Designation: D3280 − 85 (Reapproved 2014)

Standard Test Methods for

Analysis of White Zinc Pigments1
This standard is issued under the fixed designation D3280; 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 D280 Test Methods for Hygroscopic Moisture (and Other

1.1 These test methods cover procedures for the analysis of Matter Volatile Under the Test Conditions) in Pigments
white zinc pigments. D1193 Specification for Reagent Water
D1394 Test Methods for Chemical Analysis of White Tita-
1.2 The analytical procedures appear in the following order: nium Pigments
Section E11 Specification for Woven Wire Test Sieve Cloth and Test
Preparation of Sample 6
Zinc Oxide
Sieves
Total Zinc, Using Diphenylamine as Internal Indicator 7
Total Zinc, Using Uranyl Acetate as External Indicator 8 3. Summary of Test Method
Total Impurities 9
Total Sulfur 10 3.1 Zinc Oxide:
Moisture and Other Volatile Matter 11 3.1.1 Total Zinc—Determined using diphenylamine as an
Leaded Zinc Oxide
Total Lead 12 internal indicator and also using uranyl acetate as an external
Total Zinc 13 indicator. Total impurities are calculated.
Total Sulfur 14 3.1.2 Total Sulfur—Determined as BaSO4 and calculated to
Total Impurities 15
Moisture and Other Volatile Matter 16 sulfur.
Water-Soluble Salts 17 3.1.3 Moisture and Volatile Matter—Determined in accor-
Zinc Sulfide dance with Method A of Test Methods D280.
Zinc Oxide 18
Zinc Sulfide 19 3.2 Leaded Zinc Oxide:
Water-Soluble Salts 20
Moisture and Other Volatile Matter 21
3.2.1 Total Lead—Determined as PbSO4 and calculated to
Barium Sulfate 22 percent PbO.
Titanium Dioxide 23 3.2.2 Total Zinc—Determined on the filtrate from procedure
1.3 The values stated in SI units are to be regarded as the in 13.2.1 in accordance with methods in Sections 7 or 8.
standard. The values given in parentheses are for information 3.2.3 Total Sulfur—Determined as BaSO4 and calculated to
only. percent SO3.
1.4 This standard does not purport to address all of the 3.2.4 Total Impurities—Calculated from compositional data.
safety concerns, if any, associated with its use. It is the 3.2.5 Moisture and Other Volatile Matter—Determined in
responsibility of the user of this standard to establish appro- accordance with Method A of Test Methods D280.
priate safety and health practices and determine the applica- 3.2.6 Water Soluble Salts—Determined gravimetrically.
bility of regulatory limitations prior to use. 3.3 Zinc Sulfide:
3.3.1 Total Zinc—Determined using uranyl acetate external
2. Referenced Documents indicator in accordance with Section 9.
2.1 ASTM Standards:2 3.3.2 Zinc Sulfide—Determined in accordance with Sections
8 or 9 and calculating ZnO to ZnS.
3.3.3 Water Soluble Salts—Determined in accordance with
1
These test methods are under the jurisdiction of ASTM Committee D01 on Section 18.
Paint and Related Coatings, Materials, and Applications and are the direct 3.3.4 Moisture—Determined in accordance with Method A
responsibility of Subcommittee D01.31 on Pigment Specifications.
Current edition approved Dec. 1, 2014. Published December 2014. Originally of Test Methods D280.
approved in 1973. Last previous edition approved in 2009 as D3280 – 85 (2009). 3.3.5 Barium Sulfate—The sample is treated with N2SO4
DOI: 10.1520/D3280-85R14.
2
and Na2CO3 and the residue of BaCO3 is dissolved in NCl and
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
(NH4)2SO4 added to precipitate BaSO4, which is weighed.
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on 3.3.6 Titanium Dioxide—Determined in accordance with
the ASTM website. Test Methods D1394.

