PB-242 293
LITERATURE STUDY OF SELECTED POTENTIAL ENVIRONMENTAL
CONTAMINANTS TITANIUM DIOXIDE
ARTHUR D, LITTLE, INCORPORATED
PREPARED FOR
ENVIRONMENTAL PROTECTION AGENCY
MAY 1975
DISTRIBUTED BY:
National Technical Information Service
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NOTICE
This report has been reviewed by the Office of Toxic Substances,
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TABLE OF CONTENTS
Page
SUMMARY
0. INTRODUCTION i
I. Physical and Chemical Data 11
II. Environmental Exposure Factors ill
III. Health and Environmental Effects ix
IV. Regulations and Standards xii
V. Evaluation and Comments xiii
PRELIMINARY INVESTIGATION REPORT 1
I. PHYSICAL AND CHEMICAL DATA 1
A. Structure and Properties 1
B. Chemistry 6
II. ENVIRONMENTAL EXPOSURE FACTORS 8
A. Production and Consumption 8
B. Uses 26
C. Environmental Contamination Potential 35
D. Current Handling Practices and Control Technology 45
E. Monitoring and Analysis 51
III. HEALTH AND ENVIRONMENTAL EFFECTS 57
A. Environmental Effects 57
B. Biology 58
C. Toxicity - Humans 70
D. Toxicity - Birds and Mammals 74
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TABLE OF CONTENTS (Cont'd)
Page
E. Toxicity - Lower Animals 75
F. Toxicity - Plants 75
G. Toxicity - Microorganisms 75
H. Effects on Inanimate Objects and Structures 75
IV. REGULATIONS AND STANDARDS 76
A. Current Regulations 76
B. Consensus and Similar Standards 78
V. EVALUATION AND COMMENTS 81
A. Summary 81
B. Conclusions 81
REFERENCES A-l
BIBLIOGRAPHY (Not Included in Technical Data Summary) B-l
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LIST OF TABLES
Page
TABLE I Selected Electrical Properties of Titanium Dioxide . . 3
TABLE II Typical Properties of Titanium 4
TABLE III Producers of Titanium Dioxide 11
TABLE IV Analysis of Typical Ores Used for Ti02 Manufacture . 12
TABLE V Plant Locations Where Sulfate Process is Reportedly
Used 13
TABLE VI Ti02 Content and Prices for Four Types of Titanium Ore 17
TABLE VII Ti02 Commercial Shipment Values 19
TABLE VIII Plant Locations and Capacities for Ilmenite
Beneficiation by Acid-Leaching Process 24
TABLE IX Processor and Type of Process Using Other
Beneficiation Technology 25
TABLE X Percentage Distribution of Titanium Pigment
Shipments by Industries 27
TABLE XI Market Consumption of Ti02 by Industries 28
TABLE XII Sulfate Process Waste Streams in Titanium Dioxide
Manufacture 36
TABLE XIII Partial Discharge Data from Ti02 Sulfate Plants. ... 37
TABLE XIV Waste Discharge Data for'Titanium Dioxide Plants ... 39
TABLE XV Sources and Estimates of Titanium-Containing Emissions 42
TABLE XVI Installation of Neutralization Treatment and
Performance 49
TABLE XVII Composition of Plant Effluent Streams After Treatment. 53
TABLE XVIII Verification Data for the Plant 53
TABLE XIX Concentration of Titanium Dioxide in Liver, Spleen,
and Lymph Nodes 62
TABLE XX Twenty-Five-Day Retention of Ti02 in Papain
Treated Rats 66
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LIST OF FIGURES
Page
FIGURE I T102 Pigment Manufacturing Processes 15
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SUMMARY
0. INTRODUCTION
Titanium dioxide (Ti02) is the most important oxide of titanium, deriving
this importance primarily from its extensive use as a white pigment in a
variety of commercial products. Principal raw materials for the manufac-
ture of Ti02 by two major processes — the sulfate process and the chloride
process — are the minerals ilmenite and rutile.
Ilmenite, an iron-black mineral composed of iron, titanium, and oxygen,
occurs in plentiful supply throughout the world and is mined extensively
in many countries, including the United States. In 1967, world produc-
tion of ilmenite rose to approximately 3 million short tons per year and
since then has remained at that level or increased slightly. Of this
amount, the U.S. produces about 700,000 short tons. Ilmenite (40-60%
Ti02) has been the source of the titanium dioxide produced by the sulfate
process, but recently Du Pont started to use that ore in its chloride
process.
Rutile, which is a reddish-brown mineral of almost pure titanium dioxide
(usually containing a little iron), occurs chiefly in Australia. No rutile
is mined in the United States, but current world production is approximately
400,000 long tons per year. At this rate, world supplies are expected to
last only 20-25 years, a situation with serious overtones since rutile is
the basic raw material for most chloride production of titanium dioxide.
One potential source to offset the question of rutile reserves is the up-
grading of ilmenite to over 90% Ti02 through the removal of iron. It can
then be processed, utilizing the rutile chloride technology. This removal
of part or almost all of the iron content of the ilmenite ore results in
a product soluble in sulfuric acid, or one which can be chlorinated eco-
nomically, and is the nature of the beneficiation process. The relative
if
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abundance of ilmenite compared to rutlle makes beneficiation of ilmenite a
promising technology. Some ilmenite producers and rutile consumers alike
are converting to the beneficiation route. In addition, one manufacturer
has developed a process to use mixed ores in the feed; other manufacturers
are developing technology so that unbeneficiated ilmenite can be chlori-
nated.
With U.S. production capacity for titanium dioxide predicted at 939,000
tons per year, its potential impact on the environment was deemed worthy
of study. This report reflects the findings of a comprehensive review
of the literature published during the last 20 years on the physical and
chemical properties of TiC>2, on the environmental exposure factors related
to its consumption and use, on the health and environmental effects result-
ing from exposure to Ti02, and the regulations and standards governing its
use. In summary, the literature provides the following information.
I. PHYSICAL AND CHEMICAL DATA
Titanium dioxide, a white crystalline material that occurs naturally in
many minerals, is an inert compound, very resistant to chemical attack by
most acids and alkalies. It has a high refractive index, a property that
enables it to refract or bend light rays and thus to impart whiteness and
opacity to paints and other products in which it is used.
Its insulating properties have made it attractive to the plastics and
ceramics industries, and its dielectric and semiconducting properties con-
tribute to its usefulness in electronic components.
Titanium dioxide, whether manufactured from ilmenite or rutile ore, can
be produced in two crystalline forms — anatase or rutile. These manu-
factured crystals have properties very similar to the natural crystals,
crystals that exist in the ores of the same names.
ii
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The manufactured pigments, or powders, are white, but the rutile-type is
generally a yellowish-white, while the anatase is more apt to have a
bluish cast. The pigments are odorless, inert, and melt at over 1800°C.
Although every effort is made to produce a "pure" Ti02, the end product
usually contains a small percentage of one or more of the oxides of alumi-
num, silicon, zinc or antimony, compounds that are used in the manufactur-
ing process to impart particular properties to the pigment. In some in-
stances, a very small amount (in the range of parts per million) of metals,
e.g., iron, chromium, vanadium, are present.
Titanium dioxide is treated with metal oxides during the manufacturing
process to reduce its photoreactivity. Untreated pigments, apparently,
can contribute to the photodegradation of organic systems exposed to ultra-
violet radiation.
II. ENVIRONMENTAL EXPOSURE FACTORS
A. Production and Consumption
Titanium dioxide was first produced in the U.S. in 1916 by the Titanium
Pigment Company. In 1925 (after the National Lead Company had purchased
a large interest in the Titanium Pigment Company), production reached
4,000 tons. By 1971, there were eight United States producers with a
combined estimated capacity of about 800,000 tons. In 1974, nine U.S.
manufacturers had a production capacity of 939,000 tons of TiO_.
Production in 1972 was approximately 700,000 tons, while apparent consump-
tion was about 787,000 tons, including imports. Imports have ranged from
5% to 10% of total apparent consumption in recent years and are expected
to remain at about this percentage level. Exports, less than 2% to 3%
(about 15,000 tons) of production from 1966 through 1971, declined in 1972,
iii
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The paint, paper and plastics industries accounted for almost 80% of the
787,000 tons consumed in 1972, a tonnage valued at about $433 million on
a delivered basis.
In the U.S., the current plant capacity for producing titanium dioxide is
divided almost equally between the two major production processes — the
sulfate process and the chloride process. In recent years, new U.S. plants
have been built to accommodate the latter process because of such factors
as lower investment and production costs, better product quality, and
reduced quantities of waste.
U.S. titanium dioxide producers are located in Ohio, New Jersey, Delaware,
Maryland, Tennessee, Mississippi, Missouri, Georgia, and California.
Chemically pure Ti07 is prepared from rutile ore, which is chlorinated
and yields titanium chloride (principally titanium tetrachloride) vapors.
These vapors are then oxidized to TiO? in a burner supplied with air, the
burning or oxidation operation being the chief factor in a successful
process. A number of intermediate steps, of course, are necessary in this
process to remove impurities. Later, after the finely-divided TiO_ is
produced, various metallic or non-metallic oxides are added to control
pigment properties; additional treatment provides optimum pigment properties.
Ilmenite ore can be substituted for rutile in this chloride process, but
more chlorine is required, making the process costs higher.
Ilmenite is generally used to make TiO_ by the sulfate process. In this
method, ground ilmenite plus sulfuric acid, iron and water are mixed in a
digester (using air agitation), and then the soluble titanium and iron
sulfates are leached from the reaction mass. Other steps involve the
separation of the titanium from contaminating iron salts, and the conversion
of the titanium sulfate to titanium hydrate, which is then calcined (heated
to a high temperature) to form crystalline titanium dioxide. The crystalline
material (generally the anatase form) is then milled, treated to obtain cer-
tain properties, and packaged for sale.
iv
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In the early and mid-1950*s, there was a dramatic Increase in the market
price of titanium dioxide, but over the last 20 years the price of anatase
pigment increased only by about 6.5c/lb and that of rutile about 7C/lb.
From 1965 to 1971, prices were fairly stable for both forms, anatase
selling for 25
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The problems of waste and waste disposal may be considered influences on
future market potentials for TiC^. Air pollutants from the sulfate process
require control devices, such as wet scrubbers, to remove particulates, and
pollution control devices generally add to production costs. One of the
'waste products from the sulfate process is ferrous sulfate, or copperas,
a product that has little market potential because supply seems always to
exceed demand. Although new uses for copperas, e.g., in water treatment,
have been sought, so far little progress has been made. Therefore, much
of the copperas must be disposed of as waste, under increasingly strict
waste-disposal laws.
Even though chlorine is recycled in the chloride process, gaseous pollu-
tants do exist, and pollution control requirements will contribute to
changing market prices and, possibly, to reduced market demands.
B. Uses
Some 700,000 to 800,000 short tons per year of Ti02 are consumed in the
United States. In 1972, the three major users — the paint, paper, and
plastics industries — accounted for 626,000 of the total 787,000 short
tons of TK>2 consumed in the U.S. The remainder was used, in decreasing
amounts, by such industries as rubber, floor covering, printing ink,
ceramics, synthetic fibers, and roofing granules. Miscellaneous uses
accounted for 40,000 short tons.
For most of the above uses, there appears to be no alternative material
that can be substituted for Ti02« The one exception, however, is the
paper industry, which finds that lower-priced alumina and silica clays
provide brightness almost equal to that obtained with titanium dioxide.
C. Environmental Contamination Potential (Sources)
Principal environmental contaminants derive from impurities in the ores
vi
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used as raw materials in the manufacture of TiO,,, additives used in the
processing of the material, and by-products and wastes generated in the
manufacturing processes. The main problem appears, to center around the
high volume of wastes and their disposal.
The major wastes from the sulfate process are the spent sulfuric acid and
ferrous sulfate (copperas). Because the latter is in plentiful supply and
can be manufactured at low cost from certain iron scrap, there is, there-
fore, little market demand for the copperas waste from TiO„ production and
little incentive for TiO~ producers to invest in equipment to recover it.
Waste disposal of copperas involves certain expenses and must satisfy
existing waste-disposal regulations. It does not appear to be economically
feasible, either, to recover the sulfuric acid from the waste. Thus, pro-
ducers of TiO- by the sulfate process must neutralize their acid wastes
to meet water quality standards.
From the chloride process, some chlorine and product dusts are potential
air pollutants, but the magnitude of these gaseous wastes may be consid-
ered small when compared with the control of small particulates from other
industries. The non-volatile wastes, e.g., metallic impurities in the ore,
carbon, and unreacted ore have, generally, been considered non-hazardous.
Effluents contain titanium hydroxide and small amounts of metal compounds.
Titanium tetrachloride, the precursor of TiO in the chloride process, is
also used in the manufacture of titanium metal. Titanium tetrachloride
is hazardous because it decomposes in a moist atmosphere, generating TiO_
and hydrochloric acid. Chlorine is recycled. Most of the other products
involved are considered wastes and proper control equipment and/or waste
disposal methods must be considered for cost effectiveness and for compli-
ance to environmental disposal laws.
vii
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There are restrictions on ocean dumping and there is a possibility that
some trace metals (e.g., arsenic, chromium, copper, mercury, lead) may
leach out of TiO. solid wastes used as landfill.
