ASTM E106-83(1996)
(Test Method)Standard Test Methods for Chemical Analysis of Copper-Beryllium Alloys
Standard Test Methods for Chemical Analysis of Copper-Beryllium Alloys
SCOPE
1.1 These test methods cover procedures for the chemical analysis of copper-beryllium alloys having chemical compositions within the following limits: Concentration Element Range, % Copper 97 to 98 Beryllium 0.4 to 2.05 Nickel 0.0 to 0.30 Cobalt 0.0 to 0.3 Iron 0.0 to 0.30
1.2 The analytical procedures appear in the following order: Sections Copper by the Electrolytic Method 8 to 12 Beryllium: Phosphate Gravimetric Method 13 to 19 Aluminon (Photometric) Method 20 to 27 Nickel by the Dimethylglyoxime (Photometric) Method 28 to 36 Cobalt by the Nitroso-R-Salt (Photometric) Method 37 to 44 Iron by the Thiocyanate (Photometric) Method 45 to 52
General Information
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Standards Content (Sample)
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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Designation: E 106 – 83 (Reapproved 1996)
Standard Test Methods for
Chemical Analysis of Copper-Beryllium Alloys
This standard is issued under the fixed designation E 106; 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.
1. Scope E 173 Practice for Conducting Interlaboratory Studies of
Methods for Chemical Analysis of Metals
1.1 These test methods cover procedures for the chemical
analysis of copper-beryllium alloys having chemical composi-
3. Significance and Use
tions within the following limits:
3.1 These test methods for the chemical analysis of metals
Concentration
and alloys are primarily intended to test such materials for
Element Range,%
compliance with compositional specifications. It is assumed
Copper 97 to 98
that all who use these test methods will be trained analysts
Beryllium 0.4 to 2.05
capable of performing common laboratory procedures skill-
Nickel 0.0 to 0.30
Cobalt 0.0 to 0.3
fully and safely. It is expected that work will be performed in
Iron 0.0 to 0.30
a properly equipped laboratory.
1.2 The analytical procedures appear in the following order:
4. Apparatus, Reagents, and Photometric Practice
Sections
4.1 Apparatus and reagents required for each determination
Copper by the Electrolytic Method 8-12
are listed in separate sections preceding the procedure. The
Beryllium:
apparatus, standard solutions, and certain other reagents used
Phosphate Gravimetric Method 13-19
Aluminon (Photometric) Method 20-27
in more than one procedure are referred to by number and shall
Nickel by the Dimethylglyoxime (Photometric) Method 28-36
conform to the requirements prescribed in Practices E 50E50,
Cobalt by the Nitroso-R-Salt (Photometric) Method 37-44
Iron by the Thiocyanate (Photometric) Method 45-52 except that photometers shall conform to the requirements
prescribed in Practice E 60E60.
2. Referenced Documents
4.2 Photometric practice prescribed in these methods shall
2.1 ASTM Standards:
conform to Practice E 60E60.
E29 Practice for Using Significant Digits in Test Data to
5. Safety Precautions
Determine Conformance With Specification
E50 Practices for Apparatus, Reagents, and Safety Precau-
5.1 For precautions to be observed in these methods, refer-
tions for Chemical Analysis of Metals ence shall be made to Practices E 50E50. Both beryllium
E55 PracticeforSamplingWroughtNonferrousMetalsand
metal and its compounds may be toxic. Care should be
Alloys for Determination of Chemical Composition
exercised to prevent contact of beryllium-containing materials
E60 Practice for Photometric and Spectrophotometric
with the skin. The inhalation of any beryllium-containing
Methods for Chemical Analysis of Metals
substance, either as a volatile compound or as finely divided
E76 Test Methods for ChemicalAnalysis of Nickel-Copper
powder, should be especially avoided. Beryllium-containing
Alloys
residues(especiallyignitedoxide)shouldbecarefullydisposed
of.
