ASTM E478-89a(1996)

NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
Designation: E 478 – 89a (Reapproved 1996)
Standard Test Methods for
Chemical Analysis of Copper Alloys
This standard is issued under the fixed designation E 478; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope
Zinc by the (Ethylenedinitrilo)tetraacetic Acid
(EDTA) Titrimetric Test Method [2 to 40 %] 46-53
1.1 These test methods cover the chemical analysis of
1.3 This standard does not purport to address all of the
copper alloys having chemical compositions within the follow-
safety concerns, if any, associated with its use. It is the
ing limits:
responsibility of the user of this standard to establish appro-
Element Concentration, %
priate safety and health practices and determine the applica-
Aluminum 12.0 max
bility of regulatory limitations prior to use. Specific hazard
Antimony 1.0 max
statements are given in Section 5, Note 4, and Section 106.
Arsenic 1.0 max
Cadmium 1.5 max
Cobalt 1.0 max
2. Referenced Documents
Copper 40.0 min
2.1 ASTM Standards:
Iron 6.0 max
Lead 27.0 max
E 29 Practice for Using Significant Digits in Test Data to
Manganese 6.0 max 3
Determine Conformance with Specifications
Nickel 50.0 max
E 50 Practices for Apparatus, Reagents, and Safety Precau-
Phosphorus 1.0 max
Silicon 5.0 max
tions for Chemical Analysis of Metals
Sulfur 0.1 max
E 60 Practice for Photometric and Spectrophotometric
Tin 20.0 max
Methods for Chemical Analysis of Metals
Zinc 50.0 max
E 173 Practice for Conducting Interlaboratory Studies of
1.2 The test methods appear in the following order:
Methods for Chemical Analysis of Metals
Sections
E 255 Practice for Sampling Copper and Copper Alloys for
Aluminum by the Carbamate Extraction-(Ethyl-
Determination of Chemical Composition
enedinitrilo) Tetraacetate Titrimetric Test
Method 70-77
E 1024 Guide for Chemical Analysis of Metals and Metal
Copper by the Combined Electrodeposition
Bearing Ores by Flame Atomic Absorption Spectropho-
Gravimetric and Oxalyldihydrazide Photomet-
tometry
ric Test Method [50 %, minimum] 9-17
Iron by the 1,10-Phenanthroline Photometric
Test Method [0.003 to 1.25 %] 18-27
3. Significance and Use
Lead by the Atomic Absorption Test Method 89-99
3.1 These test methods for the chemical analysis of metals
Lead by the (Ethylenedinitrilo)tetraacetic Acid
(EDTA) Titrimetric Test Method [2.0 to
and alloys are primarily intended as referee methods to test
30.0 %] 28-35
such materials for compliance with compositional specifica-
Nickel by the Dimethylglyoxime Extraction Pho-
tometric Test Method [0.03 to 5.0 %] 36-45 tions. It is assumed that all who use these methods will be
Nickel by the Dimethylglyoxime Gravimetric
trained analysts capable of performing common laboratory
Test Method [4 to 50 %] 54-61
procedures skillfully and safely. It is expected that work will be
Silver in Silver-Bearing Copper by the Atomic
Absorption Test Method 100-111 performed in a properly equipped laboratory.
Tin by the Iodatimetric Titration Test Method
[0.5 to 20 %] 62-69
4. Apparatus, Reagents, and Photometric Practice
Tin by the Phenylfluorone Photometric Test
Method %] 112-122 4.1 Apparatus and reagents required for each determination
Zinc by Atomic Spectrometry 78-88
are listed in separate sections preceding the procedure. The
apparatus, standard solutions, and certain other reagents used
in more than one procedure are referred to by number and shall
conform to the requirements prescribed in Practices E 50,
These test methods are under the jurisdiction of ASTM Committee E-1 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, their Alloys and
Related Metals.
Current edition approved Oct. 27, 1989. Published January 1990. Originally Annual Book of ASTM Standards, Vol 14.02.
published as E 478 – 73. Last previous edition E 478 – 89. Annual Book of ASTM Standards, Vol 03.05.
2 5
The actual limits of application of each test method are presented in 1.2. Annual Book of ASTM Standards, Vol 03.06.
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NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
E 478 – 89a (1996)
except that photometers shall conform to the requirements 13.3 Lead Nitrate Solution (10 g/L)—Dissolve 10.0 g of
prescribed in Practice E 60. lead nitrate (Pb(NO ) ) in water and dilute to 1 L.
3 2
4.2 Photometric practice prescribed in these test methods
shall conform to Practice E 60. 14. Procedure
14.1 Transfer a 2.000-g sample, weighed to the nearest 0.1
5. Safety Precautions
mg, to a 250-mL poly(tetrafluoroethylene) or polypropylene
5.1 For precautions to be observed in the use of certain
beaker, add 2 mL of HF, and 30 mL of HNO (1 + 1). Cover
reagents in these test methods, refer to Practices E 50.
with a cover glass and allow to stand for a few minutes until the
reaction has nearly ceased. Warm but do not heat over 80°C.
