ASTM E581-17A(2022)e1
(Test Method)Standard Test Methods for Chemical Analysis of Manganese-Copper Alloys
Standard Test Methods for Chemical Analysis of Manganese-Copper Alloys
SIGNIFICANCE AND USE
4.1 These test methods for the chemical analysis of metals and alloys are primarily intended to test such materials for compliance with compositional specifications. It is assumed that all who use these test methods will be trained analysts capable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properly equipped laboratory.
SCOPE
1.1 These test methods cover the chemical analysis of manganese-copper alloys having chemical compositions within the following limits:
Element
Range, %
Copper
68.0 to 72.0
Manganese
28.0 to 32.0
Carbon
0.03 max
Iron
0.01 max
Phosphorus
0.01 max
Silicon
0.05 max
Sulfur
0.01 max
1.2 The test methods appear in the following order:
Sections
Iron by the 1,10-Phenanthroline
Spectrophotometric Method
[0.003 % to 0.02 %]
11 – 20
Manganese by the (Ethylenedinitrilo)
Tetraacetic Acid (EDTA)—
Back-Titrimetric Method [28 % to 32 %]
21 – 27
Phosphorus by the
Molybdivanadophosphoric Acid
Extraction Spectrophotometric Method
[0.002 % to 0.014 %]
28 – 38
1.3 Units—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 use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.5 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
General Information
Relations
Standards Content (Sample)
This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
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Designation: E581 − 17a (Reapproved 2022)
Standard Test Methods for
Chemical Analysis of Manganese-Copper Alloys
This standard is issued under the fixed designation E581; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
ε NOTE—Editorial changes were made throughout in September 2022.
1. Scope 2. Referenced Documents
1.1 These test methods cover the chemical analysis of
2.1 ASTM Standards:
manganese-copper alloys having chemical compositions
D1193 Specification for Reagent Water
within the following limits:
E29 Practice for Using Significant Digits in Test Data to
Determine Conformance with Specifications
Element Range, %
Copper 68.0 to 72.0
E50 Practices for Apparatus, Reagents, and Safety Consid-
Manganese 28.0 to 32.0
erations for Chemical Analysis of Metals, Ores, and
Carbon 0.03 max
Related Materials
Iron 0.01 max
Phosphorus 0.01 max
E55 Practice for Sampling Wrought Nonferrous Metals and
Silicon 0.05 max
Alloys for Determination of Chemical Composition
Sulfur 0.01 max
E60 Practice for Analysis of Metals, Ores, and Related
1.2 The test methods appear in the following order:
Materials by Spectrophotometry
Sections
E88 Practice for Sampling Nonferrous Metals and Alloys in
Iron by the 1,10-Phenanthroline 11–20
Cast Form for Determination of Chemical Composition
Spectrophotometric Method
[0.003 % to 0.02 %] E135 Terminology Relating to Analytical Chemistry for
Manganese by the (Ethylenedinitrilo)
Metals, Ores, and Related Materials
Tetraacetic Acid (EDTA)— 21–27
E173 Practice for Conducting Interlaboratory Studies of
Back-Titrimetric Method [28 % to 32 %]
Phosphorus by the
Methods for Chemical Analysis of Metals (Withdrawn
Molybdivanadophosphoric Acid 28–38 3
1997)
Extraction Spectrophotometric Method
E1601 Practice for Conducting an Interlaboratory Study to
[0.002 % to 0.014 %]
Evaluate the Performance of an Analytical Method
1.3 Units—The values stated in SI units are to be regarded
as standard. No other units of measurement are included in this
3. Terminology
standard.
3.1 Definitions—For definitions of terms used in this test
1.4 This standard does not purport to address all of the
method, refer to Terminology E135.
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
4. Significance and Use
priate safety, health, and environmental practices and deter-
mine the applicability of regulatory limitations prior to use.