6. Sampling
These test methods are under the jurisdiction of ASTM Committee E-1 on
6.1 Sampling shall conform to Practice E 55E55.
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
responsibility of Subcommittee E01.05 on Cu, Pb, Zn, Cd, Sn, Be, theirAlloys and
7. Rounding Off Calculated Values
Related Metals.
Current edition approved Feb. 25, 1983. Published April 1983. Originally
7.1 Calculated values shall be rounded off to the desired
published as E 106 – 54. Last previous edition E 106 – 72 (1978).
2 number of places in accordance with the rounding-off method
Annual Book of ASTM Standards, Vol 14.02.
Annual Book of ASTM Standards, Vol 03.05. given in 3.4 and 3.5 of Practice E 29E29.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 106 – 83 (1996)
COPPER BY THE ELECTROLYTIC TEST METHOD is cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
8. Apparatus
adequate for the contemplated use.
8.1 Electrodes for Electroanalysis—Apparatus No. 9.
BERYLLIUM BY THE PHOSPHATE GRAVIMETRIC
9. Reagents
TEST METHOD
9.1 Sulfuric-Nitric Acid Mixture—Add slowly, while stir-
13. Scope
ring, 300 mL of H SO to 750 mL of water. Cool and add 210
2 4
mL of HNO .
13.1 This test method covers the determination of beryllium
in concentrations from 0.1 to 3.0 %.
10. Procedure
10.1 Transfer 5.00 g of sample to a 300-mL electrolysis
14. Summary of Test Method
beaker. Add 42 mL of the H SO -HNO mixture, cover, and
2 4 3
14.1 Interferingelementsarecomplexedwith(ethylenedini-
allow to stand a few minutes until reaction has nearly ceased.
trilo) tetraacetate solution. Beryllium is precipitated as the
Heat at 80 to 90°C until dissolution is complete and brown
phosphate, which is filtered, ignited, and weighed as beryllium
fumes have been expelled. Wash down the cover glass and the
pyrophosphate.
sides of the beaker and dilute to about 175 mL (enough to
submerge the cathode when it is inserted).
15. Interferences
10.2 Insert the electrodes, cover the solution with a pair of
15.1 The elements ordinarily present in beryllium-copper
splitwatchglasses,andelectrolyzeatacurrentdensityofabout
2 alloys do not interfere if their concentrations are under the
0.6 A/dm for about 16 h. Wash down the cover glasses, sides
maximum limits shown in 1.1.
of beaker, and electrode stems and continue electrolysis for
about 15 min. If no copper plates on the newly exposed
16. Reagents
cathode surface, copper deposition may be considered com-
16.1 Ammonium Acetate Solution (500 g/L)—Dissolve 500
pleted.
g of ammonium acetate in water, and dilute to 1 L.
10.3 Quickly withdraw the cathode from the electrolyte
16.2 AmmoniumAcetate Wash Solution—Dilute5mLofthe
while directing a gentle stream of water from a wash bottle
ammonium acetate solution to 1 L, and adjust the pH to 5.2 6
over its surface. Rinse the cathode in a water bath and then dip
0.05 with acetic acid.
in two successive baths of ethanol or acetone. Dry in an oven
at 110°C for 3 to 5 min, cool, and weigh. Reserve the spent
NOTE 1—Use a pH meter for all pH adjustments.
electrolyte.
16.3 Ammonium Dihydrogen Phosphate (100 g/L)—
Dissolve 100 g of ammonium dihydrogen phosphate
where:
A = grams of copper, and (NH H PO ) in water and dilute to 1 L.
4 2 4
B = grams of sample used. 16.4 Ammonium (Ethylenedinitrilo) Tetraacetate Solution
(28 g/L)—To2.5gof(ethylenedinitrilo)tetraaceticacidadd30
10.4 Reserved Electrolyte—Evaporate the spent electrolyte
to dense white fumes and fume for about 5 min to dehydrate mLof water and a drop of methyl red solution. Neutralize with
silicic acid. Cool, add about 50 mL of water, and heat until all NH OH (1 + 1), and warm gently to dissolve the last traces of
salts are in solution. Filter through a small, medium-texture solid. Cool and dilute to 100 mL.
paper, catching the filtrate in a 250-mL volumetric flask. Wash 16.5 Methyl Red Indicator Solution (0.5 g/L ethanol)—
the beaker and paper thoroughly with hot H SO (1 + 99), Dissolve 0.05 g of methyl red in 100 mL of ethanol.
