1、Designation: E 581 04e1Standard Test Methods forChemical Analysis of Manganese-Copper Alloys1This standard is issued under the fixed designation E 581; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A nu
2、mber in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEEditorial changes were made throughout in July 2005.1. Scope1.1 These test methods cover the chemical analysis ofmanganese-copper alloys havin
3、g chemical compositionswithin the following limits:Element Concentration 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-PhenanthrolinePhotometri
4、c Method11-20Manganese by the (Ethylenedinitrilo)Tetraacetic Acid (EDTA)Back-Titrimetric Method21-27Phosphorus by theMolybdivanadophosphoric Acid ExtractionPhotometric Method28-381.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is therespon
5、sibility 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 ASTM Standards:2D 1193 Specification for Reagent WaterE29 Practice for Using Significant Digits in Test Data
6、toDetermine Conformance with SpecificationsE50 Practices for Apparatus, Reagents, and Safety Precau-tions for Chemical Analysis of MetalsE55 Practice for Sampling Wrought Nonferrous Metals andAlloys for Determination of Chemical CompositionE60 Practice for Photometric and SpectrophotometricMethods f
7、or Chemical Analysis of MetalsE88 Practice for Sampling Nonferrous Metals and Alloysin Cast Form for Determination of Chemical CompositionE 135 Terminology Relating to Analytical Chemistry forMetals, Ores, and Related MaterialsE 173 Practice for Conducting Interlaboratory Studies ofMethods for Chemi
8、cal Analysis of Metals3E 1601 Practice for Conducting an Interlaboratory Study toEvaluate the Performance of an Analytical Method3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology E 135.4. Significance and Use4.1 These test methods for the chemical an
9、alysis of metalsand alloys are primarily intended to test such materials forcompliance with compositional specifications. It is assumedthat all who use these test methods will be trained analystscapable of performing common laboratory procedures skill-fully and safely. It is expected that work will
10、be performed ina properly equipped laboratory.5. Apparatus5.1 Photometers shall conform to the requirements pre-scribed in Practice E60.6. Reagents and Materials6.1 Reagents required for each determination are listed inseparate sections of each test method. The standard solutionsand certain other re
11、agents used in more than one procedureshall conform to the requirements prescribed in Practices E50.6.2 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents conform to the specifications of the Committee on1These methods are
12、 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 July 9, 2004. Published July 2004. Originally approve
13、din 1976. Last previous edition approved in 1996 as E 58176 (1996).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM we
14、bsite.3Withdrawn.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Analytical Reagents of the American Chemical Society wheresuch specifications are available.4Other grades may be used,provided it is first ascertained that the reagent
15、is of sufficientlyhigh purity to permit its use 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 D 1193.7. Hazards7.1 For precautions to be observed in t
16、his method, refer toPractices E50.7.2 A warning statement is given in 24.7.8. Sampling8.1 For procedures for sampling the material, refer toPractices E55andE88.9. Rounding Calculated Values9.1 Calculated values shall be rounded to the desired num-ber of places as directed in Practice E29Rounding Met
17、hod.10. Interlaboratory Studies10.1 These test methods have been evaluated in accordancewith Practice E 173, unless otherwise noted in the precisionsection. The Reproducibility R2of Practice E 173 correspondsto the Reproducibility Index R of Practice E 1601. TheRepeatability R1of Practice E 173 corr
18、esponds to the Repeat-ability Index r of Practice E 1601.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 hydrochloric acid andhydrogen pero
19、xide, and the excess oxidant removed by evapo-ration. The iron is extracted with methyl isobutyl ketone-benzene mixture. The iron is extracted from the organic phaseinto a hydroxylamine hydrochloride solution and the red-colored 1,10-phenanthroline complex is formed. Photometricmeasurement is made a
20、t approximately 510 nm.13. Concentration Range13.1 The recommended concentration range is from 0.005to 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-cmlight path. Cells having other dimensions may be used, provided suitableadjus
21、tments 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 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
22、Hydroxylamine Hydrochloride Solution (10 g/L)Dissolve 5.0 g of 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
23、 bromine water.Boil gently until the excess bromine is removed. 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 = 0.125mg Fe) to a 1-L volumetric flask, dil
24、ute to volume with HCl(1 + 49), and mix.16.4 Methyl Isobutyl Ketone-Benzene MixtureMix 200mL of methyl isobutyl ketone (MIBK) and 100 mL of benzene.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 o
