ASTM D283-13(2019)
(Test Method)Standard Test Methods for Chemical Analysis of Cuprous Oxide and Copper Pigments
Standard Test Methods for Chemical Analysis of Cuprous Oxide and Copper Pigments
SIGNIFICANCE AND USE
3.1 This collection of test methods is used by pigment producers and paint manufacturers for process control, product acceptance, and research and development.
SCOPE
1.1 These test methods cover procedures for the chemical analysis of cuprous oxide and copper pigments.
1.2 The analytical procedures appear in the following order:
Sections
Total Copper
7
Total Reducing Power as Cuprous Oxide
8 and 9
Metallic Copper
10 and 11
Cuprous Oxide
12
Cupric Oxide
13
Metals Other than Copper
14 – 16
Chlorides and Sulfates
17 and 18
Acetone-Soluble Matter
19
Water
20
Stability
21
Coarse Particles
22
Coarse Particles Insoluble in Nitric Acid
23
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, 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.
Designation: D283 − 13 (Reapproved 2019)
Standard Test Methods for
Chemical Analysis of Cuprous Oxide and Copper Pigments
This standard is issued under the fixed designation D283; 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 D1208 Test Methods for Common Properties of Certain
Pigments
1.1 These test methods cover procedures for the chemical
analysis of cuprous oxide and copper pigments.
3. Significance and Use
1.2 The analytical procedures appear in the following order:
3.1 This collection of test methods is used by pigment
Sections
producers and paint manufacturers for process control, product
Total Copper 7
acceptance, and research and development.
Total Reducing Power as Cuprous Oxide 8 and 9
Metallic Copper 10 and 11
4. Treatment of Sample
Cuprous Oxide 12
Cupric Oxide 13
4.1 Grind dry pigments, if lumpy or not finely ground, to a
Metals Other than Copper 14–16
Chlorides and Sulfates 17 and 18 fine powder and thoroughly mix (Note 1). Large samples may
Acetone-Soluble Matter 19
be thoroughly mixed and a representative portion taken and
Water 20
powderediflumpyornotfinelyground.Inallcasesthoroughly
Stability 21
Coarse Particles 22 mix the sample before taking portions for analysis. Preserve all
Coarse Particles Insoluble in Nitric Acid 23
samples in dry, dark, airtight and completely filled bottles or
1.3 The values stated in SI units are to be regarded as
containers to prevent oxidation. Some commercial copper
standard. No other units of measurement are included in this
oxides appear to segregate or oxidize rather easily. Therefore,
standard.
the thorough mixing of the sample to ensure homogeneity and
therapidhandlingofthesample,whenexposedtolightandair,
1.4 This standard does not purport to address all of the
are extremely important factors in obtaining accurate results
safety concerns, if any, associated with its use. It is the
NOTE 1—It is very important that the sample be thoroughly mixed.
responsibility of the user of this standard to establish appro-
Some samples of cuprous oxide are not homogeneous so are likely to give
priate safety, health, and environmental practices and deter-
trouble when an attempt is made to obtain concordant results. By placing
mine the applicability of regulatory limitations prior to use.
a few grams of a sample on a sheet of white paper and drawing it out with
1.5 This international standard was developed in accor- a spatula, it is frequently found that the sample contains coarse particles
of black scale, along with small balls of bright red cuprous oxide. Thus,
dance with internationally recognized principles on standard-
it may be necessary to pass the pigment through a No. 60 (250-µm) sieve,
ization established in the Decision on Principles for the
break up any lumps of ground pigment by gentle pressure, and grind any
Development of International Standards, Guides and Recom-
coarse particles failing to pass through the sieve. Since oxidation of slight
mendations issued by the World Trade Organization Technical
or even considerable magnitude may take place, these operations should
be performed quickly, avoiding prolonged grinding and exposure to light
Barriers to Trade (TBT) Committee.
and air.
2. Referenced Documents
5. Reagents
2.1 ASTM Standards:
5.1 Purity of Reagents—Reagent grade chemicals shall be
D185 Test Methods for Coarse Particles in Pigments
used in all tests. Unless otherwise indicated, it is intended that
D1193 Specification for Reagent Water
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society,
1 where such specifications are available. Other grades may be
These test methods are under the jurisdiction of ASTM Committee D01 on
Paint and Related Coatings, Materials, and Applications and are the direct used, provided it is first ascertained that the reagent is of
responsibility of Subcommittee D01.31 on Pigment Specifications.
Current edition approved June 1, 2019. Published June 2019. Originally
approved in 1928. Last previous edition approved in 2013 as D283 – 13. DOI: Reagent Chemicals, American Chemical Society Specifications, American
10.1520/D0283-13R19. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
For referenced ASTM standards, visit the ASTM website, www.astm.org, or listed by the American Chemical Society, see Analar Standards for Laboratory
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Standards volume information, refer to the standard’s Document Summary page on and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
the ASTM website. MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D283 − 13 (2019)
sufficiently high purity to permit its use without lessening the 8.3 Ferrous Ammonium Sulfate, Standard Solution (0.03
accuracy of the determination. N)—Dissolve 12 g of ferrous ammonium sulfate
(Fe(NH ) (SO ) ·6H O) in 200 to 300 mL of water and add
4 2 4 2 2
5.2 Purity of Water—Unless otherwise indicated, references
40 mL of H SO (sp gr 1.84), while stirring constantly. Dilute
2 4
to water shall be understood to mean reagent water conforming
to 1 L in a volumetric flask. A few pieces of mossy aluminum
to Type II of Specification D1193.
may be added to stabilize the solution. The solution should be
5.3 Ammonium Sulfate—((NH ) SO ).
4 2 4 restandardized frequently against 0.1 N ceric ammonium ni-
trate solution.