2 4
combining the washings with the filtrate. Cool the solution in
17. Procedure
the volumetric flask, dilute to the mark, and mix. Reserve for
the determinations of beryllium, nickel, cobalt, and iron as
17.1 Using a pipet, transfer 50 mL of the electrolyte
described in Sections 17, 34, 43, and 51 respectively. If the
reservedin10.4toa400-mLbeaker.Add3dropsofHFand10
filtrate is not to be used for the gravimetric determination of
mL of H SO (1 + 2), and evaporate to fumes. Cool to room
2 4
beryllium, the removal of silica is not necessary and the
temperature and add 100 mLof water. Heat to dissolve soluble
electrolyte may be diluted to volume directly.
salts and again cool to room temperature.
17.2 Add 10 mL of ammonium (ethylenedinitrilo) tetraac-
11. Calculation
etate solution, and adjust the pH to 2.0 6 0.05 (see Note 1)
11.1 Calculate the percentage of copper as follows:
withNH OH(1 + 1).Boil1minandcooltoroomtemperature.
Copper, % 5 A/B 3 100 (1) Add 10 mL of ammonium dihydrogen phosphate solution and
~ !
adjust the pH to 5.2 6 0.05 with ammonium acetate solution.
17.3 Heat to boiling cautiously to prevent bumping, and
12. Precision and Bias
then maintain just below the boiling point until the precipitate
12.1 This test method was originally approved for publica- becomes granular. Remove from the source of heat and allow
tion before the inclusion of precision and bias statements to stand at least 12 h.
within standards was mandated. The original interlaboratory 17.4 Filter using an 11-cm fine paper and wash six times
test data for this test method are no longer available. The user with ammonium acetate wash solution. Discard the filtrate.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 106 – 83 (1996)
Dissolve the precipitate with 100 mL of hot HCl (1 + 4), 21. Concentration Range
collecting the solution in the original beaker.
21.1 The recommended concentration range is from 0.004
17.5 Add 2 mL of ammonium (ethylenedinitrilo) tetraac-
to 0.09 mg of beryllium in 100 mL of solution, using a cell
etate solution, and adjust the pH to 2.0 6 0.05 with NH OH 4
depth of 2 cm.
(1 + 1). Cool, add 2 mL of ammonium dihydrogen phosphate
solution, and adjust the pH to 5.2 6 0.05 with ammonium
22. Stability of Color
acetate solution. Proceed as directed in 17.3.
22.1 The intensity of the color of the beryllium lake
17.6 Filter using an 11-cm fine paper and wash six times
increases slowly on standing. Therefore, a uniform standing
with ammonium acetate wash solution. Transfer the paper to a
time must be adhered to.
weighed platinum crucible. Place the crucible in a muffle
furnace, and dry and char the paper by gradually increasing the
23. Interfering Elements
temperature to 500°C. When all the carbon has been removed,
raise the temperature to 1000°C and maintain at this tempera-
23.1 Provision is made in the procedure for preventing, or
ture for 4 h. Cool in a desiccator and weigh.
compensating for, interference from metals present in amounts
not exceeding the maximum limits given in 1.1
18. Calculation
24. Reagents
18.1 Calculate the percentage of beryllium as follows:
24.1 Aluminon-Buffer Composite Solution—Add 500 g of
Beryllium, % 5 ~A 3 0.0939/B! 3 100 (2)
ammonium acetate to 1 Lof water in a 2-Lbeaker.Add 80 mL
of glacial acetic acid and stir until dissolution is complete.