No unusual environmental situations seem to be associated with the packag-
ing, transport or storage of titanium dioxide, which is generally shipped
in paper sacks. In its industrial use, dust and fumes from electric fur-
nace operations may present a problem. Inhalation of TiO_ above the OSHA
3
employee exposure limit (8-hour time weighted average: 15 mg/m ) can cause
irritation to workers exposed to the dust or fumes.
D. Current Handling Practices and Control Technology
Under normal working conditions, however, there are no occupational safety
and health recommendations governing eye protection, protective gloves,
or respiratory protection for those handling titanium dioxide. When con-
centrations of Ti02 exceed the 8-hour time weighted average, established by
OSHA at 15 mg/m , protective gloves and glasses are required.
Under conditions of excessive dusting and/or for clean-up purposes, a
non-toxic particle mask and ventilation, such as mechanical exhaust, is
desirable. A dust respirator is required when an employee's exposure in
any 8-hour work-shift of a 40-hour week will exceed the 8-hour time weighted
average.
The fact that no major disasters have been associated with titanium dioxide,
coupled with its reputation as an inert material, argues for the lack of
stringent regulations in its shipment and storage. It is shipped in paper
sacks, containing approximately 50 pounds, or as a slurry in water in tank
trucks or rail cars. Few precautions are taken in storing TiO£ other than
the avoidance of damp or wet storage, which causes caking.
viii
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Methods practiced for the disposal of waste from the manufacture of TiO.
include ocean dumping, landfill, and deep-well injection. Acidic wastes
are neutralized before disposal. Where feasible, waste products are re-
cycled or recovered for sale.
No widespread incidence of adverse effects on marine life has been reported
from ocean dumping, although one study indicates that there may be an ef-
fect on the sand dollar. Environmental protection authorities are, however,
questioning the feasibility of ocean dumping, and manufacturers have also
shown some concern about the continuation of this practice.
Standard protective equipment, as described above, is required, if Ti02
is spilled or leaked.
There are no restrictions on the composition of Ti02 used in packaging
or food contact applications but, when Ti(?2 is used as a color additive in
foods, drugs, or cosmetics, its composition must comply with the standards
established by the U.S. Food and Drug Administration.
E. Monitoring and Analysis
The variety of analytical methods used for determining the composition
and character of wastes from the manufacture of TiC>2 are standardized
procedures in general use.
III. HEALTH AND ENVIRONMENTAL EFFECTS
A. Environmental Effects
Titanium dioxide is inert chemically. It is insoluble in water and most
acids. Since the suggested waste disposal methods for producers is sani-
tary landfill, Ti(>2 is considered persistent with no evidence of chemical
or biological degradation.
ix
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Titanium dioxide is accumulated to a lesser extent in plants, fish, mice,
etc., than are the soluble salts of titanium, such as potassium titanium
oxylate.
B. Biology
Laboratory studies with animals on a diet containing 0.25% Ti02 for 13 days
demonstrated over 90% excretion of the total dose in the feces with little
or no absorption from the digestive tract.
No absorption of Ti02 is observed after skin application.
There is deposition of TiC>2 in the lungs and lymph nodes in rats subjected
to inhalation and intratracheal injection experiments. Silica-containing
dust shows greater absorption in the lungs than TiC>2 dust, during intra-
tracheal studies.
Intravenous injection of 1 and 2 mg of Ti02 in rats produced no appre-
ciable change in blood platelet count. A dose of 4 mg, however, caused
a marked decrease in platelet count. Comparatively, a similar decrease
in the number of circulating blood platelets was noted after injection
of only 1 mg of synthetic silica.
Titanium and its alloys have been tested as a surgical implant in animal
tests with no apparent adverse effects on either tissues or bones.
C. Toxicity — Humans
No widespread incidence of illness among workers exposed to Ti02 or
titanium dust has ever been reported. According to a report from Finland,
however, three men, who had worked in a Ti02 processing factory for about
10 years, had lung problems including difficult or hard breathing, a
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cough and recurrent bronchitis associated with their work. Lung examina-
tion of two of the patients revealed changes related to lung disease due
to the inhalation of fine particles (pneumoconiosis). Surgical incision
of the wall of the chest (thoracotomy) showed one patient had lung mem-
brane adhesions and green-colored patches on the lung surface associated
with carbon, plus pigment aggregations due to an unidentified pigment.
One lung showed emphysema and chronic bronchitis, and x-ray fluorescence
analysis indicated the presence of large amounts of titanium in the lungs
of all three men.
In a larger study, however, examination of 136 workers who processed
ilmenite ore (titanium oxide with iron present), showed little incidence
of serious adverse effects. These individuals had worked with the titanium
ore for one to twelve years, with an average of 3.3 years service for the
most exposed workers. Radiological lesions were found in three workers,
only one of whom had a high degree of exposure. All three showed no
symptoms. Six workers showed respiratory symptoms since starting work
at the factory but none had abnormal physical signs or radiological
lesions. The symptoms were not judged to be a specific response of the
workers to the titanium minerals but were attributed to the dust per se.
A health survey, conducted by NIOSH, at one titanium dioxide manufacturing
plant in New Jersey on 15 randomly-selected workers revealed no health
complaints by these individuals nor knowledge of ill health of any of their
associates. Nine workers with health complaints were interviewed; none
of these suggested a relationship to exposure to titanium dioxide. Al-
though the plant was rather dusty, respirable levels of TiC^ were below
the standards permitted.
No studies on widespread diseases related to Ti02 were found in the litera-
ture. Titanium and its compounds have long been used in surgical appliances
and in the treatment of skin disorders with no reports of resulting toxicity.
xi
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There is little data available on controlled studies of the toxicity to
humans of titanium dioxide. Conversely, the use of titanium salts in
ointments and powder preparations over a 3-year period in about 100 cases
showed healing but not toxic effects. Also, Ti02 is reputedly useful in
protecting the skin from exposure to light; and, in cosmetics, pure Ti02
paste has not shown any adverse effects.
D. Toxicity — Birds and Mammals
!
Rats receiving a sing-le intratracheal injection of Ti02, 20 mg per animal,
showed no adverse reactions. No other studies pertaining to the acute
toxicity of TiC>2 were located.
Inhalation studies over a period of 9-13 months showed no evidence of any
specific pathologic lesion (body organ damage) in rats.
E, F, G. Toxicity — Other Organisms
No studies on the toxicity of Ti02 to lower animals, plants, and/or micro-
organisms were found.
H. Effects on Inanimate Objects and Structures
The literature did not reveal any information on the effects of Ti02 on
materials.
IV. REGULATIONS AND STANDARDS
A. Current Regulations
Under the Federal Food, Drug and Cosmetic Act, Ti02 used as a color addi-
tive, must be free from admixture with other substances and may not con-
tain more than very minute amounts of lead, arsenic, antimony, and mercury.
xii
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When used as a coloring in foods, amounts of T102 used may not exceed 1%
by weight of the food.
The EPA identifies Ti02 as a material "requiring special care" for ocean
dumping, and as a processing waste "requiring special care." OSHA has
set an exposure limit level for industry, but DOT does not include TiC>2
on its list of hazardous materials, and it does not appear on the National
Safety Council's list.
Titanium dioxide does not appear on the list of dangerous goods published
by the Inter-Governmental Maritime Consultative Organization.
The American Conference of Governmental Industrial Hygienists classifies
TiO as a "nuisance dust" and, in accordance with the general rule for sub-
z 3
stances in this category, they recommend a TLV of 10 mg/M for TiO . In
its summary of hygienic standards, the American Industrial Hygiene Associa-
tion concludes that it is unlikely that an emergency requiring medical
attention could arise from exposure to TiO,..
Finally, the Joint Group of Experts on the Scientific Aspects of Marine Pol-
lution (GESAMP), comprised of IMCO, FAO, UNESCO, WMO, IAETA, and UN experts,
classifies Ti02 wastes as a slight harm to living resources, a negligible
hazard to human health, and a negligible hindrance to maritime activities.
V. EVALUATION AND COMMENTS
A. Summary
Titanium dioxide is an industrially significant high volume chemical. In
itself, it is not considered hazardous, but it is a nuisance dust, causing
respiratory irritations. Such irritations, however, in no way compare to
the adverse effects of silica and asbestos. Environmental concern centers
about the waste products from TiO£ manufacture.
xiii
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B. Conclusions
Manufacturers face the problem of a depleting supply of a major raw material
for one manufacturing process, and continuing problems of processing waste
disposal.
A study of the effects of the leaching of trace metals from solid Ti02
waste is indicative of suggested research studies.
Lack of information on many parameters bearing on the health and environ-
mental effects of Ti02 hinder analysis and evaluation. In general, the
presently available information on Ti02 per ge indicates no environmental
hazard potential. However, the type and volume of wastes from Ti02 pro-
duction give rise to significant pollution control problems.
xiv
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PRELIMINARY INVESTIGATION REPORT
I. PHYSICAL AND CHEMICAL DATA
Titanium forms four well-defined oxides of which the dioxide is the only
one of real importance and commercial interest.
A. Structure and Properties
1. Chemical Structure
Titanium dioxide is identified as:
Chemical formula: TiC>2
Chemical composition (wt%): Ti 59.96
0 40.04
100.00
Molecular weight: 79.90
Synonyms include:
Titania
Anatase titanium dioxide
Rutile titanium dioxide
Trade names include:
Ti-Pure® R-900 ' (DuPont)
TITANOX® 2032 , (NL Industri
TRONOX CR-892 (Kerr-McGee)
2. Mixture Information
Not applicable.
-1-
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3. Physical Properties of Pure Material
Titanium dioxide is a white crystalline material that occurs naturally
in three crystal forms: anatase, rutile, and brookite. The two commer-
cially important forms, anatase and rutile, are tetragonal crystals.
Brookite, which is orthorhombic, is, however, rare and of no commercial
importance. Although substantially pure TiC^, these crystals are of a
dark color because of the presence of small amounts of impurities, par-
ticularly iron and iron oxides and, in some instances, minute amounts of
non-ferrous metallic oxides.
Rutile is thermally stable; anatase less so, transforming to rutile be-
tween 700° to 950°C. Physical properties of the natural crystals are
maintained by the manufactured crystals and are described later. (See:pp. 3-4)
Both the anatase and rutile crystalline forms of TiC>2 resist chemical
attack. Resistance to acid contributes to the use of Ti02 in vitreous
enamels applied on ferrous surfaces.
The outstanding ability of TiC>2 to refract or bend light rays and thus
impart whiteness and opacity to the media in which it is used, accounts
for its commercial importance. Rutile has the highest refractive index
of any white pigment, 2.76, while the refractive index of anatase is
2.55. For this reason the rutile grades of ore with higher, more econom-
ical, opacity and tinting strength are generally preferred. On the other
hand, the anatase grades of ore impart a bluer tone, whereas the rutile
I
has a yellow cast.
The insulating properties of TiC^ contribute to its usefulness in the
plastics and ceramics industries. Some selected electrical properties
for rutile titanium dioxide are given in the table following.
1. W.A. Kampfer, "Titanium Dioxide," Pigment Handbook, Volume 1.
Temple C. Patton, Editor (New York: John Wiley & Sons, Inc., 1973) p. 6
Copyright © 1973 John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.
-2-
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TABLE I
SELECTED ELECTRICAL PROPERTIES OF TITANIUM DIOXIDE
Rutile Anatase
Dielectric constant
Pigment ' 114 48
Single crystal
((-direction |70 —
c-direction 86
Loss tangent
(/-direction 0.0110 to 0.0002 —
c-direction 0.35 to 0.0016 —
Electrical
conductivity
(single crystal)
(ohor' cm"1)
((-direction
30 "C 10-'° —
227'C 10 ' —
c-direction
30'C IO-'3 —
2273C IO-" —
Breakdown voltage
(VmiT1) 600-700 —
Dipolc moment
(dcbycs) 2.8-3.3 —
Magnetic
susceptibility 0.078-0.089x10" —
The dielectric constant for anatase pigment is 48. Rutile is an electri-
cal insulator at 68°F but its specific conductivity rises rapidly at
elevated temperature, as indicated by the increased conductivity at 227°C.
It is used in electronic components for its dielectric and semiconducting
properties.
4. Properties of Commercial Material
Manufactured titanium dioxide can be obtained in either the anatase or
rutile crystalline form from both of the major production processes.
1. Harry Hyman, "Working with the Volume Inorganics," Chemical
Engineering/Deskbook Issue, 80 (8 October 1973) p. 23.
-3-
-------
For the pigments, the crystal names merely denote that they have the
same crystal structure as the natural minerals of those names, and do
not refer to the starting material from which the pigment was produced.
To insure maximum light scattering the pigment must also be manufactured
to the proper particle size. There are over 20 grades of rutile pigments
and nearly 10 grades of anatase pigments consumed by numerous industries.
Titanium dioxide pigments are white, but there are substantial differences
in hue. The rutile is more yellowish-white than the anatase, but it is
higher in brightness and opacity. The pigments also are odorless, inert
powders with a melting point of over 1800°C.
Titanium dioxide pigments are insoluble in organic solvents, polymers,
alkalies, and all acids except concentrated sulfuric and hydrofluoric.
Typical properties for the pigment form of the crystal types of titanium
dioxide are described in the table below.