5.4 Nitric Acid (sp gr 1.42)—Concentration nitric acid
(HNO
3).
8.4 Orthophenanthroline Indicator Solution (0.5 % in
water)—Orthophenanthroline ferrous complex (ferroin) shall
5.5 Perchloric Acid (70 %)—Concentrated perchloric acid
be used as the indicator.
(HClO ).
9. Procedure
6. Hazards
9.1 Weigh accurately (Note 2) 0.15 g of the sample and
6.1 Warning—Concentrated mineral acids cause burns of
place in a 250-mL, vented, glass-stoppered Erlenmeyer flask
the skin and eyes. Concentrated bases are also hazardous.
previously filled with carbon dioxide (CO ) or other inert gas.
Avoidcontactwithskinoreyes.Incaseofcontactimmediately 2
Addafewsmallglassbeadsand10mLofFeCI solution.Heat
flush skin or eyes with plenty of water. See appropriate MCA 3
gently for 15 min, stirring occasionally and maintaining at all
Safety Data Sheets for further information before handling
times an atmosphere of CO or other inert gas.
dangerous chemicals. 2
NOTE 2—The use of a 0.4-mLmicro beaker for weighing the specimen
6.2 Chemicals that have been declared toxic should be
is advised. The beaker is weighed first and the sample introduced into the
disposed of as hazardous chemicals and not discharged into a beaker, the correct weight obtained, and the entire beaker and its contents
dropped into the flask. This eliminates errors in weighing caused by
sink.
brushing the sample from glass balance pans.
TOTAL COPPER
9.2 After the specimen has been dissolved, cool, add 50 mL
of distilled water, and titrate at once with 0.1 N ceric ammo-
7. Procedure
nium nitrate solution until near the end point. Add 2 drops of
orthophenanthroline indicator solution and complete the titra-
7.1 Weigh accurately 1.0 g of the sample and transfer to a
tion. A sharp, distinct color change from orange to pale green
300-mL electrolytic beaker. Add 10 mL of concentrated nitric
occurs at the end point. Back-titrate with 0.03 N ferrous
acid (HNO ) and boil several minutes. Add 10 mL of HClO
3 4
ammonium sulfate solution to the orange color.
(70 %) and fume for 5 min. Cool, dilute to a volume of
approximately 150 mL, and add 1 mL of HNO and1gof
9.3 Calculation—Calculate the percent of total reducing
(NH ) SO .
4 2 4
power, A, as cuprous oxide (Cu O) as follows:
7.2 Carefully weigh the platinum electrode to 0.1 mg.
V N 2 V N 3 0.07154
1 1 2 2
A 5 3 100 (1)
Electroplate the copper on a rotating platinum electrode at a
S
current of 2 A for 2 h. Dilute with water and continue the
where:
electrolysis for 15 min. When the deposition is complete,
V = Ce(NH ) (NO ) solution required to titrate the
remove the electrode, wash with water and acetone, dry, and
1 4 2 3 6
specimen, mL,
weigh to 0.1 mg. Save the electrolyte for the determination of
N = normality of the Ce(NH ) (NO ) solution,
metals other than copper (Section 15).
1 4 2 3 6
V = Fe(NH ) (SO ) solution required for back-
2 4 2 4 2
7.3 Calculate the percent of total copper, Cu.
titration, mL,
N = normality of the Fe(NH ) (SO ) solution,
2 4 2 4 2
TOTAL REDUCING POWER AS CUPROUS OXIDE
S = specimen weight, g, and
0.07154 = equivalent weight of Cu O/1000.
8. Reagents
METALLIC COPPER
8.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)—
Mix 54.826 g of ceric ammonium nitrate (Ce(NH ) (NO ) )
4 2 3 6
10. Reagents
(either reagent grade or reference standard purity) with 56 mL
of sulfuric acid (H SO ) (1+1). Dissolve the salt and acid in
2 4 10.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)—
water, cool to room temperature, and dilute to 1 L. Standardize
See 8.1.
this solution against analyzed bright copper foil that has been
10.2 Denatured Alcohol (Formula No. 2B).
freed from all oxide coating.
8.2 Ferric Chloride Solution—Dissolve 75 g of ferric chlo-
ride (FeCI ·6H O) in a mixture of 150 mL of hydrochloric
3 2
This test method is based on the procedure described by Irvin Baker and R.
acid (HCl) (sp gr 1.19) and 400 mL of distilled water. Add 5
Stevens Gibbs, “Determination of Metallic Copper in Cuprous Oxide—Cupric
mL of hydrogen peroxide (H O ) (30 %) and boil to remove
2 2 Oxide Mixtures,” Industrial and Engineering Chemistry,Analytical Edition,Vol 13,
the excess. February 15, 1946, p. 124.