where:
Filter if necessary. Dissolve 1.000 g of a suitable grade of
A = grams of beryllium pyrophosphate, and
aluminon (aurin tricarboxylic acid-ammonium salt) in 50 mL
B = grams of sample used
of water and add to the buffer solution. Dissolve3gof benzoic
acid in 20 mLof methanol and add to the buffer solution while
19. Precision and Bias
stirring. Dilute the mixture to 2 L.Add 10 g of gelatin to 250
19.1 Precision—Eight laboratories cooperated in testing
mL of water in a 400-mL beaker. Place the beaker in a boiling
this method and obtained the data summarized in Table 1.
water bath and allow to remain, with frequent stirring, until the
19.2 Bias—No certified reference materials suitable for
gelatin has dissolved completely. Pour the warm gelatin
testingthistestmethodwereavailablewhentheinterlaboratory
solution into 500 mL of distilled water, while stirring. Cool to
testing program was conducted. The user of this standard is
room temperature, dilute to 1 L, and mix. Transfer the
encouraged to employ accepted reference materials, if avail-
aluminon and gelatin solutions to a 4-L chemically resistant
able, to determine the accuracy of this test method as applied
glass-stopperedbottle,mixwell,andstoreinacool,darkplace.
in a specific laboratory.
24.2 Complexone Solution—See 16.4.
24.3 Copper Chloride Solution (1 mL = 2 mg Cu)—
Dissolve 0.54 g of CuCl ·2H O in water and dilute to 100 mL
2 2
TABLE 1 Statistical Information
in a volumetric flask.
Beryllium
Repeatability Reproducibility 24.4 Standard Beryllium Solution (1 mL = 1.0 mg Be)—
Test Specimen Found,
(R , E 173E 173)(R , E 173E 173)
1 2
Dissolve 9.82 g of BeSO ·4H O in 100 mL of HCl (1 + 3).
% 4 2
(1) Beryllium copper, B-7 1.744 0.026 0.042
Filter, if necessary, and dilute to 500 mL. Standardize as
(2) Beryllium copper, C-7 0.460 0.020 0.046
follows:Transfer25mLofthesolutiontoa250-mLbeakerand
proceed in accordance with Section 17.2-17.6 and 18.1.
24.5 Standard Beryllium Solution (1 mL = 0.01 mg Be)—
Transfer 10 mLof the above solution to a 1-Lvolumetric flask,
BERYLLIUM BY THE ALUMINON
add 10 mL of HCl, dilute to the mark, and mix.
(PHOTOMETRIC) TEST METHOD
20. Principle of Test Method
This procedure has been written for a cell having a 2-cm light path. Cells
20.1 In a properly buffered solution, ammonium aurin
having other dimensions may be used, provided suitable adjustments can be made
tricarboxylate (aluminon) forms a red lake with beryllium.The
in the amounts of sample and reagents used.
Certain commercially available grades of aluminon have been found to be
addition of ethylenediamine tetraacetic acid (complexone)
unsatisfactory for this purpose. It may be necessary to prepare a small portion of the
prevents the interference of aluminum, iron, copper, and
composite reagent before use.The currently available (1954) product from Eastman
similar elements. Photometric measurement is made at ap-
Kodak appears to be satisfactory.
proximately 515 nm. Knox gelatin has been found satisfactory for this purpose.
NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Please contact ASTM International (www.astm.org) for the latest information.
E 106 – 83 (1996)
25. Preparation of Calibration Curve NICKEL BY THE DIMETHYLGLYOXIME
(PHOTOMETRIC) TEST METHOD
25.1 Calibration Solutions—Transfer 1.0, 2.0, 4.0, 5.0, 7.0,
and 9.0 mL of beryllium solution (1 mL = 0.01 mg Be) to
28. Summary of Test Method
100-mL volumetric flasks. Add 1 mL of CuCl solution (1
28.1 Nickel after oxidation with bromine, forms a red-
mL = 2 mg Cu) to each flask and dilute to about 75 mL.
colored, soluble salt with dimethylglyoxime. Photometric mea-
25.2 Reference Solution—Add 1 mL of CuCl soluti
...
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