TABLE II
TYPICAL PROPERTIES OF TITANIUM DIOXIDE
Anatase
Rutile
Appearance
Density(g/cm^)
(Ib/gal)
Refractive index
Oil absorption
(lb/100 Ib)
Tinting strength
(Reynolds)
Particle size, av.
Hardness (moh)
Compressibility
coefficient
(10-6 ^2 kg-l)
Melting point (CC)
In air
At higher % 02
Specific heat
(cal °C-1 g-1)
Dielectric constant
Brilliant white powders
3.8-4.1 3.9-4.2
4.26 (single crystal)
(ym)
32-34
2.55
18-30
1200-1300
0.3
5-6
decomposes
0.17
48
33-35
.2.76
16-48
1650-1900
0.2-0.3
6-7
0.53-0.58
1830 ± 15
1879 ± 15
0.17
114
1. Kirk-Othmer Encyclopedia of Chemical Technology. Second Revised Edition
Vol. 20 (New York: John Wiley & Sons, Inc., 1969) p. 397
2. The TITANOX® Product Data Book. (New Jersey: NL Industries)
W.A. Kampfer, op. cit:., p. 3
Copyright © 1973, John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.
-4-
-------
5. Principal Contaminants in Commercial Product
In the manufacture of the pigments, T102 is modified or treated with oxides
of alumina, silica, zinc oxide, or a combination of oxides. Such treat-
ments add to the ease of processing arid enhance the appearance and dura-
bility of the wide variety of products utilizing titanium dioxide. A small
amount of the modifiers remain in the finished prbduct.
Manufacturers' specifications usually show a minimum percentage of
(92%, 95.8%, 97%), and a "remainder" percentage. Usually, the "remainder"
is alumina (A^C^) , or a mixture of alumina and silica (Si02) • Occasion-
ally, zinc oxide (ZnO) is listed as a third "remainder," and in some formu
lations alumina and antimony oxide are present, with the latter additive
found principally in pigments used as delustrants for synthetic fibers.
A non-pigmentary product, TITANOX® 3030, recommended by NL Industries for
the preparation of titanium opacified porcelain enamel, has a typical
composition: W
Ti02 99.4% minimum
Iron 70 ppm
Chromium 10 ppm
Vanadium 25 ppm
In tests of Ti-Pure® products for heavy metals associated with Ti02 manu-
facture, conducted by Du Pont for Food and Drug Administration clearance
purposes, results showed mercury content in less than 0.1 ppm. Du Pont
states that no mercury based ingredients are used in the manufacture of
Ti-Pure® titanium dioxide. ^
Other impurities and waste products are discussed later. (See: p. 35-44)
1. The TITANOX® Product Data Book, loc. cit.
2. E.I. du Pont de Nemours & Co., Pigments Dept., Materials Safety Data Sheets
-5-
-------
B. Chemistry
Titanium dioxide is thermally stable and is very resistant to chemical
attack.
1. Reactions Involved in Uses
The material is used because it is essentially inert in all major appli-
cations.
2. Oxidation
Ti02 is the oxidized state.
3. Hydrolysis
In water, there is essentially no hydrolysis. The tendency to form the
hydrate in acid or basic medium is limited, and no Ti(OH)^ form is re-
ported. The lower hydrates of the dioxide "are not obtainable by direct
addition of water to the crystalline oxides, but may be prepared in other
ways. . . . They are weaker acids than carbonic acid."(1)
4. Photochemistry
Despite the inertness of Ti02> there is some evidence that the untreated
pigments can contribute to the photodegradation of organic systems when
exposed to ultraviolet radiation. The pigments can be treated with the
oxides of metals, such as alumina, silica, zinc, etc., in a manner which
will substantially reduce their photoreactivity. Such treatment helps
reduce the tendency of TiO? to chalk in organic media exposed to moisture
and sunlight. The pure anatase is more active than pure rutile as a photo-
catalyst for the destruction of paint films. It also chalks more rapidly
than the rutile and is therefore usually treated for use in this application.
1. P.C.L. Thorne and E.R. Roberts, Inorganic Chemistry. (Fritz Ephraim)
Sixth Edition Revised (Edinburgh and London: Oliver and Boyd Ltd. and
New York: Interscience Publishers, Inc., 1954) p. 847
-6-
-------
5. Other
Titanium dioxide is inert to most acids and alkalies, slowly soluble in
hydrofluoric acid or in hot concentrated sulfuric acid.
When TiC>2 is heated strongly in a vacuum there is a slight loss of oxygen,
accompanied by the development of a dark blue color. This loss of oxygen
is insignificant and is reversible.
Hydrogen, carbon monoxide, and carbon reduce TiC>2 only partially at high
.,'
temperatures and pressures, yielding lower oxides or mixtures of carbide
(in the case of carbon monoxide or carbon) and lower oxide.
Chlorination is accomplished only in the presence of a reducing agent,
the position of equilibrium in the system TiO_ + 2C10 £ TiCl- + 0. being
(I)
far to the left.v '
1. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 396
-7-
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II. ENVIRONMENTAL EXPOSURE FACTORS
A. Production and Consumption
1. Quantity
In 1974, the production capacity of nine U.S. Ti00 manufacturers was esti-
(1)
mated at 939,000 tons. This figure represents an increase of 114,000 tons
over 1973 capacity and indications are that TiO capacity is rising.
Reported annual production figures vary, depending on time of reporting
and other factors. One source gives 1972 production as 718,000 tons; 1973
production as 772,000 tons; and 1974 production as 815,000 tons. Production
in 1975 is estimated at 835
slowing in production rate.
(2)
in 1975 is estimated at 835,000 tons. These figures indicate an expected
Another source, however, sets 1972 production at 687,300 tons, and shows
a continued increase in annual consumption from 1967. In 1971, apparent
consumption was 723,600 tons, including imports. In 1972, it was 787,100
tons, including a much larger amount of imports — 86,400 tons, 11% of
apparent consumption. Imports, in recent years, have ranged from 5% to 10%
of apparent consumption and no great change in percentage levels is antici-
pated in the near future. Exports have been usually less than 2% to 3% of
production (about 15,000 tons) from 1966 through 1971, but declined to
10,000 tons in 1972.(3)
1. Directory of Chemical Producers. (Menlo Park, California: Chemical
Information Services, Stanford Research Institute, 1974) p. 918
2. David M. Kiefer, "U.S. Industry Girds for No-Growth Year," Chemical
& Engineering News, _52_ (23 December 1974) p. 20
3. U.S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemicals Industry, EPA-230/2-74-015
(Washington, D.C.: U.S. GPO, April 1974) pp. 58-9
-8-
-------
In 1972, the three major user industries — paint, paper, and plastics —
accounted for almost 80% of the 787,000 tons consumed, the value of which
has been reported at nearly $433 million on a delivered basis.
2. Producers, Major Distributors, and Production Sites
The companies producing titanium dioxide in 1974, their plant locations,
and their annual capacities are listed in Table III. The information is
derived from the 1974 Directory of Chemical Producers. Recent changes
include the purchase of Sherwin-Williams Company's Ashtabula, Ohio, plant
(2)
by SCM Corporation. By 1975, Du Pont anticipates that the annual capa-
city of its Edge Moor, Delaware, plant will be 160,000 tons/year.' '
3. Production Methods & Processes
a. Manufacture of Titanium Dioxide Pigments
Titanium dioxide, when used as a pigment, is in the form of fine parti-
ulate matter with a median particle diameter of about 0.2y. A pigment has
been defined as any particulate matter that is insoluble in, and essentially
physically and chemically unaffected by, the media into which it is dis-
persed. Because titanium dioxide is the most widely used white pigment,
the titanium dioxide pigment manufacture is central to the industry.
White pigments are also used with colored materials to achieve various
shades.
1. U.S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemicals Industry, op. cit., pp. 58, 60-1
2. "At Sherwin-Williams, Change is More Than Logo Deep," Chemical Week,
116 (5), (29 January 1975) pp. 34-5
3. "Cleaner Units for TiO Still Leave Du Pont at Sea," Chemical Week.
116 (1), (1 January 1975) p. 26
-9-
-------
TABLE III(1)
PRODUCERS OF TITANIUM DIOXIDE
COMPANY PLANT LOCATION ANNUAL CAPACITY
(Thousands of Tons)
American Cyanamid Co. Savannah, Ga. 112
(Pigments Division)
Combustion Engineering, Inc. Camden, N.J. n.a.
(C-E Minerals Division) Wilmington, Delaware n.a.
E.I. du Pont de Nemours & Co., Inc., Antioch, Calif. 27
(Pigments Department) Edge Moor, Delaware 112
New Johnsonville, Tenn. 228
Gulf and Western Industries, Inc., Gloucester City, N.J. 43
(The N.J. Zinc Co., Subsidiary) Ashtabula, Ohio* 27
Kerr-McGee Corp. Hamilton, Mississippi 46
(Kerr-McGee Chemical Corp., Subsidiary)
Lonza Inc. Mapleton, 111. n.a.
NL Industries Inc. St. Louis, Mo. 115
(Titanium Pigment Div.) Sayreville, N.J. 124
SCM Corp. Baltimore, Md. 78
(Glidden-Durkee Div.) Ashtabula, Ohio^ ' 27
(Pigments and Color Group)
Transelco, Inc. Penn Yan, N.Y. n.a.
TOTAL 939
*Leased from Cabot Corporation
1. Directory of Chemical Producers, loc. cit.
2. "At Sherwin-Williams, Change is More Than Logo Deep," loc. cit.
-10-
-------
The methods of titanium dioxide preparation are related to the product to
be produced and to the end use of material, as well as the grade, proper-
ties, and composition of the particular raw materials. Analyses of typical
ores used in TiO_ manufacture are shown in Table IV.
Although many modifications are introduced by individual manufacturers,
there are basically two processes for manufacturing TiO — the so-called
"sulfate" and "chloride" processes. Plant capacity in the U.S. is divided
almost equally between these two processes, of which the sulfate is the
older. The chloride process, introduced in 1956, has received widespread
acceptance because it promises: (a) reduced investment, with figures show-
ing 60-70% of a sulfate plant; (b) lower production costs with savings
up to 5-6C per pound; (c) better product quality; and (d) "cleaner" from
an environmental aspect. Since 1956, the U.S. has built no new sulfate
plants; a few have been built overseas. Table V gives the location of
those companies using either the sulfate or chloride process.
(1) Sulfate Process
The major portion of the world's titania is produced by the sulfate process.
The primary raw material used is ilmenite ore or sand containing 40-60%
Ti02. However, some types of ilmenite are not 'suitable raw materials for
pigment manufacture because of impurities which pass through the process to
contaminate the product. There are instances where Canadian slag, con-
taining 60-70% Ti02, is substituted for ilmenite. This slag has a lower
iron content and correspondingly higher titanium content than ilmenite.
In general, the sulfate process employs sulfuric acid at high temperatures
to separate and recover TiO, from ilmenite or slag.
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products. EPA-440/l-74-007-a
(Washington, D.C.: U.S. GPO March 1974) p. 175
-11-
-------
TABLE IV
ANALYSES OF TYPICAL ORES USED FOR
Constituent
_JWt. %l
T.i.02
FeO~
Fe203 •
P205
V205
A1203
CaO
MgO
EiO2
Kncf
S
Co
Cr203
Zr02~
Fe
c
Nb02
H
Adirondack
44.5
38.0
5.8
0.04
0.14
1.79
0.58
2.14
2.48
0.50
0.17
0.02
0.01
Australian
Ilmenite
55.4
23.8
16.9
0.08
0.17
0.94
0.02
0.27
0.15
0.72
0.01
0.11
0.14
TITANIUM DIOXIDE MANUFACTURE
Florida
Ilmenite
64.0
3.2
26.9
0.21
0.13
1.5
0.13
0.35
0.3
1.35
0.09
0.10
0.07
0.27
0.11
0.27
Australian
Rutile
96.3
0.28
0.03
0.56
0.39
0.01
0.05
0.28
0.01
0.20
0.6
0.30
0.02
§1*3
71.0
10.9
0.01
0.5
5.7
1.0
5.0
5.0
0.3
0.09
0.2
0.5
N.B. Blank spaces indicate low impurity level or absence of reliable
analytical data.
-12-
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TABLE
PLANT LOCATIONS WHERE SULFATE PROCESS IS REPORTEDLY USED
COMPANY PLANT LOCATION ANNUAL CAPACITY
(Thousands of Tons)
American Cyanamid Co. Savannah, Georgia 72
(Pigments Division)
Gulf and Western Industries, Inc., Gloucester City, N.J. 43
(The N.J. Zinc Co., Subsidiary)
NL Industries, Inc. St. Louis, Missouri 115
(Titanium Pigment Division) Sayreville, N.J. 124
SCM Corporation Baltimore, Maryland 53
(Glidden-Durkee Div.,
Pigments & Color Group)
PLANT LOCATIONS WHERE CHLORIDE PROCESS REPORTEDLY IS USED
COMPANY PLANT LOCATION ANNUAL CAPACITY
(Thousands of Tons)
American Cyanamid Co. Savannah, Georgia 40
(Pigments Division)
E.I. du Pont de Nemours & Co., Inc. Antioch, California 27
(Pigments Department) Edge Moor, Delaware 112*
New Johnsonville, Tenn. 228
Gulf and Western Industries, Inc., Ashtabula, Ohio** 27
(The New Jersey Zinc Co., Subsidiary)
Kerr-McGee Corp. Hamilton, Mississippi 46
(Kerr-McGee Chemical Corp., Subsidiary)
SCM Corporation Baltimore, Maryland 25
(Glidden-Durkee Div., Ashtabula, Ohio(2) 27
Pigments & Color Group)
* By 1975, annual capacity is expected to be 160,000 tons/year.
