ASTM E478-08(2017)
(Test Method)Standard Test Methods for Chemical Analysis of Copper Alloys
Standard Test Methods for Chemical Analysis of Copper Alloys
SIGNIFICANCE AND USE
4.1 These test methods for the chemical analysis of metals and alloys are primarily intended as referee methods to test such materials for compliance with composition specifications. It is assumed that all who use these 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 copper alloys having chemical ranges within the following limits:2
Element
Composition, %
Aluminum
12.0 max
Antimony
1.0 max
Arsenic
1.0 max
Cadmium
1.5 max
Cobalt
1.0 max
Copper
40.0 min
Iron
6.0 max
Lead
27.0 max
Manganese
6.0 max
Nickel
50.0 max
Phosphorus
1.0 max
Silicon
5.0 max
Sulfur
0.1 max
Tin
20.0 max
Zinc
50.0 max
1.2 The test methods appear in the following order:
Sections
Aluminum by the Carbamate Extraction-Ethyl-
enedinitrilotetraacetate Titrimetric Test Method [2 % to 12 %]
71 – 78
Copper by the Combined Electrodeposition Gravimetric and Oxalyldihydrazide Spectrophotometric Test Method [50 %, minimum]
10 – 18
Iron by the 1,10-Phenanthroline Spectrophotometric Test Method [0.003 % to 1.25 %]
19 – 28
Lead by Atomic Absorption Spectrometry [0.002 % to 15 %]
90 – 100
Lead by the Ethylenedinitrilotetraacetic Acid (EDTA) Titrimetric Test Method [2.0 % to 30.0 %]
29 – 36
Nickel by the Dimethylglyoxime Extraction Sprectophotometric Test Method [0.03 % to 5.0 %]
37 – 46
Nickel by the Dimethylglyoxime Gravimetric Test Method [4 % to 50 %]
55 – 62
Silver in Silver-Bearing Copper by Atomic Absorption Spectrometry [0.01 % to 0.12 %]
101 – 112
Tin by the Iodotimetric Titration Test Method [0.5 % to 20 %]
63 – 70
Tin by the Phenylfluorone Spectrophotometric Test Method [0.01 % to 1.0 %]
113 – 123
Zinc by Atomic Absorption Spectrometry [0.2 % to 2 %]
79 – 89
Zinc by the Ethylenedinitrilotetraacetic Acid (EDTA) Titrimetric Test Method [2 % to 40 %]
47 – 54
1.3 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 and health 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.
Designation: E478 − 08 (Reapproved 2017)
Standard Test Methods for
Chemical Analysis of Copper Alloys
This standard is issued under the fixed designation E478; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope
Tin by the Iodotimetric Titration Test Method
[0.5 % to 20 %] 63–70
1.1 These test methods cover the chemical analysis of
Tin by the Phenylfluorone Spectrophotometric
copper alloys having chemical ranges within the following Test Method [0.01 % to 1.0 %] 113 – 123
Zinc by Atomic Absorption Spectrometry [0.2 %
limits:
to 2 %] 79–89
Element Composition, % Zinc by the Ethylenedinitrilotetraacetic Acid
(EDTA) Titrimetric Test Method [2 % to 40 %] 47–54
Aluminum 12.0 max
1.3 The values stated in SI units are to be regarded as
Antimony 1.0 max
Arsenic 1.0 max standard. No other units of measurement are included in this
Cadmium 1.5 max
standard.
Cobalt 1.0 max
Copper 40.0 min 1.4 This standard does not purport to address all of the
Iron 6.0 max
safety concerns, if any, associated with its use. It is the
Lead 27.0 max
responsibility of the user of this standard to establish appro-
Manganese 6.0 max
Nickel 50.0 max priate safety and health practices and determine the applica-
Phosphorus 1.0 max
bility of regulatory limitations prior to use.
