to a 400-mL beaker. Add 1
