1、Designation: E 352 93 (Reapproved 2006)Standard Test Methods forChemical Analysis of Tool Steels and Other Similar Medium-and High-Alloy Steels1This standard is issued under the fixed designation E 352; the number immediately following the designation indicates the year oforiginal adoption or, in th
2、e case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods2cover the chemical analysis of toolsteels and other similar medium
3、- and high-alloy steels havingchemical compositions within the following limits:Element Concentration Range, %Aluminum 0.005 to 1.5Boron 0.001 to 0.10Carbon 0.03 to 2.50Chromium 0.10 to 14.0Cobalt 0.10 to 14.0Copper 0.01 to 2.0Lead 0.001 to 0.01Manganese 0.10 to 15.00Molybdenum 0.01 to 10.00Nickel 0
4、.02 to 4.00Nitrogen 0.001 to 0.20Phosphorus 0.002 to 0.05Silicon 0.10 to 2.50Sulfur 0.002 to 0.40Tungsten 0.01 to 21.00Vanadium 0.02 to 5.501.2 The test methods in this standard are contained in thesections indicated below:SectionsCarbon, Total, by the CombustionThermalConductivity Method2aCarbon, T
5、otal, by the Combustion GravimetricalMethod (0.05 to 2.50 %) 78Chromium by the Atomic Absorption Method (0.006 to 1.00 %) 174Chromium by the Peroxydisulfate OxidationTitration Method (0.10 to 14.00 %) 184Chromium by the Peroxydisulfate-OxidationTitrimetric Method2bCobalt by the Ion-ExchangePotentiom
6、etricTitration Method (2 to 14 %) 52Cobalt by the Nitroso-R-Salt PhotometricMethod (0.10 to 5.0 %) 60SectionsCopper by the Neocuproine Photometric Method (0.01 to 2.00 %) 89Copper by the Sulfide Precipitation-Electrodeposition Gravimetric Method (0.01 to 2.0 %) 70Lead by the Ion-ExchangeAtomic Absor
7、ptionMethod (0.001 to 0.001 %) 99Nickel by the Dimethylglyoxime GravimetricMethod (0.1 to 4.0 %) 144Manganese by the Periodate PhotometricMethod (0.10 to 5.00 %) 8Molybdenum by the Ion Exchange8-Hydro-xyquinoline Gravimetric Method 203Molybdenum by the Photometric Method (0.01 to 1.50 %) 162Phosphor
8、us by the Alkalimetric Method (0.01 to 0.05 %) 136Phosphorus by the Molybdenum Blue Photo-metric Method (0.002 to 0.05 %) 18Silicon by the Gravimetric Method (0.10 to 2.50 %) 45Sulfur by the Gravimetric Method2cSulfur by the Combustion-Iodate TitrationMethod (0.005 to 0.4 %) 36Sulfur by the Chromato
9、graphic GravimetricMethod2bTin by the Solvent ExtractionAtomic Absorp-tion Method (0.002 to 0.10 %) 152Vanadium by the Atomic Absorption Method (0.006 to 0.15 %) 1931.3 Test methods for the determination of several elementsnot included in this standard can be found in Test Methods E30and Test Method
10、s E 1019.1.4 Some of the concentration ranges given in 1.1 are toobroad to be covered by a single test method and therefore thisstandard contains multiple test methods for some elements.The user must select the proper test method by matching theinformation given in the Scope and Interference section
11、s ofeach test method with the composition of the alloy to beanalyzed.1.5 The values stated in SI units are to be regarded asstandard. In some cases, exceptions allowed in Practice E 380are also used.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its
12、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. Specific hazards1These test methods are under the jurisdiction of the ASTM Committee E01 onAnalytical Chemistry for
13、 Metals, Ores, and Related Materials and are the directresponsibility of Subcommittee E01.01 on Iron, Steel, and Ferroalloys.Current edition approved June 1, 2006. Published June 2006. Originallyapproved in 1968. Last previous edition approved in 2000 as E 352 93 (2000)e1.2These test methods represe
14、nt revisions of methods covered by ASTM E 30,which appear in this publication. Typical alloy specification numbers for thiscategory are listed in the Appendix.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.statements are given in Se
15、ction 5 and in special “Warning”paragraphs throughout these test methods.2. Referenced Documents2.1 ASTM Standards:3D 1193 Specification for Reagent WaterE29 Practice for Using Significant Digits in Test Data toDetermine Conformance with SpecificationsE30 Test Methods for Chemical Analysis of Steel,
16、 CastIron, Open-Hearth Iron, and Wrought Iron4E50 Practices for Apparatus, Reagents, and Safety Consid-erations for Chemical Analysis of Metals, Ores, andRelated MaterialsE60 Practice for Analysis of Metals, Ores, and RelatedMaterials by Molecular Absorption SpectrometryE 173 Practice for Conducting
17、 Interlaboratory Studies ofMethods for Chemical Analysis of Metals4E 350 Test Methods for ChemicalAnalysis of Carbon Steel,Low-Alloy Steel, Silicon Electrical Steel, Ingot Iron, andWrought IronE 351 Test Methods for Chemical Analysis of Cast IronAll TypesE 353 Test Methods for Chemical Analysis of S