D283 − 13 (2019)
10.3 Extraction Solution—Add40mLofHCl(spgr1.19)to orthophenanthroline indicator solution. Titrate with 0.1 N ceric
1Lofdenaturedalcohol.Mixthoroughly.Add40gofstannous ammoniumnitratesolutionuntilthecolorchangesfromorange
chloride (SnCI ·2H O) and stir until completely dissolved. to pale green.
2 2
11.6 Calculation—Calculate the percent of metallic copper
10.4 Ferric Chloride Solution—See 8.2.
content, B, as follows:
10.5 Orthophenanthroline Indicatior—See 8.4.
V C
B 5 3 100 (2)
S
11. Procedure
where:
11.1 Add approximately 20 mL of 4-mm diameter glass
beads to a 250-mL Phillips beaker (assay flask). Weigh V = ceric ammonium nitrate solution required for titration
of the sample, mL,
accurately 0.15 g of sample on a tared, glazed paper approxi-
C = copper equivalent of the ceric ammonium nitrate
mately 13 mm square or a small watch glass that will fit into
solution, g/mL, and
the Phillips beaker, and transfer the specimen and paper or
S = specimen weight, g.
watch glass to the beaker. 2
11.2 Add 25 mL of denatured alcohol and swirl vigorously
CUPROUS OXIDE
for approximately 1 min to remove any surface coating and
12. Calculation
break up lumps. While swirling the flask, slowly add 100 mL
of the extraction solution.
12.1 Calculate the percent of cuprous oxide (Cu O), D,as
follows:
11.3 After the addition of the extraction solution, swirl the
flask vigorously for 5 min, adding lumps of dry ice (solid
D 5 A 2 2.252B (3)
carbondioxide)(Note3)continuouslyduringthistimetolower
where:
the temperature of the solution to approximately –10°C. Break
A = total reducing power as cuprous oxide (Section 9), %
up any lumps in the solution with a glass rod or policeman.
and
11.4 Filter off the metallic copper-cupric oxide residue
B = metallic copper (Section 11), %.
using a 125-mm close-texture paper, a filter cone to support the
CUPRIC OXIDE
paper, and suction (Note 4). Continue the addition of dry ice to
the flask and filter paper during the filtration to keep the
13. Calculation
solution cold. Wash the flask and filter paper with 150 to 200
mL of denatured alcohol, continuing the use of suction. 13.1 Calculate the percent of cupric oxide (CuO), E,as
NOTE 3—During the 5-min swirling period approximately 25 to 30 g of
follows:
dryiceisaddedinapproximately5-gportions.Theinitiallumpsofdryice
E 5 1.252 F 2 B 2 1.112D (4)
~ !
volatilizerapidlyduetothetemperatureofthesolution.Approximately15
g of dry ice is added in the first 2 min with a subsequent temperature drop
where:
to 0°C. The remaining 15 g volatilizes more slowly and gradually lowers
F = total copper (Section 7), %,
the temperature to the vicinity of –10°C. These directions are not critical,
but merely serve as a guide. The solution must be kept very cold in order B = metallic copper (Section 11), %, and
to obtain correct and reproducible results. During the filtration period,
D = cuprous oxide (Section 12), %.
additions of dry ice to the flask should be continued to keep the solution
cold until all of the extraction solution has been filtered.
METALS OTHER THAN COPPER
NOTE 4—In the great majority of cases, the metallic copper-cupric
oxide residue is completely retained by the use of a suitable close-texture
14. Reagents
filter paper. The filtration is rapid and can be readily completed in 5 min
14.1 Ceric Ammonium Nitrate, Standard Solution (0.1 N)—
with proper suction. The filtrate should be carefully examined for the
presence of finely divided particles of copper. In the event that extremely 8.1.
See
finely divided particles of copper are present and pass through the filter
14.2 Diphenylamine Indicator—Dissolve1gof diphel-
paper,asevidencedbythepresenceinthefiltrateofareddishcolor,which
nylamine in 100 mL of H SO (sp gr 1.84).
may be transient, the following method of filtration should be used: Place
2 4
a 25-mm diameter, beveled-edge, perforated porcelain filter disk in a 60°,
14.3 Potassium Ferricyanide Solution (50 g/L)—Dissolve 5
75-mmdiameterglassfunnel.Usingsuction,prepareanasbestosfilterpad
g of potassium ferricyanide (K Fe(CN) ), in 100 mL of
on the porcelain disk of sufficient thickness and retentiveness to hold the
3 6
finelydividedresidue.Washtheasbestospadseveraltimeswithdenatured distilled water. Keep tightly stoppered in a dark bottle.
alcohol to remove all water from the pad. Filter the metallic copper-cupric
14.4 Potassium Ferrocyanide, Standard Solution (1 mL =
oxide residue on this asbestos pad with the suction on at the start of
0.001 g Zn)—Dissolve 5.0 g of potassium ferrocyanide
filtration. Keep the solution
...
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