ASTM D1394-76(2003)
(Test Method)Standard Test Methods for Chemical Analysis of White Titanium Pigments
Standard Test Methods for Chemical Analysis of White Titanium Pigments
ABSTRACT
These test methods cover procedures for the chemical analysis of white titanium dioxide pigments. The analytical procedures appear in the following order: sample preparation, qualitative analysis, moisture content determination, total titanium content determination by Jones Reductor and Aluminum Reduction methods, aluminum oxide content determination, and silica content determination. The reagents to be used shall include ammonium hydroxide, ammonium sulfate, hydrochloric acid, hydrogen peroxide, hydrogen sulfide, sulfuric acid, tartaric acid, tin, zinc, carbon steel, iron, ferric sulfate solution, nitric acid, sodium oxalate, potassium permanganate, aluminum metal foil, ammonium thiocyanate indicator solution, ferritic ammonium sulfate solution, sodium bicarbonate solution, sulfuric acid, titanium dioxide, acetic acid, ammonium phosphate, EDTA solution, methyl orange indicator solution, sodium bisulfate monohydrate, sodium fluoride, xylenol orange indicator solution, and zinc sulfate solution.
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: SectionsPreparation of Sample Qualitative Analysis and MoistureTotal Titanium:Jones Reductor Method Aluminum Reduction Method Aluminum Oxide Silica
1.3 The values stated in SI units are to be regarded as the standard. The values given in parentheses are for information only.
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 and health practices and determine the applicability of regulatory limitations prior to use. A specific hazard statement is given in Section 19.
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Designation:D1394–76(Reapproved2003)
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 tee onAnalytical Reagents of theAmerican Chemical Society,
where such specifications are available. Other grades may be
1.1 These test methods cover procedures for the chemical
used, provided it is first ascertained that the reagent is of
analysis of white titanium dioxide pigments.
sufficiently high purity to permit its use without lessening the
1.2 The analytical procedures appear in the following order:
accuracy of the determination.
Sections
3.2 Unless otherwise indicated, references to water shall be
Preparation of Sample 4
Qualitative Analysis 5 and 6
understood to mean reagent water conforming to Type IV of
Moisture 7
Specification D 1193.
Total Titanium:
Jones Reductor Method 8-12
4. Preparation of Sample
Aluminum Reduction Method 13-17
Aluminum Oxide 18-22
4.1 The sample shall, in all cases, be thoroughly mixed and
Silica 23-29
comminuted before taking portions for analysis.
1.3 The values stated in SI units are to be regarded as the
QUALITATIVEANALYSIS
standard. The values given in parentheses are for information
only.
5. Reagents
1.4 This standard does not purport to address all of the
5.1 Ammonium Hydroxide (sp gr 0.90)—Concentrated am-
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appro- monium hydroxide (NH OH).
5.2 Ammonium Sulfate—((NH ) SO ).
priate safety and health practices and determine the applica-
4 2 4
bility of regulatory limitations prior to use. A specific hazard 5.3 Hydrochloric Acid (sp gr 1.19)—Concentrated hydro-
chloric acid (HCl).
statement is given in Section 19.
5.4 Hydrogen Peroxide (30 %)—Concentrated hydrogen
2. Referenced Documents
peroxide (H O ).
2 2
5.5 Hydrogen Sulfide (H S).
2.1 ASTM Standards:
D 280 Test Methods for Hygroscopic Moisture (and Other 5.6 Sulfuric Acid (sp gr 1.84)—Concentrated sulfuric acid
(H SO ).
Matter Volatile Under the Test Conditions) in Pigments
D 1193 Specification for Reagent Water 5.7 Sulfuric Acid (1+19)—Carefully mix 1 volume of
H SO (sp gr 1.84) with 19 volumes of water.
E 50 Practices forApparatus, Reagents, and Safety Consid-
erations for Chemical Analysis of Metals, Ores, and 5.8 Tartaric Acid.
