ASTM D1394-76(1999)
(Test Method)Standard Test Methods for Chemical Analysis of White Titanium Pigments
Standard Test Methods for Chemical Analysis of White Titanium Pigments
SCOPE
1.1 These test methods cover procedures for the chemical analysis of white titanium dioxide pigments.
1.2 The analytical procedures appear in the following order: Sections Preparation of Sample 4 Qualitative Analysis 5 and 6 Moisture 7 Total Titanium: Jones Reductor Method 8 to 12 Aluminum Reduction Method 13 to 17 Aluminum Oxide 18 to 22 Silica 23 to 29
1.3 This standard does not purport to address all of the safety problems, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.> A specific hazard statement is given in Section 19.
General Information
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Standards Content (Sample)
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Designation: D 1394 – 76 (Reapproved 1999)
Standard Test Methods for
Chemical Analysis of White Titanium Pigments
This standard is issued under the fixed designation D 1394; 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.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope where such specifications are available. Other grades may be
used, provided it is first ascertained that the reagent is of
1.1 These test methods cover procedures for the chemical
sufficiently high purity to permit its use without lessening the
analysis of white titanium dioxide pigments.
accuracy of the determination.
1.2 The analytical procedures appear in the following order:
3.2 Unless otherwise indicated, references to water shall be
Sections
understood to mean reagent water conforming to Type IV of
Preparation of Sample 4
Qualitative Analysis 5 and 6
Specification D 1193.
Moisture 7
Total Titanium:
4. Preparation of Sample
Jones Reductor Method 8-12
Aluminum Reduction Method 13-17
4.1 The sample shall, in all cases, be thoroughly mixed and
Aluminum Oxide 18-22
comminuted before taking portions for analysis.
Silica 23-29
1.3 This standard does not purport to address all of the QUALITATIVE ANALYSIS
safety concerns, if any, associated with its use. It is the
5. Reagents
responsibility of the user of this standard to establish appro-
5.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
priate safety and health practices and determine the applica-
monium hydroxide (NH OH).
bility of regulatory limitations prior to use. A specific hazard
5.2 Ammonium Sulfate—((NH ) SO ).
statement is given in Section 19.
4 2 4
5.3 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
2. Referenced Documents
chloric acid (HCl).
5.4 Hydrogen Peroxide (30 %)—Concentrated hydrogen
2.1 ASTM Standards:
D 280 Test Methods for Hygroscopic Moisture (and Other peroxide (H O ).
2 2
5.5 Hydrogen Sulfide (H S).
Matter Volatile Under the Test Conditions) in Pigments
D 1193 Specification for Reagent Water 5.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
E 50 Practices for Apparatus, Reagents, and Safety Precau- (H SO ).
tions for Chemical Analysis of Metals 5.7 Sulfuric Acid (1+19)—Carefully mix 1 volume of
H SO (sp gr 1.84) with 19 volumes of water.
3. Reagents
5.8 Tartaric Acid.
3.1 Purity of Reagent—Reagent grade chemicals shall be 5.9 Tin or Zinc Metal.
used in all tests. Unless otherwise indicated, it is intended that
6. Procedure
all reagents shall conform to the specifications of the Commit-
tee on Analytical Reagents of the American Chemical Society, 6.1 Place about 0.5 g of the sample in a 250-mL glass
beaker, and add 20 mL of H SO (sp gr 1.84) and 7 to8gof
2 4
(NH ) SO . Mix well and boil for a few minutes. The sample
4 2 4
should go completely into solution; a residue denotes the
These test methods are under the jurisdiction of ASTM Committee D-1 on
presence of silicon dioxide (SiO ) or siliceous matter. Cool the
Paints and Related Coatings, Materials, and Applications and are the direct
solution, dilute with 100 mL of water, heat to boiling, let settle,
responsibility of Subcommittee D01.31 on Pigment Specifications.
filter, wash with hot H SO (1+19) until free of titanium, and
Current edition approved June 25, 1976. Published August 1976. Originally
2 4
published as D 1394 – 56 T. Last previous edition D 1394 – 75.
Annual Book of ASTM Standards, Vol 06.03.
Reagent Chemicals, American Chemical Society Specifications, American
Annual Book of ASTM Standards, Vol 11.01.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Annual Book of ASTM Standards, Vol 03.05.
listed by the American Chemical Society, see Analar Standards for Laboratory
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD.
Borosilicate glass has been found satisfactory for this purpose.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
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.
D 1394
test the residue for lead, etc.
6.2 Test the filtrate for calcium, zinc, iron, chromium, etc.,
by the regular methods of qualitative analysis. For the iron
determination add to a portion of the filtrate5gof tartaric acid,
render slightly ammoniacal, pass in H S in excess, and digest
on a steam bath. No precipitate after 30 min indicates the
absence of iron, nickel, cobalt, lead, copper, etc. A black
precipitate readily soluble in dilute HCl denotes iron. For
titanium, test a small portion of the original filtrate with H O
2 2
(a clear yellow-orange color should result) and another portion
with metallic tin or zinc (a pale blue to violet coloration should
result). Negative results should be shown for sulfide, carbon-
ate, or appreciable water-soluble matter.