Silicon 5.0 max
1.5 This international standard was developed in accor-
Sulfur 0.1 max
Tin 20.0 max
dance with internationally recognized principles on standard-
Zinc 50.0 max
ization established in the Decision on Principles for the
1.2 The test methods appear in the following order:
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
Sections
Aluminum by the Carbamate Extraction-Ethyl-
Barriers to Trade (TBT) Committee.
enedinitrilotetraacetate Titrimetric Test
Method [2 % to 12 %] 71–78
2. Referenced Documents
Copper by the Combined Electrodeposition
Gravimetric and Oxalyldihydrazide Spectro-
2.1 ASTM Standards:
photometric Test Method [50 %, minimum] 10–18
Iron by the 1,10-Phenanthroline Spectrophoto- E29 Practice for Using Significant Digits in Test Data to
metric Test Method [0.003 % to 1.25 %] 19–28
Determine Conformance with Specifications
Lead by Atomic Absorption Spectrometry
E50 Practices for Apparatus, Reagents, and Safety Consid-
[0.002%to15%] 90 – 100
Lead by the Ethylenedinitrilotetraacetic Acid erations for Chemical Analysis of Metals, Ores, and
(EDTA) Titrimetric Test Method [2.0 % to
Related Materials
30.0 %] 29–36
E60 Practice for Analysis of Metals, Ores, and Related
Nickel by the Dimethylglyoxime Extraction
Sprectophotometric Test Method [0.03 % to
Materials by Spectrophotometry
5.0 %] 37–46
E135 Terminology Relating to Analytical Chemistry for
Nickel by the Dimethylglyoxime Gravimetric
Metals, Ores, and Related Materials
Test Method [4 % to 50 %] 55–62
Silver in Silver-Bearing Copper by Atomic Ab-
E173 Practice for Conducting Interlaboratory Studies of
sorption Spectrometry [0.01 % to 0.12 %] 101 – 112
Methods for Chemical Analysis of Metals (Withdrawn
1998)
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, Precious Metals, For referenced ASTM standards, visit the ASTM website, www.astm.org, or
their Alloys, and Related Metals. contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Current edition approved Jan. 15, 2017. Published March 2017. Originally Standards volume information, refer to the standard’s Document Summary page on
approved in 1973. Last previous edition approved in 2008 as E478 – 08. DOI: the ASTM website.
10.1520/E0478-08R17. The last approved version of this historical standard is referenced on
The actual limits of application of each test method are presented in 1.2. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E478 − 08 (2017)
E255 Practice for Sampling Copper and Copper Alloys for 10.2 This international standard was developed in accor-
the Determination of Chemical Composition dance with internationally recognized principles on standard-
E1601 Practice for Conducting an Interlaboratory Study to ization established in the Decision on Principles for the
Evaluate the Performance of an Analytical Method Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
3. Terminology
Barriers to Trade (TBT) Committee.
3.1 For definitions of terms used in these test methods, refer
11. Summary of Test Method
to Terminology E135.
11.1 After dissolution of the sample in HNO and HF, the
4. Significance and Use
oxidesofnitrogenarereducedwithhydrogenperoxide,andthe
4.1 These test methods for the chemical analysis of metals copper deposited electrolytically. Loss of platinum from the
anode is minimized by the addition of lead. The copper
and alloys are primarily intended as referee methods to test
such materials for compliance with composition specifications. oxalyldihydrazide complex is formed with the copper remain-
ing in the electrolyte. Photometric measurement is made at
It is assumed that all who use these methods will be trained
approximately 540 nm.
analysts capable of performing common laboratory procedures
skillfully and safely. It is expected that work will be performed
12. Interferences
in a properly equipped laboratory.
12.1 The elements ordinarily present do not interfere if their
5. Apparatus, Reagents, and Spectrophotometric Practice
concentrations are under the maximum limits shown in 1.1.
5.1 Apparatus, standard solutions, and other reagents re-
13. Apparatus
quired for each determination are listed in separate sections
preceding the procedure. Spectrophotometers shall conform to 13.1 Polytetrafluoroethylene or Polypropylene Beakers,
250-mL capacity.
the requirements prescribed in Practice E60.
5.2 Spectrophotometric practice prescribed in these test 13.2 PolytetrafluoroethyleneorPolypropyleneSplitCovers.
methods shall conform to Practice E60.
13.3 Electrodes for Electroanalysis—Recommended sta-
tionary type platinum electrodes are described in 13.3.1 and
6. Hazards
13.3.2. The surface of the platinum electrode should be
6.1 Specific hazard statements are given in 33.7, 51.13, and
smooth, clean, and bright to promote uniform deposition and
107.1.
good adherence. Deviations from the exact size and shape are
6.2 Forotherprecautionstobeobservedintheuseofcertain allowable. In instances where it is desirable to decrease the
time of deposition and agitation of the electrolyte is
reagents in these test methods, refer to Practices E50.
permissible, a generally available rotating type of electrode
7. Sampling
may be employed. Cleaning of the electrode by sandblasting is
not recommended.