4.1 These test methods for the chemical analysis of metals
1.5 This international standard was developed in accor-
and alloys are primarily intended to test such materials for
dance with internationally recognized principles on standard-
compliance with compositional specifications. It is assumed
ization established in the Decision on Principles for the
that all who use these test methods will be trained analysts
Development of International Standards, Guides and Recom-
capable of performing common laboratory procedures skill-
mendations issued by the World Trade Organization Technical
fully and safely. It is expected that work will be performed in
Barriers to Trade (TBT) Committee.
a properly equipped laboratory.
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct For referenced ASTM standards, visit the ASTM website, www.astm.org, or
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, Precious Metals, contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
their Alloys, and Related Metals. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved Aug. 1, 2022. Published September 2022. Originally the ASTM website.
approved in 1976. Last previous edition approved in 2017 as E581 – 17a. DOI: The last approved version of this historical standard is referenced on
10.1520/E0581-17AR22E01. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
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E581 − 17a (2022)
5. Apparatus IRON BY THE 1,10-PHENANTHROLINE
SPECTROPHOTOMETRIC METHOD
5.1 Spectrophotometers shall conform to the requirements
prescribed in Practice E60.
11. Scope
11.1 This test method covers the determination of iron from
6. Reagents and Materials
0.003 % to 0.02 %.
6.1 Reagents required for each determination are listed in
separate sections of each test method. The standard solutions 12. Summary of Test Method
and certain other reagents used in more than one procedure
12.1 The sample is dissolved in HCl and hydrogen
shall conform to the requirements prescribed in Practices E50.
peroxide, and the excess oxidant removed by evaporation. The
6.2 Purity of Reagents—Reagent grade chemicals shall be iron is extracted with methyl isobutyl ketone-benzene mixture.
used in all tests. Unless otherwise indicated, all reagents shall The iron is extracted from the organic phase into a hydrox-
conform to the specifications of the Committee on Analytical ylamine hydrochloride solution and the red-colored 1,10-
Reagents of the American Chemical Society where such phenanthroline complex is formed. Spectrophotometric absor-
specifications are available. Other grades may be used, pro- bance measurement is made at 510 nm.
vided it is first ascertained that the reagent is of sufficiently
13. Iron Range
high purity to permit its use without lessening the accuracy of
13.1 Therecommendedrangeisfrom0.005 mgto0.125 mg
the determination.
of iron per 50 mL of solution using a 2 cm cell.
6.3 Purity of Water—Unless otherwise indicated, references
to water shall be understood to mean reagent water as defined NOTE1—Thistestmethodhasbeenwrittenforcellshavinga2 cmlight
path. Cells having other dimensions may be used, provided suitable
by Type I of Specification D1193.
adjustments can be made in the amounts of sample and reagents used.
7. Hazards
14. Stability of Color
7.1 For precautions to be observed in this method, refer to
14.1 The color develops within 5 min and is stable for at
Practices E50.
least 4 h.
7.2 A warning statement is given in 24.7.
15. Interferences
8. Sampling
15.1 Elements ordinarily present do not interfere if their
percentages are under the maximum limits shown in 1.1.
8.1 For procedures for sampling the material, refer to
Practices E55 and E88.
16. Reagents
16.1 Hydroxylamine Hydrochloride Solution (10 g/L)—
9. Rounding Calculated Values
Dissolve 5.0 g of hydroxylamine hydrochloride (NH OH·HCl)
9.1 Rounding of test results obtained using this test method
in 500 mL of water. Prepare fresh as needed.
shall be performed as directed in Practice E29, Rounding
16.2 Iron, Standard Solution A (1 mL = 0.125 mg Fe)—
Method, unless an alternative rounding method is specified by
Transfer 0.1250 g of iron (purity: 99.9 % min) to a 100 mL
the customer or applicable material specification.
beaker.Add 10 mLof HCl (1 + 1) and 1 mLof bromine water.