6. Sampling
When dissolution is complete, add 25 mL of 3 % H O and 3
2 2
6.1 For procedures for sampling the material, refer to
mL of Pb(NO ) solution. Rinse the cover glass and dilute to
3 2
Practice E 255. However, this method does not supersede any
approximately 150 mL with NH Cl solution.
sampling requirements specified in a specific ASTM material
14.2 With the electrolyzing current off, position the anode
specification.
and the accurately weighed cathode in the solution so that the
gauze is completely immersed. Cover the beaker with a split
7. Rounding Calculated Values
plastic cover.
7.1 Calculated values shall be rounded to the desired num-
14.3 Start the electrolysis and increase the voltage until the
ber of places as directed in 3.4 to 3.6 of Practice E 29.
ammeter indicates a current which is equivalent to about 1.0
A/dm and electrolyze overnight. Alternatively electrolyze at a
8. Interlaboratory Studies
current density of 4 A/dm for 1.5 h. (The more rapid procedure
8.1 These test methods have been evaluated in accordance
requires the use of gauze electrodes).
with Practice E 173 unless otherwise noted in the precision
14.4 Slowly withdraw the electrodes (or lower the beaker)
section.
with the current still flowing, and rinse with a stream of water
from a wash bottle. Quickly remove the cathode, rinse it in
COPPER BY THE COMBINED
water, and then dip into two successive baths of ethanol or
ELECTRODEPOSITION GRAVIMETRIC AND
methanol. Dry in an oven at 110°C for 3 to 5 min.
OXALYLDIHYDRAZIDE PHOTOMETRIC TEST
14.5 Return the voltage to zero, and turn off the switch.
METHOD
Reserve the electrolyte.
14.6 Allow the electrode to cool to room temperature, and
9. Scope
weigh.
9.1 This test method covers the determination of copper in
concentrations greater than 50 %.
15. Calculation
10. Summary of Test Method 15.1 Calculate the percentage of copper as follows:
Copper, % 5 A 1 B/C 3 100 (1)
10.1 After dissolution of the sample in nitric and hydrof- @~ #
luoric acids, the oxides of nitrogen are reduced with hydrogen
peroxide, and the copper deposited electrolytically. Loss of
where:
platinum from the anode is minimized by the addition of lead.
A = deposited copper, g,
The copper oxalyldihydrazide complex is formed with the
B = copper in the electrolyte as calculated in 16.10, g, and
copper remaining in the electrolyte. Photometric measurement
C = sample used, g.
is made at approximately 540 nm.
16. Photometric Determination of the Residual Copper in
11. Interferences
the Electrolyte
11.1 The elements ordinarily present do not interfere if their
16.1 Interferences—The elements ordinarily present do not
concentrations are under the maximum limits shown in 1.1.
interfere if their concentrations are under the maximum limits
shown in 1.1.
12. Apparatus
16.2 Concentration Range—The recommended concentra-
12.1 Apparatus No. 9—Gauze cathodes are recommended
tion range is from 0.0025 to 0.07 mg of copper per 50 mL of
where rapid electrolysis is used.
solution, using a 2-cm cell.
12.2 Polytetrafluoroethylene or Polypropylene Beakers,
NOTE 1—This procedure has been written for cells having a 2-cm light
250-mL capacity.
path. Cells having other dimensions may be used, provided suitable
12.3 Polytetrafluoroethylene or Polypropylene Split Covers.
adjustments can be made in the amounts of sample and reagents used.
13. Reagents
16.3 Stability of Color—The color fully develops in 20 min,
13.1 Ammonium Chloride Solution (0.02 g/L)—Dissolve and is stable for 1 h.
0.02 g of ammonium chloride (NH Cl) in water and dilute to 1 16.4 Reagents:
L. 16.4.1 Acetaldehyde Solution (40 %)—Dilute 400 mL of
13.2 Hydrogen Peroxide (3 %)—Dilute 100 mL of 30 % acetaldehyde to 1 L with water.
hydrogen peroxide to 1 L. 16.4.2 Boric Acid Solution—Reagent No. 136.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
E 478 – 89a (1996)
16.4.3 Citric Acid Solution (200 g/L)—Dissolve 200 g of 16.10 Calculation—Convert the net photometric reading of
citric acid in water and dilute to 1 L. the test solution to milligrams of copper by means of the
16.4.4 Copper, Standard Solution A (1 mL = 1.0 mg Cu)— calibration curve. Calculate the grams of copper in the total
Transfer a 1.000-g sample of electrolytic copper (purity: electrolyte as follows:
99.9 % minimum) to a 250-mL beaker and add 10 mL of HNO
Copper, g 5 ~A 3 25!/1000 (2)
(1 + 1). Evaporate till nearly to dryness. Add 5 mL of water to
dissolve the residue. Transfer to a 1-L volumetric flask, dilute
where:
to volume, and mix.
A = copper found in 50 mL of the final test solution, mg.
