ASTM E106-83(2004)
(Test Method)Standard Test Methods for Chemical Analysis of Copper-Beryllium Alloys (Withdrawn 2011)
Standard Test Methods for Chemical Analysis of Copper-Beryllium Alloys (Withdrawn 2011)
SIGNIFICANCE AND USE
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 procedures for the chemical analysis of copper-beryllium alloys having chemical compositions within the following limits: ElementConcentrationRange,%Copper97 to 98Beryllium0.4 to 2.05Nickel0.0 to 0.30Cobalt0.0 to 0.3Iron0.0 to 0.30
1.2 The analytical procedures appear in the following order:SectionsCopper by the Electrolytic MethodBeryllium:Phosphate Gravimetric MethodAluminon (Photometric) MethodNickel by the Dimethylglyoxime (Photometric) MethodCobalt by the Nitroso-R-Salt (Photometric) MethodIron by the Thiocyanate (Photometric) Method
1.3 This test method covers the determination of beryllium in concentrations from 0.1 to 3.0 %.
WITHDRAWN RATIONALE
These test methods cover procedures for the chemical analysis of copper-beryllium alloys having chemical compositions within specific limits.
Formerly under the jurisdiction of Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials, these test methods were withdrawn in January 2011. This standard was withdrawn without replacement due to its limited use by industry.
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Designation:E106–83(Reapproved2004)
Standard Test Methods for
Chemical Analysis of Copper-Beryllium Alloys
This standard is issued under the fixed designation E106; 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 E76 Test Methods for ChemicalAnalysis of Nickel-Copper
Alloys
1.1 These test methods cover procedures for the chemical
E173 Practice for Conducting Interlaboratory Studies of
analysis of copper-beryllium alloys having chemical composi-
Methods for Chemical Analysis of Metals
tions within the following limits:
Concentration
3. Significance and Use
Element Range,%
3.1 These test methods for the chemical analysis of metals
Copper 97 to 98
and alloys are primarily intended to test such materials for
Beryllium 0.4 to 2.05
compliance with compositional specifications. It is assumed
Nickel 0.0 to 0.30
Cobalt 0.0 to 0.3
that all who use these test methods will be trained analysts
Iron 0.0 to 0.30
capable of performing common laboratory procedures skill-
1.2 The analytical procedures appear in the following order:
fully and safely. It is expected that work will be performed in
a properly equipped laboratory.
Sections
Copper by the Electrolytic Method 8-12
4. Apparatus, Reagents, and Photometric Practice
Beryllium:
4.1 Apparatus and reagents required for each determination
Phosphate Gravimetric Method 13-19
Aluminon (Photometric) Method 20-27
are listed in separate sections preceding the procedure. The
Nickel by the Dimethylglyoxime (Photometric) Method 28-36
apparatus, standard solutions, and certain other reagents used
Cobalt by the Nitroso-R-Salt (Photometric) Method 37-44
Iron by the Thiocyanate (Photometric) Method 45-52 in more than one procedure are referred to by number and shall
conform to the requirements prescribed in Practices E50,
2. Referenced Documents
except that photometers shall conform to the requirements
2.1 ASTM Standards:
prescribed in Practice E60.
E29 Practice for Using Significant Digits in Test Data to
4.2 Photometric practice prescribed in these methods shall
Determine Conformance with Specifications
conform to Practice E60.
E50 Practices for Apparatus, Reagents, and Safety Consid-
5. Safety Precautions
erations for Chemical Analysis of Metals, Ores, and
Related Materials
5.1 For precautions to be observed in these methods, refer-
E55 Practice for Sampling Wrought Nonferrous Metals and
ence shall be made to Practices E50. Both beryllium metal and
Alloys for Determination of Chemical Composition
its compounds may be toxic. Care should be exercised to
E60 Practice for Analysis of Metals, Ores, and Related
prevent contact of beryllium-containing materials with the
Materials by Molecular Absorption Spectrometry
skin. The inhalation of any beryllium-containing substance,
either as a volatile compound or as finely divided powder,
should be especially avoided. Beryllium-containing residues
These test methods are under the jurisdiction of ASTM Committee E01 on
(especially ignited oxide) should be carefully disposed of.
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
6. Sampling
Related Metals.
CurrenteditionapprovedJune1,2004.PublishedJuly2004.Originallyapproved
6.1 Sampling shall conform to Practice E55.
in 1954. Last previous edition approved in 1996 as E106 – 83 (1996). DOI:
10.1520/E0106-83R04.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on Withdrawn. The last approved version of this historical standard is referenced
the ASTM website. on www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
E106–83 (2004)
7. Rounding Off Calculated Values 12. Precision and Bias
7.1 Calculated values shall be rounded off to the desired
12.1 This test method was originally approved for publica-
number of places in accordance with the rounding-off method
tion before the inclusion of precision and bias statements
given in 3.4 and 3.5 of Practice E29.
within standards was mandated. The original interlaboratory
test data for this test method are no longer available. The user
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
14. Summary of Test Method
10.1 Transfer 5.00 g of sample to a 300-mL electrolysis
beaker. Add 42 mL of the H SO -HNO mixture, cover, and
14.1 Interferingelementsarecomplexedwith(ethylenedini-
2 4 3
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
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)—
where: Dissolve 100 g of ammonium dihydrogen phosphate
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
10.4 Reserved Electrolyte—Evaporate the spent electrolyte (28 g/L)—To2.5gof(ethylenedinitrilo)tetraaceticacidadd30
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
the volumetric flask, dilute to the mark, and mix. Reserve for
17. Procedure
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.