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 D3280 − 85 (2014)
4. Significance and Use NOTE 1—Detailed requirements for this sieve are given in Specification
E11.
4.1 White zinc pigments find considerable use in white
paints, and as such it is useful to formulators and users to be 6.3 Preserve all samples in stoppered bottles or containers.
able to monitor the amounts of these pigments in whole paints. ZINC OXIDE
It is also of interest to raw material suppliers and paint
producers to check the specifications of each pigment. 7. Total Zinc, Using Diphenylamine as Internal Indicator
5. Reagents 7.1 Reagents:
5.1 Purity of Reagents—Reagent grade chemicals shall be 7.1.1 Diphenylamine Indicator Solution (10 g/L))—
used in all tests. Unless otherwise indicated, it is intended that Dissolve 1 g of diphenylamine in 100 mL of H2SO4.
all reagents shall conform to the specifications of the Commit- 7.1.2 Potassium Ferrocyanide (1 mL = 0.008 g Zn)—
tee on Analytical Reagents of the American Chemical Society, Dissolve 35 g of K4Fe(CN)6·3H2O in water and dilute to 1 L
where such specifications are available.3 Other grades may be and add 0.3 g of potassium ferricyanide (K3Fe(CN)6). Stan-
used, provided it is first ascertained that the reagent is of dardize the solution by titrating against zinc (320 to 340 mg),
sufficiently high purity to permit its use without lessening the following the procedure described in 7.2. Calculate the grams
accuracy of the determination. of zinc equivalent to 1.00 mL of the solution.
5.2 Purity of Water—Unless otherwise indicated, references 7.2 Procedure—Weigh to 0.1 mg about 0.4 g of the sample
to water shall be understood to mean Type II reagent grade into a tall form 400-mL beaker. Moisten with about 20 mL of
water conforming to Specification D1193. water, and dissolve in 15 mL of HCl. Neutralize with NH4OH,
using litmus as the indicator. Add an excess of 15 mL of H2SO4
5.3 Concentration of Reagents: (1+2) and dilute to 200 mL. Heat to approximately 60°C, add
5.3.1 Concentrated Acids and Ammonium Hydroxide— 2 drops of diphenylamine indicator solution and while stirring
When acids and ammonium hydroxide are specified by name vigorously, titrate with K4Fe(CN)6 solution to the color change
or chemical formula only it should be understood that concen- from purple to a persistent yellowish green.
trated reagents of the following specific gravities or concen-
trations are intended: NOTE 2—The true end point is a sharp, persistent change from a purple
to a yellowish green. At the beginning of the titration, a deep blue color
Acetic acid, HC2H3O2 99.5 %
is developed after addition of a few millilitres of K4Fe(CN)6 solution.
Hydrochloric acid, HCl sp gr 1.19
Hydrofluoric acid, HF 48 %
About 0.5 to 1.0 mL before the true end point is reached, the solution
Nitric acid, HNO3 sp gr 1.42 changes from a blue to a purple color. After the purple color is developed,
Sulfuric acid, H2SO4 sp gr 1.84 the titration should be continued dropwise to the persistent yellowish
Ammonium hydroxide, NH4OH sp gr 0.90 green end point.
The desired specific gravities or concentrations of all other 7.3 Calculation—Calculate the percent total zinc as ZnO, A,
concentrated acids are stated whenever they are specified. as follows:
5.3.2 Diluted Acids and Ammonium Hydroxide—
Concentrations of diluted acids and ammonium hydroxide,
except when standardized, are specified as a ratio stating the
A5 F S1 G
V 2 Z 3 1.245
3 100 (1)

number of volumes of the concentrated reagents to be diluted where:

with a given number of volumes of water, as in the following V2 = K4Fe(CN)6 solution required for titration of the
example: HCl (1+99) means 1 volume of concentrated HCl (sp specimen, mL,
gr 1.19) diluted with 99 volumes of water. Z = zinc equivalent of the K4Fe(CN)6 solution, g/mL,
S1 = specimen weight, and
6. Preparation of Sample 1.245 = molecular weight ZnO (81.38)/molecular weight Zn
6.1 Grind dry pigments, if lumpy or not finely ground, to a (65.38).
fine powder for analysis. Large samples may be thoroughly
mixed and a representative portion taken and powdered if 8. Total Zinc, Using Uranyl Acetate as External Indicator
lumpy or not finely ground. Mix the sample in all cases 8.1 Reagents:
thoroughly before taking specimens for analysis. 8.1.1 Uranyl Acetate Indicator Solution (50 g/L)—Dissolve
6.2 Separate pigments from paints or pastes, grind to a fine 5 g of UO2(C2H3O2)2·2H2O in 100 mL of water and make
powder, pass through a 180-µm (No. 80) sieve (Note 1) to slightly acid with acetic acid.
remove any skins, thoroughly mix, and oven dry at 105°C. 8.1.2 Potassium Ferrocyanide, Standard Solution (1
Moisten such pigments after weighing with a little alcohol mL = 0.008 g Zn)—Prepare and standardize as in 7.1.2. Run a
before adding reagents for analysis. blank titration with the same amounts of reagents and water.
Calculate the zinc equivalent of the solution as follows:
3
Reagent Chemicals, American Chemical Society Specifications, American Z 5 W/ ~ V 2 B ! (2)
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory where:
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia Z = zinc equivalent of the K4Fe(CN)6 solution, g/mL,
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
W = zinc used,
MD.