16.4.5 Copper, Standard Solution B (1 mL = 0.010 mg
Cu)—Using a pipet, transfer 10 mL of copper solution A (1
mL = 1.0 mg Cu) to a 1-L volumetric flask, dilute to volume
17. Precision
and mix.
17.1 Eight laboratories cooperated in testing this test
16.4.6 Oxalyldihydrazide Solution (2.5 g/L)—Dissolve 2.5
method and obtained the data summarized in Table 1.
g of oxalyldihydrazide in warm water and dilute to 1 L.
16.5 Preparation of Calibration Curve:
TABLE 1 Statistical Information
16.5.1 Calibration Solutions:
Copper Repeatability Reproducibility
16.5.1.1 Transfer 25 mL of boric acid solution to a 250-mL
Test Specimen
Found, % (R , E 173) (R , E 173)
1 2
volumetric flask and then add a solution containing 150 mL of
1. Bronze ounce metal (NBS 83.56 0.09 0.13
water, 2 mL of HF, and 30 mL of HNO (1 + 1). Dilute to
124d, 83.60 Cu)
volume, and mix.
2. AAB 521 91.98 0.03 0.08
3. AAB 655 95.38 0.09 0.14
16.5.1.2 Transfer 10 mL of this solution to each of four
4. AAB 681 57.60 0.10 0.09
50-mL volumetric flasks. Using pipets, transfer 1, 3, 5, and 7
5. AAB 715 68.95 0.08 0.21
mL of copper solution B (1 mL = 0.010 mg Cu) to the flasks.
Proceed as directed in 16.5.3.
16.5.2 Reference Solution—Add 10 mL of boric acid solu-
IRON BY THE 1,10-PHENANTHROLINE
tion prepared as directed in 16.5.1.1 to a 50-mL volumetric
PHOTOMETRIC TEST METHOD
flask and proceed as directed in 16.5.3.
18. Scope
16.5.3 Color Development—Add in order, and with mixing
after each addition, 5 mL of citric acid solution, 6 mL of
18.1 This test method covers the determination of iron in
NH OH, 10 mL of acetaldehyde solution, and 10 mL of concentrations from 0.003 to 1.25 %.
oxalyldihydrazide solution. Cool, dilute to volume, and mix.
19. Summary of Test Method
Allow to stand for 30 min and proceed as directed in 16.5.4.
16.5.4 Photometry: 19.1 The sample is dissolved in hydrochloric acid and
hydrogen peroxide, and the excess oxidant removed by evapo-
16.5.4.1 Multiple-Cell Photometer—Measure the cell cor-
rection using absorption cells with a 2-cm light path and a light ration. The iron is extracted with methyl isobutyl ketone-
benzene mixture. The iron is extracted from the organic phase
band centered at approximately 540 nm. Using the test cell,
take the photometric readings of the calibration solutions. into a hydroxylamine hydrochloride solution and the red-
colored 1,10-phenanthroline complex is formed. Photometric
16.5.4.2 Single-Cell Photometer—Transfer a suitable por-
tion of the reference solution to an absorption cell with a 2-cm measurement is made at approximately 510 nm.
light path and adjust the photometer to the initial setting using
20. Concentration Range
a light band centered at approximately 540 nm. While main-
20.1 The recommended concentration range is from 0.005
taining this adjustment, take the photometric readings of the
to 0.125 mg of iron per 50 mL of solution, using a 2-cm cell.
calibration solutions.
16.5.5 Calibration Curve—Plot the net photometric-
NOTE 3—This test method has been written for cells having a 2-cm
readings of the calibration solutions against milligrams of
light path. Cells having other dimensions may be used, provided suitable
copper per 50 mL of solution. adjustments can be made in the amounts of sample and reagents used.
16.6 Test Solution—Transfer the reserved electrolyte to a
21. Stability of Color
250-mL volumetric flask containing 25 mL of boric acid
21.1 The color develops within 5 min and is stable for at
solution, dilute to volume, and mix. Using a pipet, transfer 10
least 4 h.
mL to a 50-mL volumetric flask (Note 2). Proceed as directed
in 16.8.
22. Interferences
NOTE 2—If the solution shows a permanganate color, add sodium
22.1 Elements ordinarily present do not interfere if their
nitrite solution (20 g/L) dropwise until the color is discharged, and then
concentrations are under the maximum limits shown in 1.1.
proceed as directed in 16.8.
23. Reagents
16.7 Reference Solution—Proceed as directed in 16.5.2.
16.8 Color Development—Proceed as directed in 16.5.3. 23.1 Hydroxylamine Hydrochloride Solution (10 g/L)—
16.9 Photometry—Take the photometric reading of the test Prepare a solution as directed for Reagent No. 131, but dilute
solution as directed in 16.5.4. to 500 mL.
NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
Contact ASTM International (www.astm.org) for the latest information.
E 478 – 89a (1996)
23.2 Iron, Standard Solution A (1 mL = 0.125 mg Fe)— 25.1.2 Carry a reagent blank through the entire procedure,
Prepare a solution as directed for Reagent No. 4, but use using the same amounts of all
...