** Leased from Cabot Corporation
(3)
1. Directory of Chemical Producers, loc. cit.
2. "At Sherwin-Williams, Change Is More Than Logo Deep," loc. cit.
3. "Cleaner Units for TiO Still Leave Du Pont at Sea," loc. cit.
- •-!--• -
-13-
-------
The amount of acid required for this process ranges from 2.5 to 4.5 pounds
per pound of finished pigment, depending on the TiCL content of the ore.
An acid solution of titanyl sulfate results as an intermediate product.
The acid solutions are clarified, cooled, and sent to a vacuum crystallizer
where a portion of the ferrous sulfate crystallizes out and is separated by
centrifugation. This salt can be sold or disposed of as a waste. There are
exothermic reactions which proceed rapidly causing a temperature increase
from 125 to 200°C. The reactions are carried on continuously or as a batch
(2)
process.
FeTi03 + 3H2S04 -»• Ti(S04)2 + FeS04 + 3H20
FeTi03 + 2H2S04 -*• TiOSO^ + FeSC>4 + 2H20
In the essential step, the titanium sulfate is hydrolyzed to form a white,
nonpigmentary hydrate. The addition of water converts the titanium portion
of the salt to metatitanic acid, which precipitates.
TiOSO. + 2H~0 -»• Ti00 • H00 + SO,
H i 224
The hydrate is then calcined at temperature up to 1250°C to remove the
water and absorbed sulfur trioxide to form crystalline titanium dioxide.
Ti02 • H20 + Heat -»- TiO + H20
Finally, the Ti02 is milled, surface treated (as needed) and packaged for
sale. The final chemical form of the Ti02 pigment, anatase or rutile, is
determined by the nucleus crystal used In the seed precipitation in the
hydrolysis step.
One of the major disadvantages of the sulfate process is the resultant
large amounts of waste in the form of spent sulfuric acid and ferrous
sulfate (copperas).
1. U.S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemicals Industry, op. cit., p. 64
2. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., pp. 351-2
-14-
-------
FIGURE I
Ti00 PIGMENT MANUFACTURING PROCESSES
-~ ' - £-~' ' ' '
Ilmenite
SULFATE PROCESS
Sulfuric
Acid Titanium Slag
Digestion
Reduction
Clarification
Crystallization
Copperas
(FeS04- 7
Titanium
Salt
Digestion
Scrap
Iron
Clarification
Nuclei
Hydrolysis
Filtration
Calcination
Ti02
Rutile or Anatase
CHLORIDE PROCESS
Carbon
Waste and/or
By-product
Titanium
Salt
Pigment
Finishing and Coating
Rutile
Chlorination
Ti Cl,
Purification
Oxidation
Ti02
Rutile
Chlorine
Chlorine Recovery
Neutralization
Finished TiO£ Pigment
-15-
ci2
Recycle
-------
(2) Chloride Process
The chloride process for titanium dioxide manufacture was introduced in
the U.S. by Du Pont in 1958. In this process, rutile ores containing
90 to 97% TiO_ are reacted with chlorine over carbon or coke, as a re-
ducing agent, to produce titanium tetrachloride. The various oxides in
the ore are vaporized at a furnace temperature of 850° to 1,250°F and
leave the furnace in a gaseous state.
Ti02(+Fe203) + 2C12 + C -*• TiCl4 + CC>2(+FeCl3)
This process is attractive because the TiCl, may be produced in a high
degree of purity.
Either hydrolysis of TiCl, or oxidation in the vapor phase is used to
produce TiO_. Hydrolysis may be accomplished with water vapor to produce
Ti02 and HC1, or liquid water to produce titanic acid, H2TiO , and HC1.
The titanic acid is then precipitated and ignited to produce TiO«.
+ 4HC1
In oxidation, purified TiCl, is fed to a reaction chamber with air or
oxygen. The resultant smoke is fine particles of TiO~ in an atmosphere
of chlorine (along with nitrogen if air is used.) The TiO- is collected
and the chlorine is recycled. This reaction is exothermic and is carried
(21
out continuously at about 1000°C.
TiCl4 + 02 -*• Ti02 + 2C12
Recycling the chlorine makes the oxidation process economically attractive.
Furthermore, Du Pont has developed the capability of using ilmenite in its
chloride process which helps lower its raw material costs.
1. W.L. Faith, D.B. Keyes, and R.L. Clark, Indus trial Chemicals.
Third Edition (New York: John Wiley & Sons, Inc., 1965) p. 765
2. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 351
-16-
-------
Impurities in the chloride system, such as iron and other metal chlorides,
entrained coke and ore, carbon monoxide, carbon dioxide, and hydrogen
chloride must be removed prior to the oxidation reaction to take care of
effluent waste control problems.
4. Market Price
The market prices of titanium dioxide ore depend to a large part on the
type of ore and its percentage of TiO- content. An example of the broad
(2)
price variations is given below. It is taken from 1970 data.
TABLE VI
TiO, C'onk'iit and I'rici-s lor l;our Tjpcs ol"l ilimimn Ore
Approximate Price
(S/sliort ton)
Content As lOO'.V
Ore . TiO, (Cr! As Ore TiO.
llmeniie
llmcniic
concenir;i!e
1'iUiniuin \l;i«
Kutilc
45
60
70
% ;
20
33
45
IM)
44
56
64
167
Bulk prices have risen dramatically to over $125 to $150 per ton from an
(3)
average price of $80-85 per ton in the late 1950's.
By mid-1973, the purchase price for dry-milled anatase was about 24 cents
per pound and for wet-milled was around 28.5 cents per pound. Recent price
(4)
hikes have been attributed to rising production and pollution control costs.
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products, op. cit., p. 55
2. W.A. Kampfer, op. cit., p. 11
Copyright © 1973, John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.
3. Nicholas R. lammartino, "Troubled Times for TiO-," Chemical Engi-
neering. 7£ (1 May 1972) p. 35
4. "American Cyanamid Has Raised Titanium Dioxide Tabs," Chemical Week,
112 (28 March 1973) p. 27
-17-
-------
Late in 1974 NL Industries increased its prices for all rutile and wet
milled anatase grades of TiO_ by five cents per pound and its nonpigmen-
tary and dry milled anatase grades by three cents per pound. Thus their
current prices for rutile grades range from 40 to 41 cents per pound for
carloads or 20-ton minimum truckloads; 40 3/4 to 41 3/4 cents per pound
for 10 to 20 tons; 42 to 43 cents per pound for 5 to 10 tons; and 43 to
44 cents per pound for less than five tons. Their current prices for
anatase range from 35 to 43 cents per pound depending on the grade and
for nonpigmentary grade range from 35 to 38 cents per pound. There is an
additional one cent per pound charge for shipments west of the Rocky Moun-
tains and a $15 charge for small quantities of less than 2,500 pounds.
Prices for N.J. Zinc Company's anatase and rutile grades of TiO_ are 43.5
cents and 38.5 cents per pound respectively. An increase of 3.5 cents per
(2)
pound is scheduled to be effective as of March 1, 1975. However, in
March 1975, the Glidden-Durkee Division of SCM Corporation rescinded the
five cents per pound increase in the price of its Zopaque TiO- products
that had been announced in January. Bulk prices will remain at the July
1974 level of 40 cents per pound while there is an revision on smaller
(3)
shipments as follows:
5-ton lots 1 cent/pound differential over bulk prices
(down from 2 cents/pound)
less than 5-ton lots 1.5 cents/pound differential over bulk prices
(down from 3 cents/pound)
The prices of anatase pigment has increased about 6 1/2 cents per pound
over the last twenty years, rutile by about 7 cents per pound, 30% ex-
tended Ti00 pigment by 2 1/2 cents per pound, and 50% extended TiO, pig-
(4)
ment by 13/4 cents per pound. The greatest increase, however, occurred
in the early and middle 1950's.
1. "Titanium Dioxide," Rubber Age, 106 (December 1974) p. 12
2. "Titanium Dioxide," Rubber Age, 107 (February 1975) p. 14
3. "Pigments," Rubber Age, 107 (March 1975) p. 12
4. W.A. Kampfer, op. cit., p. 9
-18-
-------
Table VII shows the smoothing out of the list prices from 1965 through
1971. Commercial shipment values of titanium dioxide are also given in
that table.(1)
TABLE VII
TiCK COMMERCIAL SHIPMENT VALUES
1965
1966
1967
1968
1969
1970
1971
4.
(Shipments in Thousands of
Commercial Total.. 2
Shipments Value Value/Lb .
524.5
545.4
542.6
564.4
590.1
560.9
581.2
274.7
279.7
277.2
288.8
301.1
277.8
262.4
.261
.256
.255
.256
.255
.248
.226
Tons)
List
Anatase
.25
.25
.25
.25
.26
.26
.26
Prices3
Rutile
.26
.26
.26
.26
.27
.27
.26
Value in $ Millions.
2
Value in $ per Pound.
3
Car lot, $ per Pound.
Source: Current Industrial Reports, U.S. Department of Commerce.
1. U.S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemicals Industry, op. cit., p. 78
-19-
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5. Market Trends
In 1974, there were nine producers of T102 in the U.S. with fifteen
plants in operation, only one of which is in the western portion of the
country. Although both the sulfate process and the chloride process
are being employed, new titanium dioxide pigment plant construction since
1956 has been chloride facilities with capacities between 25 to 30,000
tons. Du Pont, the company responsible for introducing the chloride process
initially, is increasing the capacity of its New Johnsonville, Tennessee,
plant to 195,000 tons (scheduled for completion year-end 1973) and is ac-
(2)
tively considering a new 100,000 ton chloride facility in Georgia.
Furthermore, Du Pont Pigments Department stated in the Fall of 1974 that
when it completes its construction program at Edge Moor and other locations,
it will have about doubled its output of titanium dioxide in this decade to
(3)
well over a half-million tons a year. Although the overall growth in
titanium dioxide production has been generally and steadily up and is ex-
(4)
pected to increase into 1975, there are signs of a slowing:
1972 718,000 tons
1973 772,000 tons
1974 815,000 tons
1975 835,000 tons
It is felt in some sectors, however, that demand could catch up to current
capacity as early as 1976.
1. Directory of Chemical Producers, loc. _
2. U. S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemistry Industry, op. cit., p. 66
3. "Progress in Pigments Comes From Du Pont," Chemical Week, 115
(20 November 1974) p. 1
4. David M. Kiefer, log, cit.
-20-
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a. Raw Materials and Market Trends
Along with production of titanium dioxide, market price bears an influence
on market trends. The stability of the titanium dioxide market price
depends greatly on the ready supply of raw materials. The more abundant
ilmenite ores can be used to feed the sulfate process while the supply
of rutile ore, which feeds the chloride process, is in question. The
supply and cost of rutile have been considered factors influencing the
closing or possible closing of two plants — one being PPG Industries'
Natrium, West Virginia chloride plant in 1971 and the other NL Industries'
Sayreville, N.J. chloride plant. Thus, one of the major and current
concerns to the Ti09 industry is the availability of raw materials.
Extensive deposits of ilmenite are found throughout the world. It is
mined extensively in many countries, the biggest producers being the
United States, Australia, and Norway. World production, since 1967,
has been approximately 3 million short tons per year, with the U.S.
contributing about 700,000 short tons to this total.
Known reserves of rutile, which is mined principally in Australia, are
considered limited and barely able to meet demand. No rutile is mined
in the United States. Current world production of about 400,000 long
tons per year will probably deplete known reserves within 20-25 years.
Because no new deposits of natural rutile have been found, Ti09 manu-
facturers must seek sources of rutile other than the natural ores.
Ilmenite is ferrous titanate, FeO-TiO_ or FeTiO-, usually containing
some ferric ion, and sometimes occurring associated with other ores.
It occurs massive in some areas of the world; as a constituent of beach
sands in other areas. In these latter areas, the action of waves and/or
wind causes a degree of concentration in the ore, which is also altered
by oxidation and leaching. The result of these actions is an increase
1. Nicholas R. lammartino, op. cit., pp 34-6
-21-
-------
in the ratio of ferric to ferrous iron, and a decrease in the amount of
iron present with a corresponding increase in the amount of TiO.. This
form of titanium dioxide also changes, passing through a leucoxene stage
to rutile. Leucoxene is still too high in iron content for economic
use in chlorine processes that depend on availability of rutile ore. In
addition some types of ilmenite are unsuitable for pigment manufacture
because of impurities which pass through the process to contaminate the
product.
The relative abundance of ilmenite compared to rutile makes beneficiation
(2)
of ilmenite promising technology. One potential source to offset the
question of rutile reserves is the upgrading of ilmenite to over
TiCL through the removal of iron. It can then be processed, utilizing
the rutile chloride technology. This removal of part or all of the iron
content of the ilmenite ore whereby there remains a product soluble in
sulfuric acid, or which can be chlorinated economically, is the nature of
the beneficiation process. Some ilmenite producers and rutile consumers
alike are interested in beneficiation. Furthermore, Du Pont has a process
to use mixed ores in their feed and still other manufacturers are develop-
ing technology so that unbeneficiated ilmenite can be chlorinated.