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 D3280 − 85 (2014)

V = K4Fe(CN)6 solution required for titration of the zinc, 10.3 Calculation—Calculate the percent sulfur, A, as fol-
mL, and lows:
B = K4Fe(CN)6 solution required for titration of the blank,
mL. A5 F~ S2 G
P 3 0.1374!
3 100 (5)

8.2 Procedure: where:

8.2.1 Weigh to 0.1 mg about 0.4 g of the sample into a
P = BaSO4 precipitate, g,
tall-form 400-mL beaker. Moisten with about 20 mL of water
S2 = specimen weight, g, and
and dissolve by adding 10 mL of HCl. Add NH4OH until 0.1374 = molecular weight of sulfur (32.064)/molecular
slightly alkaline to litmus paper. Add HCl until just acid, and weight BaSO4 (233.43).
then add 3 mL in excess. Dilute to about 250 mL with hot water
and heat nearly to boiling. Titrate with K4Fe(CN)6 solution,
11. Moisture and Other Volatile Matter
stirring constantly, until a drop of uranyl acetate indicator
tested in a white porcelain spot plate shows a brown tinge after 11.1 Procedure—Determine moisture and other volatile
standing 1 min. matter in accordance with Method A of Test Methods D280.
8.2.2 Blank—Run a blank titration with the same amounts
of reagents and water. LEADED ZINC OXIDE
8.3 Calculation—Calculate the percent total zinc as ZnO, A, 12. Total Lead
as follows:
12.1 Procedure:
A5 F ~~ V 2 B ! Z 3 1.245!
S G 3 100 (3) 12.1.1 Weigh to the nearest 0.1 mg about 0.5 g of the sample
into a 400-mL beaker. Dissolve in 250 mL of water and 20 mL
where: of HNO3 (Note 2). Add 5 mL of H2SO4 and evaporate to dense
V = K4Fe(CN)6 solution required for titration of the white fumes. Cool, add 50 mL of 95 % alcohol and 200 mL of
sample, mL, water, and let stand cold 1 to 2 h. Filter, using a weighed Gooch
S = sample used, g, and crucible. Wash the precipitate with H2SO4 (1+99) and combine
1.245 = molecular weight ZnO (81.38)/molecular weight Zn the filtrate and washings. If the zinc content of the sample is
(65.38). known to be 40 % or over, reserve the filtrate and washings for
the determination of total zinc (Section 13).
9. Total Impurities
9.1 Calculation—Calculate the percent total impurities, A, NOTE 3—If the sample contains calcium or barium, the lead and zinc
should be separated by precipitation with H2S after solution in HCl,
as follows: making alkaline with NH4OH and then acid with acetic acid. Dissolve the
A 5 100 2 ~ L1Z 1 1S 5 ! (4) PbS and ZnS in dilute HNO3 and determine the lead and zinc as above.

where: 12.1.2 Ignite the precipitate in the crucible at dull red heat
(550 6 50°C) for 20 min, cool, and weigh.
L = total lead as PbO, %,
Z1 = total zinc as ZnO, %, and 12.2 Calculation—Calculate the percent total lead as PbO,
S5 = total sulfur as SO3, %. A, as follows:
10. Total Sulfur
10.1 Reagents:
A5 F~ S3 G
P 1 3 0.736!
3 100 (6)