25、fCH3COOH, and, while cooling, carefully add 265 mL ofNH4OH. Cool 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
26、.1.1 Using pipets, transfer 1, 2, 5, 10, 15, and 20 mL ofiron 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 volumet
27、ric flask and proceed as directed in 17.1.2.17.3 Color DevelopmentAdd 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.17.4 Photometry:17.4.1 Multiple-Cell PhotometerMeasure the cell correc-tion using absorptio
28、n 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 calibration solutions.17.4.2 Single-Cell PhotometerTransfer a suitable portionof the reference solution to an absorption cell with a 2-cm light4Reagent Chemical,
29、American Chemical Society Specifications , AmericanChemical Society, Washington, DC, www.chemistry.org. For suggestions on thetesting of reagents not listed by the American Chemical Society, see the UnitedStates Pharmacopeia and National Formulary, U.S. Pharmaceutical Convention,Inc., (USPC), Rockvi
30、lle, MD, www.usp.org.TABLE 1 Statistical InformationTest Sample LabsIron Found, % Repeatability(r, E 1601)Reproducibility(R, E 1601)ManganeseCopper7 0.0137 0.0013 0.0028E58104e12path and adjust the photometer to the initial setting, using alight band centered at approximately 510 nm. While maintain-
31、ing this adjustment, take the photometric readings of thecalibration solutions.17.5 Calibration CurvePlot the net photometric readingsof the calibration solutions against milligrams of iron per 50mL of solution.18. Procedure18.1 Test Solution:18.1.1 Transfer a 2.0-g sample, weighed to the nearest 10
32、mg, to a 400-mL beaker.18.1.2 Carry 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 H2O2as neededto dissolve the alloy completely. When dissolution is complete,add 20 mL of HCl and heat carefully
33、to decompose excessperoxide. Cool to room temperature, 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,
34、 wash the organic phase 3times with 3 to 5-mL portions of HCl (1 + 1) to remove copper,and discard the washings. Extract the iron from the organicphase by shaking vigorously 30 s with 10 mL of NH2OHHClsolution. Transfer the aqueous phase to a 50-mL volumetricflask. Repeat the extraction with a secon
35、d 10-mL portion ofNH2OHHCl solution, and transfer the extract to the 50-mLflask. 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
36、 17.4.19. Calculation19.1 Convert the net 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 r
37、epresented in 50 mL of the final testsolution.20. Precision and Bias20.1 Seven laboratories cooperated in testing this testmethod and obtained the precision data shown in Table 1,which were calculated in accordance with Practice E 1601.Although samples covered by this test method with ironconcentrat
38、ions near the lower limit of the scope were notavailable for testing, the precision data obtained should apply.20.2 The accuracy of this test method could not be evalu-ated because adequate certified standard reference materialswere unavailable at the time of testing. The user is encouragedto verify
39、 by the use of certified reference materials, if available,that the accuracy of this test method is adequate for thecontemplated use.MANGANESE BY THE(ETHYLENEDINITRILO)TETRAACETIC ACID(EDTA)BACK-TITRIMETRIC METHOD21. Scope21.1 This test method covers the determination of manga-nese in concentrations
40、 from 28.0 to 32.0 %.22. Summary of Test Method22.1 The sample is dissolved in nitric acid. 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
41、 determined by back-titration withstandard 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, dis
42、solve in 500 mL of water,add 350 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 ofHNO3(1 + 1). When dissolution is complete, boil to expeloxides of nitrogen. Cool, dilute to 1
43、00 mL, and mix.24.3 Disodium (Ethylenedinitrilo)tetraacetic Acid Dihy-drate (EDTA), Standard Solution (0.05 M)Dissolve 18.6127g of disodium (ethylenedinitrilo) tetraacetate dihydrate inwater, transfer to a 1-L volumetric flask, dilute to volume, andmix. The solution is stable for several months when
44、 stored inplastic 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.Add 25 mL of buffer solution and dilute to about 250 mL. Add4 to 6 drops of eriochrome black-T indicator solution andtitrate with EDT
45、A standard solution to the color change frommagenta to blue. Calculate the molarity of the EDTA solutionas follows:Molarity of EDTA solution, A 51.25B(2)where:A = molarity of EDTA solution, andB = millilitres of EDTA solution required to titrate 25 mLof zinc standard solution (0.050 M).24.4 Eriochro
46、me Black-T Indicator 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 3 months when kept in atightly closed plastic dropping bottle.E58104e1324.5 Hydroxylamine Hydrochloride Solut
47、ion (100 g/L)Dissolve 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 de
48、siccator. Transfer 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 t
49、he 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 10 mL ofcopper solution. Proceed as directed in 25.2. Calculate theEDTA equivalent of the solution as follows:EDTA equivalent, mL EDTA/mLMn 5 30.00/25.00 3 C! (3)where:C = millilitres of manganese solution required for titrationof excess EDTA solution.24.7 Sodium Cyanide Solution (200 g/L)Dissolve