The initial trend away from sulfate to chloride manufacture of TiO_
was due in part to the introduction and development of the chloride
process and further reinforced by environmental questions surrounding
the sulfate process. However, the chloride process is not trouble free.
There are examples of investment, economic and maintenance difficulties
in a few chloride plants that illustrate expenses and down-time well
beyond initial estimates. The possibility of raw materials problems
for the chloride plants and the development of pollution control facili-
1. Kirk-Othmer Encyclopedia of Chemical Technology. ££. cit., p. 398
2. Ibid., p. 399
-22-
-------
ties for sulfate plants may shift the emphasis and concern regarding current
dilemmas facing the Ti02 manufacturer. "Although estimates indicate that
the cost of chloride process plants is only 60 to 70% that of sulfate plants,
the chloride process requires 96% rutile Ti02 ore at about $160/ton compared
to about $33/ton for ilmenite concentrate containing 60% TiO,. Present day
economics appear to favor the modern automated sulfate plant (with control-
led emission and by-product utilization) for the production of a titanium
dioxide that is completely equivalent to the chloride product."^
b. Waste Disposal and Market Trends
Of the two methods of manufacturing TiO?, the older sulfate process is
considered to be plagued with environmental troubles. Waste disposal
problems center around the spent sulfuric acid and copperas (FeSO,-7H90).
For the most part wet scrubbers reduce the air pollution problems result-
ing from the particulates emitted from sulfate manufacture. Technology
exists for the recovery of copperas, a portion of which is sold as a
flocculating agent, with the remainder either being stockpiled or disposed
of with the acid waste.
On the other hand, the chloride process is reputed to have simpler waste
disposal requirements than the sulfate process. The primary reason for
this is that rutile ore is the customary raw material in the chloride
manufacture of TiO_. Since the starting ore contains a high percentage
of TiO-, there is a minimum of iron chloride by-product and waste.
With the dwindling known supply of rutile, however, comes the question
of modifying existing chloride plant technologies for TiO_ manufacture
to accommodate other feed, such as beneficiated ilmenite or to chlorinate
unbeneficiated ilmenite. An acid-leaching process for ilmenite benefi-
ciation seems to be the one most used commercially. Existing plant capa-
cities are shown in Table VIII. Waste disposal is a limiting factor with
ilmenite beneficiation, as is iron oxide pulp tailing.
1. W.A. Kampfer, op. cit., p. 12
2. Nicholas R. lammartino, op. cit., p. 35
-23-
-------
TABLE VIII
PLANT LOCATIONS AND CAPACITIES
FOR ILMENITE BENEFICIATION
BY ACID-LEACHING PROCESS
COMPANY AND PLANT LOCATION CAPACITY
BENEFICIATED
ILMENITE
Gulf Chemical and Metallurgical Corporation
Texas City, Texas *40,000 tons/yr.
Western Titanium N.L.
Australia **12-13,000 tons/yr.
Benilite Corporation of America
Corpus Christi, Texas 2,000 tons/yr.
* limited by waste disposal problems to 10,000 tons/yr. in 1971
** with some Fe,0, pulp tailing
-24-
-------
Other beneflciation technologies follow different routes, such as those
shown in Table IX below:
TABLE IX
PROCESSOR AND TYPE OF PROCESS
USING OTHER BENEFICIATION TECHNOLOGY
PROCESSOR
AND
LOCATION
TYPE OF PROCESS AND YIELD
BASIC
TECHNOLOGY
U.S. Bureau of Mines
Albany, Oregon
pyrometallurgical process
with 90-97% Ti02 concentrate
selling for over $80/ton and
marketable pig iron
oxidation and
fluxing of ilmenite
slag in electric
furnace
Rolla Metallurgy
Research Center
Rolla, Missouri
carbonyl process
iron penta-carbonyl
by-product can be
decomposed to iron
powder and CO (for
recycle)
CSIRO and
Murphy Ores Inc.
Brisbane, Australia
Murso Process Product
with 95-96% TiO,,
oxidation and separa-
tion of iron and
other impurities
(1) Nicholas R. laminartino, op. cit., p. 36
-25-
-------
B. Uses for Titanium Dioxide
Consumption of titanium dioxide is usually divided into two general cate-
gories - the pigment industry and non-pigment uses. The coarse particle
size is preferable for nonpigmentary purposes with its "ease of handling,
freedom from dusting, ease of blending with other materials, and, in the
ceramic industry, ease of shrinkage control during firing."
On the other hand, improvements in technology over the years from about
1954 to about 1959 made it possible to produce chloride process pigments
possessing superior tinting strength, hiding power, and color by virtue
of their smaller particle size and narrower distribution range compared
to their sulfate counterparts. More recently sulfate process pigments
have been manufactured in the necessary, closely controlled particle
size range that is considered the single most significant factor in the
(2)
production of titanium dioxide with optimum properties.
1. Major Uses
The distribution of titanium pigment shipments by industries is an indi-
cation of the end use pattern of the titanium dioxide produced. In 1967,
the percentage distribution by gross weight was reported as listed in
Table X.(3)
1. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 396
2. W.A. Kampfer, op. cit., p. 12
3. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit,, p. 408
-26-
-------
TABLE X
PERCENTAGE DISTRIBUTION
OF TITANIUM PIGMENT SHIPMENTS
BY INDUSTRIES
Industry % (Distribution by Gross Wt.)
paints, varnishes & lacquers 61.9
paper 14.6
floor coverings 2.7
rubber 2.8
coated articles & textiles (oil cloth,
shade cloth, artificial leather etc.) 1.4
printing ink 2.0
roofing granules 1.1
ceramics 1.9
plastics (except floor coverings and
vinyl-coated fabrics and textiles 5.1
other (including export) 6.5
The percentage distribution of TiO_ in total pigment used by the two prin-
cipal industries at that time was:
Industry % (Distribution by TiO. Content)
paints, varnishes and lacquers 57.5
paper 17.2
The percentages above refer to 587,995 short tons as the total U.S. pro-
duction (TiO» content) in 1967.
1. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 408
Copyright © 1969, John Wiley & Sons, Inc. Reprinted by permission of
John Wiley & Sons, Inc.
-27-
-------
More recent figures are given in Table XI to show market consumption of
titanium dioxide in 1970 and 1972 distributed by industries.
TABLE XI
MARKET CONSUMPTION OF Ti02 BY INDUSTRIES
INDUSTRY
Ti02 MARKET CONSUMPTION
Paint and Coatings
Paper
Plastics
Rubber
Floor Covering
Printing Ink
Ceramics
Synthetic Fibers
Roofing Granules
Other
TOTAL
(Thousands
1970
375
147
59
35
30.
18
17
10
5
34
730
of Tons)
1972
390
158
78
35
30
20
21
10
5
40
787
1. U.S. Environmental Protection Agency, Economic Analysis of Effluent
Guidelines for the Inorganic Chemicals Industry, op. cit., p. 60
-28-
-------
a. Paints, Varnishes, Lacquers
Although paint producers consumed 66.9% of the T10- sold in 1950 in the
U.S., by 1969 paint accounted for only 54.3% of the TiO. sales. The actual
quantity of TiO utilized in coatings has steadily increased at an annual
(1)
rate of growth about 4.37% per year.
Both particle size and surface treatment are specially controlled with
pigmentary rutile which is used primarily for opacity, color, and tinting
strength. Special treatments and manufacture provide resistance to chalk-
ing and fading in organic media (paints) exposed to the weather. Enamel
grades are designed for all types of gloss and semigloss architectural
and industrial coatings. Dry hiding grades are designed for flat paints
including oil, alkyd and latex based products.
Pigmentary anatase is generally used in exterior paints to induce chalk-
ings and thereby promote clean-up, to maintain a white appearance as the
paint weathers. In these coatings, a blue-white color is of higher
priority than is opacity.
b. Paper
The paper industry is another large user of titanium dioxide. In paper
making, water dispersibility and wire retention are probably the two most
important properties required of the pigment. It is treated specially to
insure high solids dispersion in aqueous systems. In the paper product as
a filler, interfaces between pigment and air contribute to opacity, and
(2)
provide a reduction of "show-through" in printed papers.
Titanium dioxide is also used in paper coatings.
1. W.A. Kampfer, op. cit., p. 12
2. Ibid., p. 20
-29-
-------
In minimum opacity applications, such as glassine waxed paper, unbleached
board and specialty papers, chloride process rutile effects economies
and brightness over anastase pigments. Some pigmentary rutile is de-
signed for use in melamine laminate compositions where its resistance to
ultraviolet light discoloration is outstanding. Likewise it is recommended
for use in printing inks which are applied to melamine formaldehyde lami-
nate systems and resins.
Consumption of TiO» by the paper industry has increased over the last
twenty years at a rate of growth of approximately 7.1% per year. A contin-
uation in this rate of growth may be somewhat optimistic, however, in view
of the increased use of fine particle size, high brightness extenders in
(2)
paper manufacture. Titanium dioxidt
its high refractive index and opacity.
(2)
paper manufacture. Titanium dioxide will continue to be necessary for
c. Plastics, Rubber, and Floor Tile
Very fine particle size titanium dioxide pigment is necessary to produce
brightness and blue tone in plastics with pigmentation ranging from 0.5 pph
(3)
of resin to 15 pph. Regular particle size grades are used in plastisols
and some specialized areas for chalk resistance. In addition, TiCL pro-
tects polymers which can be degraded by light, as well as all types of
materials packaged in plastic containers.
Although the tonnage of TiO_ used by the plastics and paper industries is
low compared to that consumed by the paint industry, individual plastic
products may contain a higher fraction of TiO... Titanium dioxide pigment
is used in polyvinyl chloride, polyethylene, polystyrene, vinyl-asbestos
floor tile, etc. In plastics applications, such properties as opacity,
tinting strength, wettability, low abrasion and the ease of dispersion of
1. The TITANOX® Product Data Book, loc. cit.
2. W.A. Kampfer, op. cit., p. 12
3. Ibid., p. 20
-30-
-------
titanium dioxide can be obtained by treating the surfaces. Thermal dis-
coloration in the presence of certain phenol base antioxidants and ultra-
violet light absorbers can be controlled in polyolefins and vinyls. Special
grades of rutile pigments are designed for high temperature exposure en-
countered in manufacturing blown and cast film for rigid weather resistant
siding, and for acrylic plastic sheet. On the other hand, special grades
of anatase pigments are recommended for white side wall rubber stock.
Consumption of TiO. by the plastics industry has increased over the last
twenty years at a rate of growth of approximately 10% per year. As the
applications for plastic products increases, greater consumption of tita-
nium dioxide in the plastics industry follows. There is also an increasing
trend toward the utilization of pigmented plastics where paints and coatings
were previously used.
2. Minor Uses of Titanium Dioxide
The three major use industries — paint, paper, and plastics — account
for over 80% of the TiO- pigment consumed. Howe^
other industries which utilize titanium dioxide.
for over 80% of the TiO- pigment consumed. However, there are numerous
a. Printing Inks
Titanium dioxide pigments are used extensively in printing inks: offset,
metal decorating, textile and silkscreen. High gloss pigments are used
in letterpress, gravure, and spirit flexographic inks while chloride
rutile pigments with high-hiding properties are applied to low-gloss water-
based flexographic inks. The low abrasivity of these Ti09 pigments is
another property which contributes to the utilization in inks.
1. W.A. Kampfer, op. cit. p. 12
-31-
-------
b. Ceramics
The coarser grades of TiO_ are employed by the ceramics industry for por-
celain enamels applied to sheet steel or aluminum, glass decorating enamels,
glass, and glazes. They are regenerated in the proper size through preci-
pitation or crystallization from the frit on firing the enamel. Nonpig-
mentary grades of TiO are efficient ultraviolet screening agents for glass
containers of all types, providing protection for food and beverages there-
in contained. To obtain these properties the absorption edge at the blue
end of the spectrum is shifted to longer wavelengths.
c. Textiles
Anatase is utilized more often in the textile industry as rutile, is not so
soft and may cause excessive abrasion of high-speed spinning and process-
ing equipment. Because TiO~ has a very high refractive index compared to
that of synthetic fiber, the pigment offers good light scattering or de-
lustering quality to synthetic fibers.
For internal delustering, anatase Ti09 is incorporated at a level of 1%
(1)
to 3% into the liquid mass before extrusion into fiber. For external
delustering and light stability, titanium dioxide is employed with suitable
organic binders in aqueous dispersions applied as coatings or dulling-agents
to the final fabric, such as polyamide, polyester, acetate, or viscose.
d. Food and Cosmetics
A highly purified grade of TiO. is approved for use in the food and cos-
metic industries. One special grade has been manufactured for years for
lipstick and face powder applications. Other grades have been labelled
"color additive" or "food additive" in such foods as cheeses. Titanium
dioxide is also approved for use in packaging materials which are in con-
tact with foods and special toiletries.