5.9 Tin or Zinc Metal.
Related Materials
3. Reagents 6. Procedure
6.1 Place about 0.5 g of the sample in a 250-mL glass
3.1 Purity of Reagent—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that 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
all reagents shall conform to the specifications of the Commit-
4 2 4
should go completely into solution; a residue denotes the
These test methods are under the jurisdiction of ASTM Committee D01 on
Paints and Related Coatings, Materials, and Applications and are the direct
Reagent Chemicals, American Chemical Society Specifications, American
responsibility of Subcommittee D01.31 on Pigment Specifications.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved Oct. 1, 2003. Published October 2003. Originally
listed by the American Chemical Society, see Analar Standards for Laboratory
approved in 1956. Last previous edition approved in 1976 as D 1394 – 76 (1999). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Annual Book of ASTM Standards, Vol 06.03. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
Annual Book of ASTM Standards, Vol 11.01. MD.
4 6
Annual Book of ASTM Standards, Vol 03.05. Borosilicate glass has been found satisfactory for this purpose.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D1394–76 (2003)
presence of silicon dioxide (SiO ) or siliceous matter. Cool the
solution, dilute with 100 mLof water, heat to boiling, let settle,
filter, wash with hot H SO (1+19) until free of titanium, and
2 4
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
determinationaddtoaportionofthefiltrate5goftartaricacid,
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.
TOTALTITANIUM BYTHE JONES REDUCTOR
METHOD
8. Scope
8.1 This method gives results similar to those obtained with
the Aluminum Reduction Method, Sections 13-17.
FIG. 1 Jones Reduction
9. Apparatus
9.1 Jones Reductor having a zinc column at least 450 mm
10.4 Ferric Sulfate Solution (1 mL = 0.02 g Fe)—Dissolve
in length, and 19 mm in diameter (Fig. 1 and Fig. 2). The
20 g of iron or carbon steel in a slight excess of HCl, oxidize
filtering pad must be tight enough to hold all the particles of
with approximately 12 mL of HNO , add about 80 mL 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, 1 mL = 0.008 gTiO )—Dissolve 3.16 g of KMnO
2 4
monium hydroxide (NH OH).
inwateranddiluteto1L.Letstand8to14days,siphonoffthe
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
standard sample No. 40 of sodium oxalate (Na C O)as
2 2 4
follows: In a 400-mL beaker dissolve 250 to 300 mg Na C O
2 2 4
Treadwell,F.P.,andHall,WilliamT., QualitativeAnalysis,JohnWiley&Sons,
in 250 mL of hot water (80 to 90°C) and add 15 mL of H SO
2 4
Inc., New York, NY, Vol. 1, Ninth English Ed., 1937.
(1+1). Titrate at once with the KMnO solution, stirring the
8 4
Directions for preparing a Jones Reductor may be found in Hillebrand, W. F.,
liquid vigorously and continuously. The KMnO solution must
et al., Applied Inorganic Analysis, John Wiley & Sons, Inc., NewYork, NY, Second 4
Ed., 1953, p. 108. not be added more rapidly than 10 to 15 mL/min, and the last
D1394–76 (2003)
11. Procedure
11.1 Determine the dry weight of a weighing bottle and cap
to 0.1 mg.Weight to 0.1 mg 300 to 350 mg of the sample to be
analyzed into the weighing bottle.
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
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 mLchemical-
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
(usuallyrequiresnotover5minofboiling)oritisapparentthat
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 mLand add
about5mLofNH OHtolowertheaciditytoapproximately10
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
shouldrequirenotmorethanoneortwodropsof0.1NKMnO
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.