10. Interlaboratory Studies
Boil gently until the excess bromine is removed.Add 20 mLof
HCl, cool, transfer to a 1 L volumetric flask, dilute to volume,
10.1 These test methods have been evaluated in accordance
and mix.
with Practice E173, unless otherwise noted in the precision
section. The Reproducibility R of Practice E173 corresponds 16.3 Iron, Standard Solution B (1 mL = 0.00625 mg Fe)—
to the Reproducibility Index R of Practice E1601. The Repeat-
Using a pipet, transfer 50 mL of iron solution A
ability R of Practice E173 corresponds to the Repeatability (1 mL = 0.125 mg Fe) to a 1 L volumetric flask, dilute to
Index r of Practice E1601.
volume with HCl (1 + 49), and mix.
16.4 Methyl Isobutyl Ketone-Benzene Mixture—Mix
200 mL of methyl isobutyl ketone (MIBK) and 100 mL of
Reagent Chemicals, American Chemical Society Specifications, American benzene.
Chemical Society, Washington, DC, www.acs.org. For suggestions on the testing of
16.5 1,10-Phenanthroline-Ammonium Acetate Buffer
reagents not listed by the American Chemical Society, see the United States
Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. Solution—Dissolve 1.0 g of 1,10-phenanthroline monohydrate
(USPC), Rockville, MD, http://www.usp.org.
in 5 mLof HCl in a 600 mLbeaker.Add 215 mLof acetic acid
(CH COOH), and, while cooling, carefully add 265 mL of
TABLE 1 Statistical Information
NH OH. Cool to room temperature. Using a pH meter, check
Iron Found, % Repeatability Reproducibility
the pH; if it is not between 6.0 and 6.5, adjust it to that range
Test Sample Labs (r, Practice (R, Practice
byaddingaceticacidorNH OHasrequired.Diluteto500 mL.
E1601) E1601)
Manganese 7 0.0137 0.0013 0.0028
17. Preparation of Calibration Curve
Copper
17.1 Calibration Solutions:
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E581 − 17a (2022)
17.1.1 Using pipet, transfer (1, 2, 5, 10, 15, and 20) mL of 19. Calculation
iron solution B (1 mL = 0.00625 mg Fe) to 50 mL volumetric
19.1 Convertthenetspectrophotometricabsorbancereading
flasks. Dilute to 20 mL.
of the test solution to milligrams of iron by means of the
17.1.2 Add 20 mL of NH OH·HCl solution, mix, and allow
calibration curve. Calculate the percentage of iron as follows:
to stand 1 min. Proceed as directed in 17.3.
Iron,% 5 A/ B 310 (1)
~ !
17.2 Reference Solution—Transfer 20 mL of water to a
where:
50 mL volumetric flask and proceed as directed in 17.1.2.
A = milligrams of iron found in 50 mL of the final test
17.3 Color Development—Add 5 mL of 1,10-
solution, and
phenanthroline-ammonium acetate buffer solution, dilute to
B = grams of sample represented in 50 mL of the final test
volume, and mix. Allow to stand at least 5 min but not more
solution.
than 4 h.
20. Precision and Bias
17.4 Spectrophotometry:
20.1 Precision—Seven laboratories cooperated in testing
17.4.1 Multiple-Cell Spectrophotometer—Measure the cell
thistestmethodandobtainedtheprecisiondatashowninTable
correction using absorption cells with a 2 cm light path and a
1, which were calculated in accordance with Practice E1601.
light band centered at 510 nm. Using the test cell, take the
Although samples covered by this test method with iron
spectrophotometric absorbance readings of the calibration
percentagesnearthelowerlimitofthescopewerenotavailable
solutions.
for testing, the precision data obtained should apply.
17.4.2 Single-Cell Spectrophotometer—Transfer a suitable
portion of the reference solution to an absorption cell with a 20.2 Bias—The accuracy of this test method could not be
2 cm light path and adjust the spectrophotometer to the initial evaluated because adequate certified standard reference mate-
rials were unavailable at the time of testing. The user is
setting, using a light band centered at 510 nm. While main-
taining this adjustment, take the spectrophotometric absor- encouragedtoverifybytheuseofcertifiedreferencematerials,
if available, that the accuracy of this test method is adequate
bance readings of the calibration solutions.
for the contemplated use.