18、tainless,Heat-Resisting, Maraging, and Other Similar Chromium-Nickel-Iron AlloysE 380 Practice for Use of the International System of Units(SI) (the Modernized Metric System)4E 882 Guide for Accountability and Quality Control in theChemical Analysis LaboratoryE 1019 Test Methods for Determination of
19、 Carbon, Sulfur,Nitrogen, and Oxygen in Steel and in Iron, Nickel, andCobalt AlloysE 1024 Guide for Chemical Analysis of Metals and MetalBearing Ores by Flame Atomic Absorption Spectropho-tometry5E 1806 Practice for Sampling Steel and Iron for Determi-nation of Chemical Composition2.2 Other Document
20、:ISO 5725 Precision of Test MethodsDetermination ofRepeatability and Reproducibility for Inter-LaboratoryTests63. Significance and Use3.1 These test methods for the chemical analysis of metalsand alloys are primarily intended as referee methods to testsuch materials for compliance with compositional
21、 specifica-tions particularly those under the jurisdiction of ASTM Com-mittee A1 on Steel, Stainless Steel, and Related Alloys. It isassumed that all who use these test methods will be trainedanalysts capable of performing common laboratory proceduresskillfully and safely. It is expected that work w
22、ill be performedin a properly equipped laboratory under appropriate qualitycontrol practices such as those described in Guide E 882.4. Apparatus, Reagents, and Instrumental Practices4.1 ApparatusSpecialized apparatus requirements arelisted in the “Apparatus” Section in each method. In somecases refe
23、rence may be made to Practices E50.4.2 Reagents:4.2.1 Purity of ReagentsUnless otherwise indicated, allreagents used in these test methods shall conform to the“Reagent Grade” Specifications of the American ChemicalSociety.7Other chemicals may be used, provided it is firstascertained that they are of
24、 sufficiently high purity to permittheir use without adversely affecting the expected performanceof the determination, as indicated in the section on “Precisionand Bias.”4.2.2 Purity of WaterUnless otherwise indicated, refer-ences to water shall be understood to mean reagent water asdefined by Type
25、II of Specification D 1193.4.3 Photometric PracticePhotometric practice prescribedin these test methods shall conform to Practice E60.5. Hazards5.1 For precautions to be observed in the use of certainreagents and equipment in these methods, refer to PracticesE50.6. Sampling6.1 For procedures for sam
26、pling the material, referenceshall be made to Practice E 1806.7. Interlaboratory Studies and Rounding CalculatedValues7.1 These test methods have been evaluated using PracticeE 173 or ISO 5725.7.2 Calculated values shall be rounded to the desired num-ber of places as directed in 3.4 to 3.6 of Practi
27、ce E29.MANGANESE BY THE METAPERIODATEPHOTOMETRIC METHOD8. Scope8.1 This method covers the determination of manganese inconcentrations from 0.10 to 5.00 %.9. Summary of Method9.1 Manganous ions are oxidized to permanganate ions bytreatment with periodate. Tungsten when present at concentra-tions grea
28、ter than 0.5 % is kept in solution with phosphoricacid. Solutions of the samples are fumed with perchloric acid3For 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 s
29、tandards Document Summary page onthe ASTM website.4Withdrawn.5Withdrawn.6Available from American National Standards Institute, 11 West 42nd Street,13th Floor, New York, NY 100367“Reagent Chemicals, American Chemical Society Specifications,” Am. Chemi-cal Soc., Washington, DC. For suggestions on the
30、testing of Reagents not listed bytheAmerican Chemical Society, see“ Reagent Chemicals and Standards,” by JosephRosin, D. Van Nostrand Co., Inc., New York, NY, and the “United StatesPharmacopeia.” United States Pharmacopeial Convention, Rockville, MD 20852.E 352 93 (2006)2so that the effect of period
31、ate is limited to the oxidation ofmanganese. Photometric measurement is made at approxi-mately 545 nm.10. Concentration Range10.1 The recommended concentration range is 0.15 to 0.8mg of manganese per 50 mL of solution, using a 1-cm cell(Note 1) and a spectrophotometer with a band width of 10 nmor le
32、ss.NOTE 1This method has been written for cells having a 1-cm lightpath and a “narrow-band” instrument. The concentration range dependsupon band width and spectral region used as well as cell optical pathlength. Cells having other dimensions may be used, provided suitableadjustments can be made in t
33、he amounts of sample and reagents used.11. Stability of Color11.1 The color is stable for at least 24 h.12. Interferences12.1 Perchloric acid treatment, which is used in the proce-dure, yields solutions which can be highly colored due to thepresence of Cr (VI) ions.Although these ions and other colo
34、redions in the sample solution undergo no further change in colorquality upon treatment with metaperiodate ion, the followingprecautions must be observed when filter photometers are used:Select a filter with maximum transmittance between 545 and565 nm. The filter must transmit not more than 5 % of i