FIG. 2 Jones Reductor, Assembled
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
0.5 to 1 mL must be added dropwise with particular care to
11.4.4 Finallyrunthroughabout100mLofwater.Takecare
allow each drop to be fully decolorized before the next is
that the reductor is always filled with solution or water to the
introduced. The solution shall not be below 60°C by the time
upper level of the zinc.
the end point has been reached. (More rapid cooling may be
11.5 Gradually release the suction, wash thoroughly the
prevented by allowing the beaker to stand on a small hot plate
glass tube that was immersed in the ferric sulfate solution,
during the titration. The use of a small type thermometer as a
remove the receiver, and titrate immediately with 0.1 N KMnO
stirring rod is most convenient.) Keep the KMnO solution in
4 solution. Run a blank determination, using the same reagents
a glass-stoppered bottle painted black to keep out light or in a
and washing the reductor as in the above determination.
brown glass bottle stored in a dark place. Calculate the TiO
equivalent in grams of TiO per millilitre of the KMnO
2 4
12. Calculation
solution as follows:
12.1 Calculate the percent of TiO as follows:
TiO equivalent 5 ~W 3 1.192!/V
~V 2 B! 3 T
TiO,% 5 3 100
where:
S
W =Na C O used, g, and
2 2 4
where:
V = KMnO solution required for the titration, mL.
V = KMnO solution required for titration of specimen,
10.10 SulfuricAcid(spgr1.84)—Concentratedsulfuricacid 1 4
mL
(H SO ).
2 4
B = KMnO solution required for titration of the blank,
10.11 Sulfuric Acid (1+1)—Carefully mix 1 volume of
mL
H SO (sp gr 1.84) into 1 volume of water with rapid stirring.
T =TiO equivalent of the KMnO solution, g/mL, and
2 4
10.12 Sulfuric Acid (1+19)—Carefully mix 1 volume of
S = dried specimen, g.
H SO into 19 volumes of water with rapid stirring.
2 4
D1394–76 (2003)
12.2 The results calculated in accordance with 12.1 will 16. Procedure
include iron, chromium, arsenic, and any other substance that
16.1 Determine the dry weight of the weighing bottle and
isreducedbyzincandacid.However,appreciablequantitiesof
cap. Weigh to the nearest 0.1 mg, 190 to 210 mg of the sample
interferingmaterialsarenotlikelytobeencounteredinnormal,
to be analyzed into the weighing bottle.
white titanium pigments.
16.2 Drythespecimenintheopenweighingbottlefor2hat
105to110°C.Coolinadesiccator,capthebottle,andweighas
TOTALTITANIUM BYTHEALUMINUM
rapidly as possible. Calculate the dry weight of the specimen
REDUCTION METHOD
and use in the actual calculation.
16.3 Transfer the dry specimen to a 500-mL dry, wide-
13. Scope
mouthErlenmeyerflask.Add7to9gof(NH ) SO and20mL
4 2 4
of H SO . Mix well, heat on a hot plate until dense white
13.1 This method gives results similar to those obtained
2 4
fumes are evolved, and continue the heating over a strong
with the Jones Reductor Method (Sections 8-12).
flame until solution is complete (usually requires not over 5
min of boiling) or it is apparent that the residue is composed of
14. Apparatus
SiO or siliceous matter. Cool and, with caution, add 120 mL
14.1 Delivery Tube, made of about 4-mm inside diameter
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.
heat.
(152mm)andaverticaldropofabout3in.(76mm)atoneend,
16.4 Insert the short end of the delivery tube into one hole
and a vertical drop of about 6 in. at the other end.
of a two-hole rubber stopper suitable for the Erlenmeyer flask.
14.2 Weighing Bottle, wide-mouth, with an external-fitting
Insert a glass rod with a slight hook or collar at the bottom end
cap, and no larger than necessary for the required amount of
into the other hole of the stopper in such a way that the bottom
sample.
end will be near the bottom of the flask when the stopper is
inserted into the flask. Attach approximately1gof aluminum
15. Reagents
foil to the bottom end of the rod by crumpling or coiling the
15.1 Aluminum Metal Foil, electrolytic grade.
foil around the rod. It may be possible to use a thermometer
15.2 Ammonium Sulfate—((NH ) SO ).
4 2 4
instead of a collared glass rod and, if one ranging from 0 to
15.3 Ammon
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