17.5 Calibration Curve—Plot the net spectrophotometric
absorbance readings of the calibration solutions against milli-
MANGANESE BY THE
grams of iron per 50 mL of solution.
(ETHYLENEDINITRILO)TETRAACETIC ACID
(EDTA)—BACK-TITRIMETRIC METHOD
18. Procedure
21. Scope
18.1 Test Solution:
21.1 This test method covers the determination of manga-
18.1.1 Transfer a 2.0 g sample, weighed to the nearest
nese from 28.0 % to 32.0 %.
10 mg, to a 400 mL beaker.
18.1.2 Process a reagent blank through the entire procedure,
22. Summary of Test Method
using the same amounts of all reagents but with the sample
22.1 The sample is dissolved in HNO . Manganese is
omitted.
chelated with disodium (ethylenedinitrilo) tetraacetate
18.1.3 Add 25 mL of HCl (7 + 3) and then H O as needed
2 2
(EDTA), which is added in excess. The pH of the solution is
to dissolve the alloy completely.When dissolution is complete,
adjusted to 10 and sodium cyanide is added to complex copper.
add 20 mL of HCl and heat carefully to decompose excess
The manganese is then determined by back-titration with
H O . Cool to room temperature, transfer to a 125 mL conical
2 2
standard manganese solution.
separatory funnel. Add HCl (1 + 1), as required, to adjust the
volume to 50 mL.
23. Interferences
18.1.4 Add 20 mL of MIBK – benzene mixture to the
23.1 The elements ordinarily present do not interfere if their
separatory funnel and shake 1 min. Allow the phases to
percentages are under the maximum limits shown in 1.1.
separate, discard the aqueous phase, wash the organic phase
three times with 3 mL to 5 mL portions of HCl (1 + 1) to
24. Reagents
removecopper,anddiscardthewashings.Extracttheironfrom
24.1 Buffer Solution (pH 10)—Transfer 54 g of ammonium
the organic phase by shaking vigorously 30 s with 10 mL of
chloride (NH Cl) to a 1 Lbeaker, dissolve in 500 mLof water,
NH OH·HCl solution. Transfer the aqueous phase to a 50 mL 4
add 350 mL of NH OH, dilute to 1 L, and mix. Store in a
volumetric flask. Repeat the extraction with a second 10 mL
polyethylene bottle.
portion of NH OH·HCl solution, and transfer the extract to the
50 mL flask. Dilute to 40 mL and proceed as directed in 18.3.
24.2 Copper Solution (25 g/L)—Transfer 2.50 g of copper
(purity: 99.9 % min) to a 250 mLbeaker.Add 20 mLof HNO
18.2 Reference Solution—Use the reagent blank solution
(1 + 1). When dissolution is complete, boil to expel oxides of
prepared as directed in 18.1.2.
nitrogen. Cool, dilute to 100 mL, and mix.
18.3 Color Development—Proceed as directed in 17.3.
24.3 Disodium (Ethylenedinitrilo)tetraacetic Acid Dihy-
18.4 Spectrophotometry—Proceed as directed in 17.4. drate (EDTA), Standard Solution (0.05 M)—Dissolve
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E581 − 17a (2022)
18.6127 g of disodium (ethylenedinitrilo) tetraacetate dihy- 24.9 Sulfurous Acid (H SO ).
2 3
drate in water, transfer to a 1 L volumetric flask, dilute to
24.10 Zinc, Standard Solution (0.050 M)—Transfer
volume, and mix. The solution is stable for several months
3.2690 g of zinc (purity: 99.9 % min) to a 400 mL beaker, and
when stored in plastic or borosilicate glass bottles.
cover.Add 25 mL of HNO (1 + 1) and warm gently until the
24.3.1 Standardize the solution as follows: Using a pipet,
zinc is dissolved. Boil to expel oxides of nitrogen. Cool,
transfer 25 mL of zinc solution (0.050 M)
...
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