35、tsmaximum at a wavelength shorter than 530 nm. The bandwidth of the filter should be less than 30 nm when measured at50 % of its maximum transmittance. Similar restrictions applywith respect to the wavelength region employed when other“wide-band” instruments are used.12.2 The spectral transmittance
36、curve of permanganate ionsexhibits two useful minima, one at approximately 526 nm, andthe other at 545 nm. The latter is recommended when a“narrow-band” spectrophotometer is used.12.3 Tungsten, when present in amounts of more than 0.5 %interferes by producing a turbidity in the final solution. Aspec
37、ial procedure is provided for use with samples containingmore than 0.5 % tungsten which eliminates the problem bypreventing the precipitation of the tungsten.13. Reagents13.1 Manganese, Standard Solution (1 mL = 0.032 mgMn)Transfer the equivalent of 0.4000 g of assayed, high-purity manganese (purity
38、: 99.99 % minimum), to a 500-mLvolumetric flask and dissolve in 20 mL of HNO3by heating.Cool, dilute to volume, and mix. Using a pipet, transfer 20 mLto a 500-mL volumetric flask, dilute to volume, and mix.13.2 Nitric-Phosphoric Acid Mixture Cautiously, whilestirring, add 100 mL of HNO3and 400 mL of
39、 H3PO4to 400mL of water. Cool, dilute to 1 L, and mix. Prepare fresh asneeded.13.3 Potassium Metaperiodate Solution (7.5 g/L)Dissolve 7.5 g of potassium metaperiodate (KIO4) in 200 mLof hot HNO3(1 + 1), add 400 mL of H3PO4, cool, dilute to 1 L,and mix.13.4 Water, Pretreated with MetaperiodateAdd 20
40、mL ofKIO4solution to 1 L of water, mix, heat at not less than 90Cfor 20 to 30 min, and cool. Use this water to dilute solutions tovolume that have been treated with KIO4solution to oxidizemanganese, and thus avoid reduction of permanganate ions byany reducing agents in the untreated water. CautionAv
41、oidthe use of this water for other purposes.14. Preparation of Calibration Curve14.1 Calibration SolutionsUsing pipets, transfer 5, 10,15, 20, and 25 mL of manganese standard solution (1mL = 0.032 mg Mn) to 50-mL borosilicate glass volumetricflasks, and, if necessary, dilute to approximately 25 mL.P
42、roceed as directed in 14.3.14.2 Reference SolutionTransfer approximately 25 mL ofwater to a 50-mL borosilicate glass volumetric flask. Proceedas directed in 14.3.14.3 Color DevelopmentAdd 10 mL of KIO4solution,and heat the solutions at not less than 90C for 20 to 30 min(Note 2). Cool, dilute to volu
43、me with pretreated water, andmix.NOTE 2Immersing the flasks in a boiling water bath is a preferredmeans of heating them for the specified period to ensure complete colordevelopment.14.4 Photometry:14.4.1 Multiple-Cell PhotometerMeasure the cell correc-tion using the Reference Solution (14.2) in abso
44、rption cellswith a 1-cm light path and using a light band centered atapproximately 545 nm. Using the test cell, take the photometricreadings of the calibration solutions versus the ReferenceSolution (14.2)14.4.2 Single-Cell PhotometerTransfer a suitable portionof the Reference Solution (14.2) to an
45、absorption cell with a1-cm light path and adjust the photometer to the initial setting,using a light band centered at approximately 545 nm. Whilemaintaining this adjustment, take the photometric readings ofthe calibration solutions.14.5 Calibration CurvePlot the net photometric readingsof the calibr
46、ation solutions against milligrams of manganeseper 50 mL of solution.15. Procedure15.1 Test SolutionsSelect and weigh a sample in accor-dance with the following:Manganese, %SampleWeight, gTolerance inSampleWeight, mgDilu-tion,mLAliquotVolume,mL0.10 to 0.5 0.80 0.5 100 200.45 to 1.0 0.35 0.3 100 200.
47、85 to 2.0 0.80 0.5 500 200.95 to 5.0 0.80 0.5 500 10Transfer it to a 300-mL Erlenmeyer flask.15.1.1 For Samples Containing Not More Than 0.5 %Tungsten:15.1.1.1 To dissolve samples that do not require HF, add 8to 10 mL of HCl (1+1), and heat. Add HNO3as needed tohasten dissolution, and then add 3 to
48、4 mL in excess. Whendissolution is complete, cool, then add 10 mL of HClO4;evaporate to fumes to oxidize chromium, if present, and toexpel HCl. Continue fuming until salts begin to separate. Cool,add 50 mL of water, and digest if necessary to dissolve theE 352 93 (2006)3salts. Cool and transfer the
49、solution to either a 100- or 500-mLvolumetric flask as indicated in 15.1. Proceed to 15.1.3.15.1.1.2 For samples whose dissolution is hastened by HF,add 8 to 10 mL of HCl (1+1), and heat. Add HNO3and a fewdrops of HF as needed to hasten dissolution, and then add 3 to4mLofHNO3. When dissolution is complete, cool, then add10 mL or HClO4, evaporate to fumes to oxidize chromium, ifpresent, and to expel HCl. Continue fuming until salts begin toseparate. Cool, add 50 mL of water, digest if necessary todissolve the salts, cool, and transfer the solution to eith