1. W. A. Kampfer, op. cit., p. 21
-32-
-------
e. Other Rutile and Anatase Pigmentary Products
The other miscellaneous industries utilizing titanium dioxide pigments
include both anatase and rutile applications. The extensive list includes
cement base coatings, caulking compounds, roof granules, leather and shoe
dressings and finishes for other leather products, ceiling tile and ceiling
tile coatings, and welding rod coatings, to name a few.
f. Other Predispersed and Nonpigmentary Applications
Predispersed titanium dioxide is stable in hard water and compatible with
calcium carbonate extenders. Examples of typical applications are gloss
and semigloss latex finishes, filler and coatings for some paper makers,
(2)
aqueous flexographic inks where full gloss coating is needed.
Other nonpigmentary uses include particular ceramic applications. Special
grades of titanium dioxide impart acid resistance to aluminum and glass
label enamels and to dry process enamels for cast iron, porcelain enamels
and glazes. Others aid in smelting fast fire glazes, as well as contri-
buting high opacity. Electrical ceramic specialty applications include
thermistors and capacitors and space applications.
g. Gems for Jewelry
Large titanium dioxide crystals with their translucent water-white or
yellowish cast are suitable for use in jewelry. A substantially pure and
massive single crystal of rutile has the properties of a precious gem
with a very light straw color and with reflectance, refraction and bril-
(4)
liance measuring greater than those of a diamond. However, the hard-
ness of diamonds is lacking in TiO_ crystals, and this is not a large use.
1. W.A. Kampfer, op. clt., p. 22
2. TITANOX® Product Data Book, loc. cit.
3. Loc. cit.
4. The Merck Index. Eighth Edition (Rahway, N.J.: Merck & Co., Inc.,
1968) p. 1054
-33-
-------
3. Discontinued Uses
No information was found.
4. Projected or Proposed Uses
No information was found.
5. Possible Alternatives to Uses
Only in the paper industry is the consumption of TiO. threatened by sub-
stitute products. Although it is an effective opacifier, it is at a cost
disadvantage to alumina and silica clays, some of which offer nearly
equivalent brightness.
To the plastics and rubber industries TiO^ offers the best combination of
white pigment cost, dispersability, and resistance to discoloration.
In the paint industry no equally effective white pigment in terms of
hiding power has been found in years of extensive research. Titanium
dioxide is also considered a key to the current trend of one-coat paint
applications.
There are no apparent substitute products which are currently competitive
in any of the other product application areas.
The captive consumption of T±0 pigment is in the paint industry where
three out of the top six have their own pigment plants and where captive
use as a percentage of apparent consumption has risen from 8% in 1965 to 14%
in 1971. Du Pont, SCM Corporation's Glidden-Durkee Division, and NL Industries
are major so-called "captive" users of titanium dioxide. (Sherwin-Williams
no longer appears on that list with the purchase by Glidden-Durkee of the
Sherwin-Williams' Ashtabula, Ohio, Plant.)
1. "At Sherwin-Williams, Change is More Than Logo Deep," loc. cit.
-34-
-------
C. Potential Sources of Environmental Contamination
1. General
Researchers, producers, and users throughout the titanium dioxide industry
have given consideration to the environmental contamination potential from
TICK. Principal contaminants to the environment are associated with the
impurities resulting from titanium dioxide raw materials processing and
the disposal of process waste. There has been considerably less environ-
mental attention given to the transport, packaging, storage and usage of
titanium dioxide.
Titanium dioxide is purchased in volumes, which are comparable to those
of some commodities, but in terms of marketing, it is more like a specialty
chemical than a commodity. It is utilized in numerous products for its
enhancing properties. However, it retains its chemical and physical
stability in end-use products.
2. Potential Environmental Contamination from Production
Each of the two processes for manufacturing titanium dioxide are based
on somewhat different raw materials and involve quite different tech-
nologies. Consequently, each process is discussed separately below from
the point of view of environmental contamination.
a. Potential Environmental Contamination from the Sulfate Process
As mentioned in the earlier discussion concerning the sulfate process,
there are contaminants which are generated from the metallic impurities in
the ilmenite ore, as well as pollutants resulting from the chemical pro-
cessing of the raw materials into TiCL. Silica, coke or carbon, and other
sulfuric acid insoluble ore residues result from the sulfate process.
The acid wastes, however, from the sulfate processing, are of concern.
The technology exists to recover sulfuric acid from the waste, but the
general opinion held by those who have attempted it is that it is not
-35-
-------
economically feasible to handle the acid problem in this manner. Therefore,
the acid wastes must be neutralized to meet water quality standards. Follow-
ing neutralization, there results large amounts of waste products, including
iron oxides or hydroxides and trace amounts of hydroxides of manganese and
chromium.
A list of raw wastes, which have come from typical plant manufacture of
TiO- by the sulfate process is given in Table XII below.
TABLE XII
SULFATE PROCESS WASTE STREAMS IN TITANIUM DIOXIDE MANUFACTURE
•1. Dissolving and
Filtration
2. Copperas (if
produced)
3. Strong Acid
U. Weak Acid
5. Vent and Kiln
Scrubbing
6. TiO2 Losses
Ore fjnd scrap .i ron
plus flocculonts
H2SOi|
Organic Carbon
FeSO
-------
Following the digestion of ilmenite ore in processing with concentrated
sulfuric acid (about 150% of the weight of the ore), resulting sulfates
of titanium and iron are leached from the reaction mass with water. In
the next step, any ferric salts present are reduced to ferrous by treat-
ment with iron scrap to prevent coloration of the final TiO~ product.
The resultant solutions are clarified and cooled. Ferrous sulfate (copperas),
which is crystallized and separated by centrifugation, is either sold
(generally as a flocculating agent) or disposed of as a solid waste
(1)
The effluents from four titanium dioxide plants which utilize the sulfate
process are listed below in Table XIII and show considerable variation
(2)
from plant to plant. It is noted that none has a pH discharge in the
6.-9.0 range for all streams. All contain 3000 mg/1 dissolved solids.
TABLE XIII
PARTIAL DISCHARGE DATA FROM Ti02 SULFATE PLANTS
Paramatgr*
BOD5
COD~
pH
Alkalinity 220
Total Dis- '""
solved
Solids
Plant 142 <2) (3) Plant 122
Streams P1ant °46 Streams Streams
. 1 No. 2 No. 1 No. 2 No. 3 No. 1 NO. 2
10 3 6 3
71 145
.0 1.2 6.5 5.6
20 —
60 22,371
15,316
21,300
287
1.0
14,000 15,400
0.3
42
2.6
3,000
No. 3
0.5
27
5.0
2,700
Plant
008
No. 1
5 min
5,OOC
Iron
Sulfate
Chloride
Acidity
Flow,
cu m/day
(MGD)
0.02
1,170
51.5
—
823
12,377
105
11,435
10,200Combined
(2.7)
--
0.5
1,617
6,394
36
20,000
(5.5)
1.7
1,378
7,900
—
123,400
(32.6)
31,000
131,000
—
—
6,100
(1.6)
1.
6,
20,
20,
(5
000
800
625
000
000
•5)
2.
40,
(10
45
187
480
160
900
.8)
15
125
2,830
1000
30,300
(8.0)
100
— —
—
--
(1) One~plant~of one manufacturer is not listed here. Data on titanium dioxid
and chromate concentrations were provided.
(2) The corporation owning this facility is currently developing a process
for recovery and recycle of the sulfuric acid used. This process is
still under testing on the pilot plant scale.
(3) This plant barges its strong acid wastes out to sea for disposal. This
method of disposal of highly acid wastes containing large amounts of
dissolved heavy metals is not considered satisfactory. Effluent No. 3
is the available data on material dumped at sea.
*mg/l unless otherwise specified
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products, op. cit., p. 173
2. Ibid., p. 179
-37-
-------
b. Potential Environmental Contamination from the Chloride Process
As mentioned in the earlier discussion concerning the chloride process,
titanium dioxide ores are chlorinated^ using coke to promote the reaction,
to produce titanium tetrachloride (as an intermediate) plus carbon dioxide
and iron chloride. In the next step, the titanium tetrachloride is oxi-
dized to TiO_ and chlorine, which is recycled.
Carbon, unreacted ore, and some non-volatile chlorides of metallic impuri-
ties in the ore, result from the chlorination and are considered non-
hazardous. The products of chlorination are cooled and the undesired
metal chlorides condensed. The solid waste stream, however, usually
contains titanium hydroxide and small amounts of compounds of vanadium,
aluminum, copper, chromium, zirconium, and niobium. The use of copper
is not considered representative of the industry, but where added in the
purification stage, it will be the major constituent in the waste.
c. Potential Contamination from Titanium Dioxide Plants
Waste discharge data for nine titanium dioxide plants are summarized in
Table XIV. The information therein was obtained from both discharge
permit applications and data sheets. The parameter 'loadings' were cal-
culated from reported daily average concentrations, discharge flow rates
and annual production rates. The computation for each plant was made for
350 days operation during the year. Of the nine plants, four use the
chloride process only, three use the sulfate process only and two use
both processes. Three of the plants in this group dispose of part of
their wastes in landfills, two discharge part in the ocean by barge trans-
port and one uses deep-well injection. For six of the plants, the data
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products, op. cit., p. 53
-38-
-------
represent the total discharge of plant effluents to streams and to land-
fill, deep well, or ocean. For the other three plants, the data given
in the Table represent only a part of the total wastes. Although the
treatment of wastes discharged to streams varies considerably, all of
the nine plants reported that their waste disposal systems were in the
process of being modified or improved.
(2)
TABLE XIV
WASTE DISCHARGE DATA FOR TITANIUM DIOXIDE PLANTS
Parameter
Average wastewater
discharge, millions
of liters/day
Total dissolved solids
Total suspended solids
Total volatile solids
Acidity/alkalinity
BOD 5
COD
Oil and grease
Total organic carbon
Total organic nitrogen
Ammonia, as N
Chloride
Fluoride
Nitrate
Sulfate
Sulfide
Phosphorus, total
Iron
Titanium
Antimony
Arsenic
Cadnium
Chromium
Lead
Manganese
Mercury
Nickel
Selenium
Zinc
Waste loading, Kq7rr.otric ton of product" »c
Plant A
Cl, SO.
112
2,650
46
1,043
1,652
4.6
40
3.3
1.5
1.0
0.4
316
-
-
484
-
0.2
449
26
300
-
3
440
150
14,000
0.04
-
500
600
Plant E
SO,
35.2
2,274
24
-
-
0.6
26
0
-
1.3
7.7
13
-
-
980
-
0.5
656
19
-
-
0
1,100
0
-
0
-
-
1,100
Plant Cd
Cl, S0k
135
3,72C
53
-
-
0
26
0
-
0
0
35
-
-
3,170
1.0
0.06
192
40
-
-
-
1,900
200
-
0
-
' -
600
Plant Dd
SO,,
146
7,240
595
1,060
20
2.1
-
- .
2.2
1.4
<0.1
3,540
-
-
205
<0.03
0.05
7
0.9
-
-
<1
30
<0.3
-
<0.3
-
-
40
Plant Ed
Cl
11.0
601
7.1
-
15
0.6
9.1
<0.1
3.5
0.3
0.7
453
0.2
-
32
0.008
0.2
0.05
9.8
-
-
<0.6
50
3
-
<0.1
10
<0.6
3
Plant F
Cl
J34
1,330
15
-
-
-
-
-
-
-
-
877
-
-
26
-
-
330
-
-
-
-
-
_
-
-
-
-
—
Plant G
Cl
2.8
175
-
-
-
-
-
-
-
-
-
181
-
-
35
-
-
27
1.4
_
-
-
0.2
_
-
0.02
1
-
—
Plant !!
Cl
2.6
169
0.2
4.4
2.2
<0.4
1.1 '
-
Plant I
Cl, SCk
109
_
-
-
-
-
-
1.0
0.6 j 2.0
0.01
<0.01
47
0.05
0.05
16
-------
d. Air Pollution
In both the chloride and sulfate processes, gases are treated to recover
valuable constituents for recycle, especially chlorine and product dusts.
Although complete removal of all gaseous pollutants is rarely possible,
the magnitude of the gaseous emissions should be small when compared with
the control of fine particulates. As with all particulate removal pro-
cesses, the installation of air pollution control devices depends upon
either recovery of an economically valuable product or a threat of penal-
ties from regulatory agencies for failure to meet emission standards. Al-
though technology is available to remove large size particulates, many
processes such as encountered in the manufacture of titanium dioxide
generate fumes or smokes which have particulate sizes approaching the size
of molecules which make their collection very difficult or impossible.
The nature of titanium dioxide emissions is largely dependent on its
boiling point (given at 2700°C). Because it is substantially higher than
the combustion temperatures of coal or incinerator refuse, the emission
in both cases, is probably physically and chemically the same as the feed
material.
Fine particles (1 micrometer in diameter and smaller) from TiO emissions
may travel considerable distances before being deposited or being washed
out of the air by natural processes. Hard-rock mining of ilmenite produces
particles ranging from 1/2 to 10 micrometers in diameter with an average
(2)
diameter of approximately 5 micrometers. Furthermore, since ilmenite
is a moderately hard material, the beneficiating operations, which involve
intense mechanical pulverization, result in a moderate amount of fine
particles.
1. GCA Corporation, Emissions Inventory of Sources and Emissions of
Titanium. EPA-450/3-74-208 (Research Triangle Park, N.C.: U.S. EPA,
May 1973) p. 27
2. loc. cit.