Add 10 mL of ammonium dihydrogen phosphate solution and
Copper, % 5 ~A/B! 3 100 (1)
adjust the pH to 5.2 6 0.05 with ammonium acetate solution.
E106–83 (2004)
17.3 Heat to boiling cautiously to prevent bumping, and 21. Concentration Range
then maintain just below the boiling point until the precipitate
21.1 The recommended concentration range is from 0.004
becomes granular. Remove from the source of heat and allow
to 0.09 mg of beryllium in 100 mL of solution, using a cell
to stand at least 12 h.
depth of 2 cm.
17.4 Filter using an 11-cm fine paper and wash six times
with ammonium acetate wash solution. Discard the filtrate.
22. Stability of Color
Dissolve the precipitate with 100 mL of hot HCl (1 + 4),
22.1 The intensity of the color of the beryllium lake
collecting the solution in the original beaker.
increases slowly on standing. Therefore, a uniform standing
17.5 Add 2 mL of ammonium (ethylenedinitrilo) tetraac-
time must be adhered to.
etate solution, and adjust the pH to 2.0 6 0.05 with NH OH
(1 + 1). Cool, add 2 mL of ammonium dihydrogen phosphate
23. Interfering Elements
solution, and adjust the pH to 5.2 6 0.05 with ammonium
23.1 Provision is made in the procedure for preventing, or
acetate solution. Proceed as directed in 17.3.
compensating for, interference from metals present in amounts
17.6 Filter using an 11-cm fine paper and wash six times
not exceeding the maximum limits given in 1.1
with ammonium acetate wash solution. Transfer the paper to a
weighed platinum crucible. Place the crucible in a muffle
24. Reagents
furnace, and dry and char the paper by gradually increasing the
24.1 Aluminon-Buffer Composite Solution—Add 500 g of
temperature to 500°C. When all the carbon has been removed,
ammonium acetate to 1 Lof water in a 2-Lbeaker.Add 80 mL
raise the temperature to 1000°C and maintain at this tempera-
of glacial acetic acid and stir until dissolution is complete.
ture for 4 h. Cool in a desiccator and weigh.
Filter if necessary. Dissolve 1.000 g of a suitable grade of
18. Calculation aluminon (aurin tricarboxylic acid-ammonium salt) in 50 mL
of water and add to the buffer solution. Dissolve3gof benzoic
18.1 Calculate the percentage of beryllium as follows:
acid in 20 mLof methanol and add to the buffer solution while
Beryllium, % 5 ~A 3 0.0939/B! 3 100 (2)
stirring. Dilute the mixture to 2 L.Add 10 g of gelatin to 250
mL of water in a 400-mL beaker. Place the beaker in a boiling
water bath and allow to remain, with frequent stirring, until the
where:
A = grams of beryllium pyrophosphate, and gelatin has dissolved completely. Pour the warm gelatin
B = grams of sample used solution into 500 mL of distilled water, while stirring. Cool to
room temperature, dilute to 1 L, and mix. Transfer the
19. Precision and Bias
aluminon and gelatin solutions to a 4-L chemically resistant
glass-stopperedbottle,mixwell,andstoreinacool,darkplace.
19.1 Precision—Eight laboratories cooperated in testing
24.2 Complexone Solution—See 16.4.
this method and obtained the data summarized in Table 1.
24.3 Copper Chloride Solution (1 mL = 2 mg Cu)—
19.2 Bias—No certified reference materials suitable for
Dissolve 0.54 g of CuCl ·2H O in water and dilute to 100 mL
testingthistestmethodwereavailablewhentheinterlaboratory 2 2
in a volumetric flask.
testing program was conducted. The user of this standard is
24.4 Standard Beryllium Solution (1 mL = 1.0 mg Be)—
encouraged to employ accepted reference materials, if avail-
Dissolve 9.82 g of BeSO ·4H O in 100 mL of HCl (1 + 3).
able, to determine the accuracy of this test method as applied
4 2
Filter, if necessary, and dilute to 500 mL. Standardize as
in a specific laboratory.
follows:Transfer25mLofthesolutiontoa250-mLbeakerand
proceed in accordance with Section 17.2-17.6 and 18.1.
TABLE 1 Statistical Information
24.5 Standard Beryllium Solution (1 mL = 0.01 mg Be)—
Beryllium Transfer 10 mLof the above solution to a 1-Lvolumetric flask,
Repeatability Reproducibility
Test Specimen Found,
add 10 mL of HCl, dilute to the mark, and mix.
(R , E173) (R , E173)
1 2
%
(1) Beryllium copper, B-7 1.744 0.026 0.042
(2) Beryllium copper, C-7 0.460 0.020 0.046 25. Preparation of Calibration Curve
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
100-mL volumetric flasks. Add 1 mL of CuCl solution (1
BERYLLIUM BY THE ALUMINON
mL = 2 mg Cu) to each flask and dilute to about 75 mL.
(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.
E106–83 (2004)
25.2 Reference Solution—Add 1 mL of CuCl solution (1 29. Concentration Range
mL = 2 mg Cu) to a 100-mL volumetric flask and dilute to
29.1 The recommended concentration range is from 0.02 to
about 75 mL. 4
0.40 mg of nickel per 100 mL of solution, using a cell depth
25.3 Color Development—Add 2 mL of complexone solu-
of 2 cm.
tion and 15 mL of aluminon buffer composite solution to each
flask, mixing well between additions. Dilute to the mark and 30. Stability of Color
mix without de
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