7.1 For procedures for sampling the material, refer to
13.3.1 Cathodes—Platinum cathodes may be either open or
Practice E255. However, this practice does not supersede any
closed cylinders formed from sheets that are plain or
sampling requirements specified in a specific ASTM material
perforated, or from gauze. Gauze cathodes are recommended;
specification.
preferably from 50-mesh gauze woven from approximately
8. Rounding Calculated Values
0.21-mm diameter wire. The top and bottom of gauze cathodes
should be reinforced by doubling the gauze about 3 mm onto
8.1 Calculated values shall be rounded to the desired num-
itself, or by the use of platinum bands or rings. The cylinder
ber of places as directed in Practice E29.
should be approximately 30 mm in diameter and 50 mm in
9. Interlaboratory Studies
height. The stem should be made from a platinum alloy wire
such as platinum-iridium, platinum-rhodium, or platinum-
9.1 These test methods were evaluated in accordance with
ruthenium, having a diameter of approximately 1.3 mm. It
Practice E173 unless otherwise noted in the precision section.
should be flattened and welded the entire length of the gauze.
Practice E173 has been replaced by Practice E1601. The
The overall height of the cathode should be approximately
Reproducibility R corresponds to the Reproducibility Index R
130 mm. A cathode of these dimensions will have a surface
of Practice E1601. The Repeatability R of Practice E173
area of 135 cm exclusive of the stem.
corresponds to the Repeatability Index r of Practice E1601.
13.3.2 Anodes—Platinum anodes may be a spiral type when
COPPER BY THE COMBINED
anodic deposits are not being determined, or if the deposits are
ELECTRODEPOSITION GRAVIMETRIC AND small (as in the electrolytic determination of lead when it is
OXALYLDIHYDRAZIDE SPECTROPHOTOMETRIC
present in compositions below 0.2 %). Spiral anodes should be
TEST METHOD
made from 1.0 mm or larger platinum wire formed into a spiral
of seven turns having a height of approximately 50 mm and a
10. Scope
diameter of 12 mm with an overall height of approximately
10.1 This test method covers the determination of copper in 130 mm.Aspiralanodeofthesedimensionswillhaveasurface
compositions greater than 50 %. area of 9 cm . When both cathode and anode plates are to be
E478 − 08 (2017)
determined,theanodeshouldbemadeofthesamematerialand 17. Spectrophotometric Determination of the Residual
design as the electrode described in 13.3.1. The anode cylinder Copper in the Electrolyte
should be approximately 12 mm in diameter and 50 mm in
17.1 Interferences—The elements ordinarily present do not
height and the overall height of the anode should be approxi-
interfere if their composition is under the maximum limits
mately 130 mm. A gauze anode of these dimensions will have
shown in 1.1.
a surface area of 54 cm exclusive of the stem.
17.2 Concentration Range—The recommended concentra-
13.3.3 Gauze cathodes are recommended where rapid elec-
tion is from 0.0025 mg to 0.07 mg of copper per 50 mL of
trolysis is used.
solution, using a 2-cm cell.
14. Reagents
NOTE 1—This procedure has been written for cells having a 2-cm light
path. Cells having other dimensions may be used, provided suitable
14.1 Ammonium Chloride Solution (0.02 g⁄L)—Dissolve
adjustments can be made in the amounts of sample and reagents used.
0.02 g of ammonium chloride (NH Cl) in water and dilute to
17.3 Stability of Color—The color fully develops in 20 min
1L.
and is stable for 1 h.
14.2 Hydrogen Peroxide (3 %)—Dilute 100 mL of 30 %
17.4 Reagents:
hydrogen peroxide to 1 L.
17.4.1 Acetaldehyde Solution (40 %)—Dilute 400 mL of
14.3 Lead Nitrate Solution (10 g⁄L) —Dissolve 10.0 g of
acetaldehyde to 1 L with water.
lead nitrate (Pb(NO ) ) in water and dilute to 1 L.