MOISTURE
7. Procedure
7.1 Determine moisture and other volatile matter in accor-
dance with Test Method A of Test Methods D 280.
TOTAL TITANIUM BY THE JONES REDUCTOR
METHOD
8. Scope
8.1 This method gives results similar to those obtained with
the Aluminum Reduction Method, Sections 13-17.
9. Apparatus
9.1 Jones Reductor having a zinc column at least 450 mm
FIG. 1 Jones Reduction
in length, and 19 mm in diameter (Fig. 1 and Fig. 2). The
filtering pad must be tight enough to hold all the particles of
amalgamated zinc resting on it, and may be made of asbestos
H SO , and heat to dense white fumes. Cool, dilute with water
2 4
or, preferably, glass-wool supported by platinum gauze or a
to 1 L, digest on a steam bath until sulfates are dissolved, and
perforated porcelain plate. Use the least amount (0.1 to 1.0 %)
filter if necessary. To oxidize any ferrous iron that may be
of mercury that will enable satisfactory control of hydrogen
present, add 0.1 N KMnO solution until a faint pink color
evolution, since heavy amalgamation tends to reduce the rate
persists for 5 min. Ferric ammonium sulfate (FeNH (SO ) ·
4 4 2
of reaction. Prepare the amalgam by washing 20-mesh zinc for
12H O) may also be used to prepare this solution (See 15.4).
1 min in enough 1 N HCl to cover it, adding the proper amount
10.5 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
of 0.25 M mercuric nitrate or chloride solution, and stirring
chloric acid (HCl).
rapidly for 3 min. Decant the solution and wash the amalgam
10.6 Iron or Carbon Steel—Pure iron or plain carbon steel.
with water and store under water to which a few drops of HCl
10.7 Nitric Acid (sp gr 1.42)—Concentrated nitric acid
have been added. After using, keep the reductor filled with
(HNO ).
water when not in use, in order that basic salts will not be
10.8 Sodium Oxalate—National Institute of Standards and
formed and clog it.
Technology standard reference material No. 40 of sodium
oxalate (Na C O ).
2 2 4
10. Reagents
10.9 Potassium Permanganate, Standard Reference Mate-
10.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
rial (0.1 N,1mL 5 0.008 g TiO )—Dissolve 3.16 g of KMnO
2 4
monium hydroxide (NH OH).
in water and dilute to 1 L. Let stand 8 to 14 days, siphon off the
10.2 Ammonium Sulfate ((NH ) SO ).
clear solution (or filter through sintered glass, medium poros-
4 2 4
10.3 Carbon Steel or Iron—Pure iron or plain carbon steel.
ity), and standardize against the National Bureau of Standards
10.4 Ferric Sulfate Solution (1 mL 5 0.02 g Fe)—Dissolve
standard sample No. 40 of sodium oxalate (Na C O)as
2 2 4
20 g of iron or carbon steel in a slight excess of HCl, oxidize
follows: In a 400-mL beaker dissolve 250 to 300 mg Na C O
2 2 4
with approximately 12 mL of HNO , add about 80 mL of
in 250 mL of hot water (80 to 90°C) and add 15 mL of H SO
2 4
(1+1). Titrate at once with the KMnO solution, stirring the
liquid vigorously and continuously. The KMnO solution must
Treadwell, F. P., and Hall, William T., Qualitative Analysis, John Wiley & Sons,
not be added more rapidly than 10 to 15 mL/min, and the last
Inc., New York, NY, Vol. 1, Ninth English Ed., 1937.
0.5 to 1 mL must be added dropwise with particular care to
Directions for preparing a Jones Reductor may be found in Hillebrand, W. F.,
allow each drop to be fully decolorized before the next is
et al., Applied Inorganic Analysis, John Wiley & Sons, Inc., New York, NY, Second
Ed., 1953, p. 108. introduced. The solution shall not be below 60°C by the time
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.
D 1394
weigh as rapidly as possible. Calculate the dry weight of the
specimen and use in the actual calculation.
11.3 Transfer the dried specimen to a dry 250 mL chemical-
and heat-resistant glass beaker, add 20 mL of H SO (sp gr
2 4
1.84) and 7 to8gof(NH ) SO . Mix well and heat on a hot
4 2 4
plate until dense white fumes are evolved, and then continue
the heating over a strong flame until solution is complete
(usually requires not over 5 min of boiling) or it is apparent that
the residue is composed of SiO or siliceous matter. Caution
should be observed in visually examining this hot solution.
Cool the solution, dilute with 100 mL of water, stir, heat
carefully to boiling while stirring, let settle, filter through
paper, and transfer the precipitate completely to the paper.