10.1.1 Bromine Water (saturated). where:

10.1.2 Aluminum—Reagent grade granular aluminum. P1 = PbSO4 precipitate, g,
10.1.3 Barium Chloride Solution (100 g BaCl2 L)—Dissolve S3 = sample used, g, and
117 g BaCl2·2H2O in water and dilute to 1 L. 0.736 = molecular weight PbO (223.21)/molecular weight
10.2 Procedure: PbSO4 (303.28).
10.2.1 Weigh to 0.1 g about 10 g of the sample into a 400-
mL beaker. Add 50 mL of saturated bromine water, 100 mL of 13. Total Zinc
water, and 35 mL of HCl. Boil until all the bromine has been 13.1 Reagents—See 7.1 or 8.1, whichever is applicable.
expelled, cool, and add 3 to 5 g of granular aluminum. Heat to
boiling, filter, and wash well with hot water. 13.2 Procedure:
10.2.2 Dilute the filtrate to 300 mL with water, neutralize 13.2.1 If the zinc content of the sample is known to be 40 %
with NH4OH, and add 6 drops of HCl. Heat to boiling and add or over, determine zinc on the filtrate obtained in 12.1.1. If the
25 mL of hot BaCl2 solution dropwise, with constant stirring. zinc content is known to be under 40 %, weigh to the nearest
Allow to stand in a warm place for at least 2 h. 0.1 mg about 1 g of the sample, precipitate and filter off the
10.2.3 Filter, using a weighed Gooch crucible, or a fine lead as PbSO4 as described in 12.1.1, and determine zinc on the
textured filter paper and wash well with hot water. Dry and filtrate.
ignite in a muffle furnace for 30 min. Cool and weigh as 13.2.2 Evaporate the appropriate filtrate to dryness and
BaSO4. determine zinc as directed in Sections 7 or 8.

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 D3280 − 85 (2014)
14. Total Sulfur
14.1 Reagents—See 10.1.3.
W5 F~ S5 G
R 2 B 2!
3 100 (9)

14.2 Procedure: where:

14.2.1 Weigh to the nearest 0.1 mg about 1 g of the sample, R = dry salts obtained from the sample, g,
into a 400-mL beaker. Add 10 mL of water, 3 g of NH4Cl, and B2 = water-soluble salts obtained from the blank, g, and
5 mL of HCl saturated with bromine. Heat on a steam bath for S5 = sample represented in the aliquot used, g.
about 15 min. Add 50 mL of water, neutralize with dry Na2CO3
ZINC SULFIDE
in excess. Boil 10 to 15 min. Allow to settle, dilute to 250 mL
with hot water, filter, and wash with hot water.
14.2.2 Redissolve the residue in HCl, reprecipitate as 18. Zinc Oxide
before, and wash with hot water. Acidify the combined filtrates 18.1 Reagents—See 8.1.
with HCl, adding 5 mL in excess. Boil 10 to 15 min. Neutralize 18.2 Procedure:
with NH4OH and add 6 drops excess HCl. Heat to boiling and
18.2.1 Weigh to 1 mg about 5 g of the sample into a 500-
add 25 mL of hot BaCl2 solution dropwise, with constant
mL Erlenmeyer flask and add 200 mL of acetic acid (3+97).
stirring. Allow to stand in a warm place for at least 2 h.
Shake continuously for 20 min and transfer to a 500-mL
14.2.3 Filter, using a weighed Gooch crucible or a fine
volumetric flask. Dilute to the mark and filter through a dry,
textured filter paper, and wash well with hot water. Dry and
fine paper.
ignite in a muffle furnace for 30 min. Cool and weigh.
18.2.2 Transfer 400 mL of the clear filtrate to a 600-mL
14.3 Calculation—Calculate the percent sulfur as SO3, A, as beaker. Add 20 mL of HCl and neutralize with NH4OH, using
follows: litmus paper. Add HCl until just acid and then add 3 mL in
A5 F~ P 2 3 0.343!
S4 G3 100 (7)
excess. Heat nearly to boiling and titrate with K4Fe(CN)6
solution as described in 8.2.
where: 18.3 Calculation—Calculate the percent zinc oxide, A, as
P2 = BaSO4 precipitate, g, follows:
S4 = specimen weight, g, and
0.343 = molecular weight SO3 (80.07)/molecular weight A5 F ~~ V 3 2 B 3 ! Z 3 1.245!
S6 G
3 100 (10)
BaSO4 (233.43).
where:
15. Total Impurities V3 = K4Fe(CN)6 solution required for titration of the
specimen, mL,
15.1 Calculation—Calculate the percent of total impurities,
B3 = K4Fe(CN)6 solution required for titration of the
A, as follows:
blank, mL,
A 5 100 2 ~ L1Z 1 1S 5 ! (8) Z = zinc equivalent of the K4Fe(CN)6 solution, g/mL,
S6 = sample represented in the aliquot used, g, and
where: 1.245 = molecular weight ZnO (81.38)/molecular weight Zn
L = total lead as PbO, %, (65.38).
Z1 = total zinc as ZnO, %, and
S5 = total sulfur as SO3, %. 19. Zinc Sulfide
16. Moisture and Other Volatile Matter 19.1 Reagents—See Section 7 or 8, whichever is applicable.
16.1 Procedure—Determine moisture and other volatile 19.2 Procedure—Weigh to the nearest 0.1 mg a portion of
matter in accordance with Method A of Test Methods D280. the sample into a tall-form 400-mL beaker. Moisten with water,
add 10 mL of H2SO4 (1+1), and evaporate to dryness. Cool,
17. Water-Soluble Salts and proceed as directed in 7.2 or 8.2.
17.1 Procedure: 19.3 Calculation—Calculate the percent zinc sulfide, C, as
17.1.1 Weigh to the nearest 1 mg about 5 g of the sample follows:
into a 500-mL graduated flask. Add 250 mL of water at room
temperature and shake for 10 min. Dilute the solution to the
mark with water, mix by shaking, and filter through a dry, fine
C5 F ~~ V 4 2 B 4 ! Z 3 1.491!
S7 G
3 100 2 1.20A (11)