-40-
-------
About 9.8% of total U.S. TiO_ emissions comes from pigment handling pro-
cesses, including incineration of paper containing pigment coatings.
Particle size estimates from one pigment manufacturer are given as 0.1 to
1.0 micrometer in diameter, with an average diameter of 1/4 micrometers;
another gave nearly all particles under 0.2 micrometers, with about 2%
ranging up to 0.40 micrometers.
(2)
Estimates of Ti00 content in emissions by source are given in Table XV.
3. Potential Environmental Contamination from Package, Transport and Storage
Packaged shipments of titanium dioxide primarily for pigment use are made
in paper sacks containing 25 kg. (50-56 pounds). Bulk shipments are made
(3)
in tank rail cars and tank trucks. Paper mills receive a slurry of
anatase in water shipped via tank cars and tank trucks. Paint manufacturers
(4)
receive shipments of rutile as a slurry.
Titanium dioxide is handled as an inert material. However, damp or wet
storage areas may promote the degrading of its physical properties.
4. Potential Environmental Contamination from Application and Use
The primary focus for environmental concern when TiO~ is utilized indus-
trially is the aerosol dispersion. Occupational exposures to TiO_ consist
1. GCA Corporation, op. cit., p. 28
2. Ibid., pp. 10-12
3. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 408
4. Harry Hyman, loc. cit.
5. loc. cit.
-41-
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TABLE XV
SOURCES AMD ESTIMATES 0? TITAHIUM-COHTAIHING EMISSIONS
1. MINING & BENEFICIATION
Open Fit Mining
Beneflciatlon
Open Pit
Dredging
2. METAL PROCESSING
Metal Ingots
Carbides
Alloys:
Titanium- Base
Ferrotitanluffl
Steel Production
3. OTHER MINERAL USES
Welding Rod Coating
Ceramics
Fiberglass
Pigment Production
Sulfate Calcining
Grinding
Drying & Sacking
-------
chiefly of dust and fumes from electric furnace operations. Above the
OSHA-established exposure limit of 15 mg/M , TiO dust can cause irritation
to those working with it or present in the work areas.
Available information on users of titanium dioxide pigments indicate that
occupational exposure may be considerable in some manufacturing processes
(e.g., rubber) while it is negligible in others (e.g., hosiery). "This
(2)
information, however, is fragmentary and should be viewed as such."
5. Environmental Contamination Potential from Disposal
Wastes from the sulfate process have long been recognized as one of the
major problems facing the industry. Indeed the type and volume of these
wastes have made the pollution control problems as significant as any
industrial pollution control problem. An example of one such problem
involves the dumping of wastes from a new factory for titanium dioxide
manufacture at Scarlino in central Italy. Marine scientists raised con-
cerns over the approximately 3,000 tons of waste containing residuals of
minerals, sulfuric acid, and small quantities of heavy metals (such as
chromium) derived from the ilmenite processing and being dumped daily by
small boats just off the shore from the factory. As the factory reaches
full operation the amounts dumped will increase. Although laboratories
have been gathering data and toxicity studies are in progress, it is not
possible to run toxicity tests on all the species in the affected part
of the Mediterranean, nor can the long-term influence ever be totally
evaluated for all living organisms. The movement of waves, currents and
1. Frank A. Patty, Editor, Industrial Hygiene and Toxicology, Volume II,
Toxicology (New York: Interscience Publishers, 1967) p. 1155
2. W. Kenneth Poole and Donald R. Johnston, Estimating Population Exposure
to Selected Metals — Titanium. Final Report, NIH-ES-2434, PB-195 819
(Springfield, Virginia: NTIS, U.S. Dept. of Commerce, March 1969) p. 48
-43-
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tides will probably prevent high concentrations occurring in the immediate
dumping area for some time, but the dispersion of the so-called red mud
("melma rosa") is considered a "serious blow" to the already precarious
life of the Mediterranean.
With the reduction or possible elimination of ocean dumping, the sulfate
process has faced increasing pressure on waste disposal. The recovery of
ferrous sulfate (copperas) is possible, but the markets for this product
are limited especially since it can be produced as a by-product from the
sulfuric acid pickling of steel. Although neutralization of waste is pos-
sible, the resulting large volumes of hard to dewater solids create a sig-
nificant solid waste disposal problem. The long-term disposal of those
solids into land areas presents potential for hazards due to the leaching
of iron and trace metals (such as arsenic, chromium, copper, mercury, lead)
into ground or surface waters. Consequently, the pressure on environmentally
safer methods of waste disposal accelerated conversion to the chloride
process. Although the chloride process should reduce the magnitude and
difficulties of waste disposal, land disposal of the remaining solids
will remain a problem.
1. Aristeo Renzoni, "Trouble for the Mediterranean," Marine Pollution
Bulletin. 4. (February 1973) p. 19
-44-
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D. Current Handling Practices and Control Technology
1. Special Handling in Current Use
From an occupational health standpoint, titanium dioxide is considered to
be non-toxic, chemically non-irritating, and classified as a nuisance dust.
General occupational safety and health recommendations do not stipulate
eye protection, protective gloves, or respiratory protection for those using
TiO_ under normal handling conditions. However, under certain conditions
it is considered an air contaminant, and special handling is required, in-
cluding protective gloves and glasses. A non-toxic particle mask and venti-
lation, such as mechanical exhaust, may be desirable under conditions of
excessive dusting and/or for clean-up. U.S. Department of Labor's OSHA
suggests mine safety appliance //66 CM 73053 type filter. ' Although con-
sidered not injurious, titanium dioxide in contact with the eye should be
flushed with water.
A typical Materials Safety Data Sheet for coatings, resins and related
materials suggests (per OSHA Standards Section 1910-93 as amended 8-13-71 —
2
Air Contaminant) a TLV of 15 mg/m for titanium dioxide pigment. For respi-
ratory protection, a dust respirator is required when an employee's exposure
in any 8-hour work-shift of a 40-hour work week will exceed the OSHA 8-hour
time weighted average of 15 milligrams per cubic meter, and the use of a
(2)
local exhaust fan is recommended.
Because it is non-combustible, TiO« is not considered a fire and explosion
hazard.
1. E.I. du Pont de Nemours & Co., Pigments Dept., Materials Safety Data Sheets
2. Kerr-McGee Chemical Corp., Materials Safety Data Sheet
3. NL Industries, Titanium Pigment Division, Materials Safety Data Sheet
-45-
-------
Being stable, TiO_ is compatible with other materials and does not decompose.
It has a specific gravity approximately 4 ± (with H_0 = 1) depending on the
(1)
formulation and its percent volatility by volume is maximum 0.5. General
chemical properties of inertness and insolubility may account for general
industrial experience where TiO. has not been associated with organic disease.
2. Current Methods for Transport and Storage
Many consumers of titanium dioxide pigments are currently obtaining bulk
shipments in two forms: dry bulk and aqueous slurry, as both of these are
offered at a lower price than the bagged material. In addition, the consumer
realizes savings.in labor and economies in elimination of waste and bag disposal.
In dry bulk form, titanium dioxide pigments are considered more versatile
than aqueous slurries, which are limited to use in water-based systems.
On the other hand, titanium dioxide pigments in aqueous slurry can be
used upon receipt without requiring additional dispersion.
In general, storage and handling systems for the aqueous slurry require
only relatively standard equipment. However, the dry bulk systems require
more sophisticated pneumatic handling techniques due to the fact that TiO~
pigments are not free flowing powders. Live bottom bins, vibration heavy
duty rotary powder valves and automatic self-cleaning bag filters are
necessary.
In either case, the choice of packaging systems is largely one of economics,
(2)
It is based generally on minimum yearly consumption of pigment.
1. E.I. du Pont de Nemours & Co., Pigments Dept., Materials Safety Data Sheets
(R)
2. E.I. du Pont de Nemours & Co., Du Pont Ti-Pure^ Titanium Dioxide for
Plastics. (Wilmington, Delaware: E.I. du Pont de Nemours & Co., 1974) p. 19
-46-
-------
Titanium dioxide must be stored in a clean dry area. Protection from water
or moisture is necessary to maintain dispersibility. In addition, con-
densation of water or moisture may degrade physical properties.
1. Current Treatment and Disposal Methods
Several treatment and disposal methods for titanium dioxide wastes have been
in practice for years, but there are many instances where for a variety of
reasons, both environmental and economic, alternatives to current practices
are being sought. The factors involved in the choice of alternatives range
from stream classification and the assimilative capacities of a given body
of water to aesthetic considerations and efforts to improve air and water
quality. Whenever possible or feasible, waste products are recycled or
recovered as saleable products. Acidic wastes are neutralized before final
disposal. An estimate for installation of neutralization treatment and
performance is shown in Table XVI.
Conventional waste disposal methods have been ocean dumping, landfill, and,
to a lesser extent, deep-well injection. Ocean dumping has been widely
used for disposal of iron-acid sludge, while landfill is commonly used for
disposal of chloride-process wastes.
a. Ocean Dumping
Despite its costs, the barging of Ti02 plant wastes to the sea has been in
fairly widespread use throughout the industry for many years, where reason-
ably convenient. The total capital investment costs of initiating a barg-
ing operation was $2.1 million, according to one plant manager; of this
$1 million was spent to complete on-shore facilities. Costs for barging
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products, op. cit., p. 178
2. Samuel W. Fader, "Barging Industrial Liquid Wastes to the Sea,"
Journal of the Water Pollution Control Federation, ^4 (2),
(February 1972) p. 316
-47- :
-------
during the first 8 months of 1971 were approximately $3,80/1,000 gallon
for a 200 nautical mile round trip from the dock. This cost included
the operation, maintenance, and depreciation of shore facilities, barge
leasing and towing, and dry dock overhaul and repainting of the barge on
a 3-year frequency.
The utilization of ocean dumping avoids complicated developmental tech-
nology. Barging to the sea has the advantage of reducing waste loads to
streams and rivers. Shore facilities supporting this method of disposal
include pumps, lines, storage tanks and barge loading equipment, usually
gravity fed.
b. Neutralization and Landfill
In some instances the wastes are collected and concentrated for the re-
moval of solid matter. However, due to the fine particle size, extensive
settling time and area are required. The residual solids are neutralized
and hauled for sanitary landfill. Due to its inertness, discharge into
sewers would impart turbidity which is one of the reasons landfill of
this waste is chosen.
c. Deep-Well Injection
The plant location and the difficulty of finding appropriate deep-well
storage capability is central to the question of TiO? waste disposal by
means of deep-well injection. In general, the acid wastes are diluted
before discharge into the wells.
1. Samuel W. Fader, op. cit., p. 318
-48-
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TABLE XVI
INSTALLATION OF NEUTRALIZATION TREATMENT AND PERFORMANCE
Methods
Neutralization of acid
to CaSO^ and oxidation
of iron, and remove
for sale or stockpile
(as ferrous sulfate)
of process wastes and
cooling water
Additional settling
ponds for cooling
waters
Estimated
Installation
Time
22 mos
22 mos
Estimated
Performance
Reduce C.O.D. to Nil
Reduce acidity to Nil
Reduce Fe, Mn, V,
and Cr to Nil
IDS 50 mg/1
Reduction of suspended
solids formed due to
neutralization by 95%
4. Current Accident Procedures
In the case of TiO spillage or leakage, standard protective equipment is
required for the clean-up. As described in the first part of this section,
respiratory protection of the Mine Safety Appliance //66 CM 73054 Type
Filter is required, along with protective gloves, glasses and mechanical
ventilation.
5. Current Controls
According to the U.S. Food and Drug Administration's regulations, a.
special grade of TiO« for use as a color additive in foods, drugs or cos-
metics is necessary. The essential requirements involve the control of
impurities, including 99.0% TiO- minimum, 10 ppm acid soluble lead maximum,
1 ppm acid soluble arsenic maximum, 2 ppm acid soluble antimony maximum,
1 ppm acid soluble mercury maximum.
(1)
However, there are generally no restrictions on the TiO_ composition for
use as a component in food packaging.
1. "Color Additives" -- Part 8, Title 21, Federal Register, 31 (18),
(27 Jan. 1966) pp. 1065
-49-
-------
6. Control Technology Under Development
Out of the many research and development efforts currently under way to
discover new and improved technology for treating and/or disposal of pro-
cess wastes, some directions for the future of Ti07 control are emerging.
For example, American Cyanamid is reported to have investigated neutrali-
zation, chemical, catalytic and atmospheric oxidation, acid concentration
and recovery-, electrodialysis, ion exchange, deep-well injection, and
production and sale of a sulfate by-product. A company spokesman, however,
has said that none of these methods proved "technologically practical,
sound and economically feasible."
On the other hand, Du Pont has spent "well over $1 million" to research
alternatives to the treatment and disposal of TiO» wastes. "Electrolytic
oxidation of ferric chloride manufacture for the waste-treatment market"
(2)
is considered the most promising from this research effort. Du Pont
emphasizes that TiO~ waste-treatment and disposal is both an engineering
and an economic problem.
Under an EPA grant of $149,000, New Jersey Zinc has been operating a
(3)
sulfuric acid recovery pilot plant for its TiO_ wastes. The general
opinion is that acid recovery is technologically but not economically
feasible although New Jersey Zinc has not made full disclosure of its
findings.