11.4 Wash the insoluble residue with cold H SO (1+19)
2 4
until titanium is removed. Dilute the filtrate to 200 mL and add
about 5 mL of NH OH to lower the acidity to approximately 10
to 15 % H SO (by volume). Wash out the Jones reductor with
2 4
H SO (1+19) and water, leaving sufficient water in the
2 4
reductor to fill to the upper level of the zinc. (These washings
should require not more than one or two drops of 0.1 N KMnO
solution to obtain a pink color.) Empty the receiver, and put in
it 25 mL of ferric sulfate solution. Reduce the prepared
titanium solution as follows:
11.4.1 Run 50 mL of H SO (1+19) through the reductor at
2 4
such a uniform rate as to require 5 to 10 min for passage.
11.4.2 Follow this with the titanium solution at such a
uniform rate as to require 10 min to pass through the reductor.
11.4.3 Wash out with 100 mL of H SO (1+19).
2 4
11.4.4 Finally run through about 100 mL of water. Take care
that the reductor is always filled with solution or water to the
upper level of the zinc.
FIG. 2 Jones Reductor, Assembled
11.5 Gradually release the suction, wash thoroughly the
glass tube that was immersed in the ferric sulfate solution,
the end point has been reached. (More rapid cooling may be remove the receiver, and titrate immediately with 0.1 N KMnO
prevented by allowing the beaker to stand on a small hot plate 4 solution. Run a blank determination, using the same reagents
during the titration. The use of a small type thermometer as a and washing the reductor as in the above determination.
stirring rod is most convenient.) Keep the KMnO solution in
12. Calculation
a glass-stoppered bottle painted black to keep out light or in a
12.1 Calculate the percent of TiO as follows:
brown glass bottle stored in a dark place. Calculate the TiO 2
equivalent in grams of TiO per millilitre of the KMnO
~V 2 B! 3 T
2 4
TiO ,% 5 3 100
solution as follows: S
TiO equivalent 5 W 3 1.192!/V
~
where:
V 5 KMnO solution required for titration of specimen,
1 4
where:
mL
W 5 Na C O used, g, and
2 2 4
B 5 KMnO solution required for titration of the blank,
V 5 KMnO solution required for the titration, mL.
mL
10.10 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
T 5 TiO equivalent of the KMnO solution, g/mL, and
2 4
(H SO ).
2 4
S 5 dried specimen, g.
10.11 Sulfuric Acid (1+1)—Carefully mix 1 volume of
12.2 The results calculated in accordance with 12.1 will
H SO (sp gr 1.84) into 1 volume of water with rapid stirring.
include iron, chromium, arsenic, and any other substance that
10.12 Sulfuric Acid (1+19)—Carefully mix 1 volume of
is reduced by zinc and acid. However, appreciable quantities of
H SO into 19 volumes of water with rapid stirring.
2 4
interfering materials are not likely to be encountered in normal,
white titanium pigments.
11. Procedure
11.1 Determine the dry weight of a weighing bottle and cap
TOTAL TITANIUM BY THE ALUMINUM
to 0.1 mg. Weight to 0.1 mg 300 to 350 mg of the sample to be
REDUCTION METHOD
analyzed into the weighing bottle.
13. Scope
11.2 Dry the specimen in the opened weighing bottle for 2
h at 105 to 110°C. Cool in a desiccator, cap the bottle, and 13.1 This method gives results similar to those obtained
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.
D 1394
with the Jones Reductor Method (Sections 8-12). fumes are evolved, and continue the heating over a strong
flame until solution is complete (usually requires not over 5
14. Apparatus
min of boiling) or it is apparent that the residue is composed of
14.1 Delivery Tube, made of about 4-mm inside diameter SiO or siliceous matter. Cool and, with caution, add 120 mL
of water and 20 mL of HCl. Bring to a boil and remove from
glass tubing bent so that there is a horizontal run of about 6 in.
(152 mm) and a vertical drop of about 3 in. (76 mm) at one end, heat.
and a vertical drop of about 6 in. at the other end.
16.4 Insert the short end of the delivery tube into one hole
14.2 Weighing Bottle, wide-mouth, with an external-fitting
of a two-hole rubber stopper suitable for the Erlenmeyer flask.
cap, and no larger than necessary for the required amount of
Insert a glass rod with a slight hook or collar at the bottom end
sample.
into the other hole of the stopper in such a way that the bottom
end will be near the bottom of the flask when the stopper is
15. Reagents
inserted into the flask. Attach approximately1gof aluminum
15.1 Aluminum Metal Foil, electrolytic grade. foil to the bottom end of the rod by crumpling or coiling the
15.2 Ammonium Sulfate—((NH ) SO ).
foil around the rod. It may be possible to use a thermometer
4 2 4
15.3 Ammonium Thiocyanate Indicator Solution—Dissolve instead of a collared glass rod and, if one ranging from 0 to
24.5 g of ammonium thiocyanate (NH CNS) in 80 mL of hot
150°C is used, it can be
...
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