paper. where:
17.1.2 Transfer 400 mL of the clear filtrate to a weighed V4 = K4Fe(CN)6 solution required for titration of the
platinum dish and evaporate to dryness at 105 6 2°C, cool in specimen, mL,
a desiccator, and weigh rapidly. B4 = K4Fe(CN)6 solution required for titration of the
17.1.3 Blank—Make a blank determination at the same time blank, mL,
in a similar manner. Z = zinc equivalent of the K4Fe(CN)6 solution, g/mL,
17.2 Calculation—Calculate the percent water-soluble salts, S7 = sample used, g,
A = percent of zinc oxide (Section 17),
W, as follows:

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1.20 = factor for conversion of percentage of ZnO to the burner. Cool and leach the fusion with 200 mL of hot water in
ZnS equivalent, and a 400-mL beaker. Filter and wash with hot Na2CO3 solution.
1.491 = molecular weight ZnS (97.44)/molecular weight Zn 22.2.3 Dissolve the BaCO3 with hot HCl (1+4), catching the
(65.38). filtrate in a 600-mL beaker. Wash the paper with water.
Neutralize with NH4OH, using methyl orange as the indicator.
20. Water-Soluble Salts Add HCl until just acid and then add 6 drops in excess. Dilute
to 400 mL, heat to boiling, and add 25 mL of hot (NH4)2SO4
20.1 Procedure—Determine water-soluble salts as directed
solution slowly, while stirring. Allow to stand in a warm place
in Section 17.
for at least 4 h.
22.2.4 Filter off the precipitate, using a weighed Gooch
21. Moisture crucible or a fine textured filter paper, and wash with hot water
21.1 Procedure—Determine moisture and other volatile until free of chlorides. Dry, ignite in a muffle furnace for 30
matter in accordance with Method A of Test Methods D280. min, cool, and weigh.
22.3 Calculation—Calculate the percent barium sulfate
22. Barium Sulfate (BaSO4), A, as follows:
22.1 Reagents:
22.1.1 Ammonium Sulfate Solution (30 g/L)—Dissolve 30 g A5 S DP3
S8
3 100 (12)
of (NH4)2SO4 in water and dilute to 1 L.
22.1.2 Methyl Orange Indicator Solution—Dissolve 0.1 g of where:
methyl orange in 100 mL of water. Filter if necessary. P3 = BaSO4 precipitate, g, and
22.1.3 Sodium Carbonate Solution (2 g/L)—Dissolve 2 g of S8 = sample used, g.
Na2CO3 in water and dilute to 1 L. 23. Titanium Dioxide
22.2 Procedure: 23.1 Procedure—Determine titanium dioxide in accordance
22.2.1 Weigh to the nearest 1 mg about 1 g of the sample with Sections 9 to 13 of Test Methods D1394. If the pigment
into a 400-mL beaker. Moisten with water, and add 100 mL of being analyzed is relatively low in TiO2, the use of a larger
H2SO4 (1+1), and evaporate to dryness. Cool, add 200 mL of specimen than that specified in Test Methods D1394 should
water, and carefully break up the residue. Boil for 15 min. give more accurate results.
Filter, and wash with water.
22.2.2 Transfer the residue and paper to a platinum crucible 24. Keywords
and burn off the paper. Cool, add 6 g of Na2CO3, and mix. 24.1 analysis; barium sulfate; lead; sulfur; uranyl acetate;
Cover with 2 g of Na2CO3, and fuse for 40 min over a Meker white zinc pigment; zinc

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