3 2
17.4.2 BoricAcidSolution(50g⁄L)—Dissolve 50 g of boric
acid (H BO ) in hot water, cool, and dilute to 1 L.
3 3
15. Procedure
17.4.3 Citric Acid Solution (200g⁄L)—Dissolve 200 g of
15.1 Transfer a 2.000-g sample, weighed to the nearest
citric acid in water and dilute to 1 L.
0.1 mg, to a 250-mL polytetrafluoroethylene or polypropylene
17.4.4 Copper, Standard Solution A (1mL=1.0mg Cu)—
beaker, add 2 mL of HF, and 30 mL of HNO (1 + 1). Cover
Transfer a 1.000-g sample of electrolytic copper (purity:
withacoverglassandallowtostandforafewminutesuntilthe
99.9 % minimum) to a 250-mL beaker and add 10 mL of
reaction has nearly ceased. Warm but do not heat over 80 °C.
HNO (1 + 1). Evaporate nearly to dryness.Add 5 mLof water
When dissolution is complete, add 25 mL of 3 % H O and
2 2
to dissolve the residue. Transfer to a 1-L volumetric flask,
3 mLof Pb(NO ) solution. Rinse the cover glass and dilute to
3 2
dilute to volume, and mix.
approximately 150 mL with NH Cl solution.
17.4.5 Copper, Standard Solution B (1 mL = 0.010 mg
15.2 With the electrolyzing current off, position the anode
Cu)—Using a pipet, transfer 10 mL of Copper Solution A
and the accurately weighed cathode in the solution so that the
(1 mL = 1.0 mgCu)toa1-Lvolumetricflask,dilutetovolume,
gauze is completely immersed. Cover the beaker with a split
and mix.
plastic cover.
17.4.6 OxalyldihydrazideSolution(2.5g/L)—Dissolve2.5 g
of oxalyldihydrazide in warm water and dilute to 1 L.
15.3 Start the electrolysis and increase the voltage until the
ammeter indicates a current which is equivalent to about
17.5 Preparation of Calibration Curve:
1.0 A⁄dm and electrolyze overnight.Alternatively electrolyze
17.5.1 Calibration Solutions:
at a current density of 4 A⁄dm for 1.5 h. (The more rapid
17.5.1.1 Transfer 25 mL of boric acid solution to a 250-mL
procedure requires the use of gauze electrodes).
volumetric flask and then add a solution containing 150 mL of
15.4 Slowly withdraw the electrodes (or lower the beaker)
water, 2 mL of HF, and 30 mL of HNO (1 + 1). Dilute to
with the current still flowing, and rinse with a stream of water
volume and mix.
from a wash bottle. Quickly remove the cathode, rinse it in
17.5.1.2 Transfer 10 mL of this solution to each of four
water, and then dip into two successive baths of ethanol or
50-mL volumetric flasks. Using pipets, transfer (1, 3, 5, and
methanol. Dry in an oven at 110 °C for 3 min to 5 min.
7) mL of Copper Solution B (1 mL = 0.010 mg Cu) to the
flasks. Proceed as directed in 17.5.3.
15.5 Return the voltage to zero and turn off the switch.
17.5.2 Reference Solution—Add 10 mL of boric acid solu-
Reserve the electrolyte.
tion prepared as directed in 17.5.1.1 to a 50-mL volumetric
15.6 Allow the electrode to cool to room temperature and
flask and proceed as directed in 17.5.3.
weigh.
17.5.3 Color Development—Add in order, and with mixing
after each addition, 5 mL of citric acid solution, 6 mL of
16. Calculation
NH OH, 10 mL of acetaldehyde solution, and 10 mL of ox-
16.1 Calculate the percentage of copper as follows:
alyldihydrazide solution. Cool, dilute to volume, and mix.
Allow to stand for 30 min and proceed as directed in 17.5.4.
Copper, % 5 @~A1B!/C# 3100 (1)
17.5.4 Spectrophotometry:
where:
17.5.4.1 Multiple-Cell Spectrophotometer—Measure the
A = deposited copper, g,
cellcorrectionusingabsorptioncellswitha2-cmlightpathand
B = copper in the electrolyte as calculated in 17.10,g,and
a light band centered at approximately 540 nm. Using the test
cell, take the spectrophotometric readi
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