Another development is related to the fact that Universal Gypsum of Indiana
has filed application for patents on their process of making acid wastes
into gypsum. It is hoped that the Universal process can be applied to
TiO wastes in a manner similar to its applications to treat and convert
a calcium sulfate waste stream from pharmaceutical plants into pharma-
ceutical-grade gypsum.
1. "Heavy Going Ahead for Wastes Discharging at Sea," Chemical Week, 112
(26), (27 June 1973) p. 45
2. Loc. cit.
3. Loc. cit.
4. Ibid., p. 47
-50-
-------
E. Monitoring and Analysis
1. Analytical Methods
In general, the analytical methods for wastes from the manufacture of
TiO_ vary, depending on the medium, i.e., air, water. From an environ-
mental standpoint analysis is usually performed to determine the presence
of total titanium. If titanium is not found, no further tests are per-
formed for titanium dioxide.
a. Analysis of Air
Analyses of emissions are generally made for any titanium particulate and
not TiO. per se. The primary standard colorimetric method employed for
measuring titanium originated with Weller in 1882 and was used further by
Lundell and others. It is one in which the yellow complex formed by the
addition of hydrogen peroxide to an acid solution of titanium sulfate is
measured spectrophotometrically. This method is sensitive with a range
of 5 to 50 ppm. In another method, the use of Tiron, an extremely sensitive
reagent, imparts a yellow color in the presence of Ti in the 0.3 to 3.0 ppm.
range. Another possible method is atomic absorption with optimum concen-
tration in the 5 to 100 ppm range. Both the colorimetric methods and
atomic absorption require complete dissolution of the sample, a procedure
which can be somewhat tedious. For qualitative purposes, emission spec-
trography can be used for titanium. X-ray diffraction is used specifically
for the crystalline forms of TiO and can differentiate between anatase
and rutile.
b. Analysis of Water
In the analysis of water the solubility of TiO? is so slight that filtration
is usually necessary prior to performing x-ray diffraction. For the same
reason, one must filter for the purpose of an x-ray fluorescent scan of a
water sample. Once a trace is found, atomic absorption techniques are
utilized. The only specifically applicable qualitative measure for TiO-
is x-ray diffraction or electron diffraction performed by an electron
microscope. It is particularly important during sampling to determine
-51-
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that the titanium is not from the clay or some other natural and non-
polluting source.
In some instances a mobile water testing unit is employed to monitor given
sampling sites. Methods may vary from site to site and from parameter to
parameter measured, e.g., flow rates may be measured by installed meters,
direct collection of small outfall streams, volumetric measurement, dye
tracer for velocity measurement, etc.
Tables XVII and XVIII show the analyses of the composition of effluent
streams after treatment. The effluent is from a plant utilizing the
chloride process. The raw material feed for this plant is over 95% TiO.
grades of rutile and upgraded ilmenite.
2. Current Monitoring
There are monitoring programs being employed at TiO- plants by the manu-
facturers, as well as those programs concerned with the environment sur-
rounding the facility. At Du Pont, for instance, continuing tests of
their products for heavy metals associated with TiO,. manufacture show
mercury content in amounts less than 0.1 ppm. This determination of
mercury is carried out by an independent laboratory by Multi-Channel Gamma
Ray Spectrometry. Based on a doped sample with 1,000 ppb of mercury fixed
as HgS, the apparent recovery is 96% and confirms Du Font's own extraction
data.(2)
Waste originating from a NL Industries' TiO- plant and barged to the
N.Y. Bight, off the N.J. coast, has been monitored. The waste consists of
10% ferrous sulfate and 8.5% sulfuric acid dissolved in fresh water. The
1. U.S. Environmental Protection Agency, Development Document for Effluent
Limitations Guidelines...Major Inorganic Products, op. cit., p. 171-2
2. E.I. du Pont de Nemours & Co., Pigments Dept., Materials Safety Data Sheet
-52-
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TABLE XVII. COMPOSITION OF PLANT EFFLUENT STREAMS AFTER TREATMENT
Parameter*
Suspended Solids
Total Dissolved Solids
COD
PH
Temperature, °C
Stream No. 1
Range
Stream No. 2
Average Range
18
3300
50
7.8
16
Organics
Turbidity '(Jackson Units) 20
Color (APHA Units) 10
Chloride 1650
Sulfate
Sulfate
Iron 0.2
Conper 0.015
Chromate 0.01
Total Chromium 0.05
Arsenic 0.02
Mercury 0.001
Lead 0.1U
*mg/l unless otherwise specified
1-50
1500-U500
40-90
6.0-9.0
7-27
None were
10-80
10-20
750-2050
1-2.5
— -
0-3.0
0.01-0.03
0.01-0.15
0.1-0.19
15
300
20
6.8
16
found
20
10
50
—
150
0.2
0.015
0.01
0.05
0.02
0.001
0.02
0-40
180-900
5-45
6.0-9.0
2-32
(Ambient Temp.)
10-50
10-20
70-100
1-2.5
90-450
0.1-1.0
0.01-0.03
0.01-0.15
0.02
TABLE XVIII. VERIFICATION DATA FOR THE PLANT
Parameter*
Flow, cu m/day (MGD)
Temperature, °C
Color (APHA Units)
Turbidity (FTU)
C'-. •" I:*'-ivj' v
Suspended Solids
pH
Acidity: Total
Free
Alkalinity (Total) P
T
Hardness: Total
Calcium
Halogens: Chlorine
Chloride
Fluoride
Sulfate
Phosphates (Total)
Nitro-jen (Tot*!)
Heavy Metals:
Iron
Chromate
Oxygen (Dissolved)
Lake
Intake Water
Effluent
Stream #1
Effluent
Stream #2
3650 (0.964)
9
100
35
100 (Nad)
25.0
7.9
N/A
N/A
0 (CaCO3)
93 (CaC03)
129 (CaCO3)
97 (CaC03)
0
36.5
0
32.0
1.4
0.24
6060 (1.60)
16
140
35
2100 (NaCl)
10
7.6
N/A
N/A
0 (CaCO3)
22 (CaC03)
2600 (CaC03)
1920 (CaCO3)
0
2250
0.3
240
0.025
0.14
2240 (0.590)
26.5
90
30
170 (NaCl)
30
6.85
0 (CaCO3)
0 (CaCO3)
0 (CaC03)
28 (CaC03)
185 (CaC03)
139 (CaCO3)
0
49.5
0.25
175
0.225
1.3
0.225
0 (Crt6)
10.8
1.6
0 (Cr+6)
9.0
0.4
0 (Cr+6)
6.2
*mg/l unless otherwise specified
-53-
-------
turbulent wake of the barge dilutes and neutralizes the discharge rapidly,
so that the acidification of the sea water is short lived. Turbidity of
the water results, however, from the formation of ferrous hydroxide.
In a federal government support grant, The Marine Laboratories of the
University of Delaware developed a biological and bottom-monitoring pro-
gram for the disposal area associated with the nearby TiCL pigment plants.
Conclusions from this study showed (a) "no change in ocean quality or
accumulation of waste materials in the disposal area" with wastes being
transported to sea by normal ocean currents; (b) relatively rapid
(10 to 20 minutes) initial dispersion of wastes behind the barge, about
1 to 5,000-fold dilution; (c) the marked influence of a "thermocline"
on the vertical dispersion or mixing of the wastes, resulting in protection
of marine life on the ocean bottom from contact with the dispersing wastes
during the warm seasons but not the cold; (d) a mathematical model simu-
lating the dispersion pattern observed; (e) no changes in the marine
life of the water column attributable to the disposal operation with the
(2)
possible exception of the sand dollar.
Although the evidence in relation to possible effects on the sand dollar
was inconclusive, the sand dollar is considered important in the general
ecology of the sea. The sand dollar, Meoma ventrioosa, also called the
cake dollar, is an irregular echinoid identified as one of the 6,000
existing species of echinoderms. Echinoderms are marine invertebrates
that are important to the general ecology of the sea, serving as scavengers
of decaying matter on the sea floor and consumers of various organisms.
1. Jelks Barksdale, Titanium, Its Occurrence, Chemistry and Technology,
(New York: Ronald Press Co., 196£, Second Edition) p. 370
2. Samuel W. Fader, op. cit., pp. 317-18
-54-
-------
Du Font's technical manager of plants, Hal Clark, has been quoted as saying
that the typical waste stream in 100 Ibs. of Ti02 production from the
sulfate process contains:
220 Ibs. sulfuric acid
150 Ibs. ferric sulfate
15 Ibs. other sulfates
6 Ibs. neutral salts
Total 391 Ibs. waste
and from the chloride process contains:
18 Ibs. hydrochloric acid
85 Ibs. ferric chloride
10 Ibs. other chlorides
6 Ibs. neutral salts
Total 119 Ibs. waste
Another example of a monitoring program is one being carried out in the
German Bight in connection with the TiO factory near Breraerhaven. The
pH in the samples is measured by a glass electrode, Fe concentration is
determined by gravimetry and photometry and the 0~ concentration by
titration. The most important; changes noted in this case include a re-
duction in the pH of the sea.water from 8.1 to 8.2 and marked increase in
the CO^ partial pressure. In addition, the ferrous sulfate increases
tnd ]
(2)
2+ 3+
the iron concentration, and the Fe is oxidized to Fe and precipitated
as hydroxide, resulting in.an 0- deficit in the sea water.
Tests were made to determine the penetration of the wastes (with a density
of 1.25 g/cm ) to the sea bed. Contrary to expectations, the wastes did
not reach the sea bed during the first hours after release. The pH and
1. "Heavy Going-Ahead for Waste Discharging at Sea," op. cit., p. 47
2. G. Weichart, "Chemical and Physical Investigations on Marine Pollution
by Wastes of a Titanium Dioxide Factory," Marine Pollution and Sea Life,
Mario Ruivo, General Editor (London: Fishing News Ltd., 1972) pp 186-8
-55-
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0_ content returned to about normal but the Fe concentration in the bottom
layer increased shortly after release. After five and a half months, the
highest Fe concentration in the sea water 5 m below the surface was 0.5 mg/1,
and there was no change in pH. Although ferric hydroxide, formed by re-
action of the wastes with sea water, sank to the sea bed, it was determined
after 51/2 and 16 months that the Fe content in the upper layers of the
sediment was no greater than that measured before the disposal of waste.
1. G. Weichart, loc. cit.
-56-
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III. HEALTH AND ENVIRONMENTAL EFFECTS
A. Environmental Effects
1. Persistence
As mentioned 'in previous sections, titanium dioxide is insoluble in water,
HC1, HNO. or dilute H2SO,. The suggested waste disposal method has
been sanitary landfill. Under these conditions, the compound would be
expected to be very persistent. No information appeared in the literature
reviewed concerning biological degradation, and chemical degradation seems
unlikely under normal circumstances.
2. Environmental Transport
No information was found concerning environmental transport of TiO_. How-
ever, movement would be expected as with any inert particulate.
3. Bioaccumulation
Concentration of titanium in plants is extremely variable. Green portions
of plants generally contain more than roots or stems. There is no evidence
that plants preferentially accumulate the element, nor are there data
(2)
available as to the form of titanium taken up by plants. Schroeder et al
mention that A.P. Vinogradov at the Sears Foundation for Marine Research,
Yale University, reported in a study of the elementary composition of
marine organisms, published in 1953, that titanium can be absorbed and
concentrated by factors of 4 to 180 by algae, plankton, protozoa, sponges,
corals, starfish and crustaceans. Fish, however, absorb and store it
poorly.
Samplings of wild animal tissues suggest that titanium is not accumulated
to any degree. The wild animals (woodchuck, muskrat, red squirrel, red
fox, deer, etc.) were from Southern Vermont. For the woodchuck, concen-
trations (wet wt) of titanium were reported as 0.0 or 0.32 yg/g in the
1. The Merck Index, op. cit., p. 1054
2. H.A. Schroeder, J.J. Balassa, and I.H. Tipton, "Abnormal Trace Metals
in Man: Titanium," Journal of Chronic Diseases, l^. (1963) pp 55-69
3. Ibid., p. 63
-57-
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kidney, and as 0.53, 1.00, and 1.50 yg/g in the spleen. For the deer,
concentrations in the kidney ranged from 0.31 to 3.10 yg/g.
Studies in laboratory animals (mice) given soluble salts of titanium showed
that considerable quantities were accumulated, as much as 32.49 yg/g being
(2)
found in albino mice.
Despite this large accumulation, continuing investigation showed no evi-
dence of toxicity of titanium for mice. There was no increase in mortality
during 18 months in mice given the metal, and mature weights of the animals
were significantly greater than those of the controls.
The available literature, therefore, suggests that the form, e.g., solubility,
of titanium is a major determining factor in its bioaccumulation. Titanium
dioxide which is insoluble would be expected to be taken up and accumulated
to a lesser extent than soluble salts.
4. Biomagnification
There were no data available concerning biomagnification.
B. Biology
1. and 2. Absorption and Excretion
There is no apparent evidence that titanium dioxide is absorbed from the
gastrointestinal tract following oral administration in animals. In a
study to test the value of titanium dioxide as an index material for
determining apparent digestibility of a rat diet, thirty male albino rats,
averaging 60 days of age, were fed a diet containing 0.25% TiO_ for a
13-day period. The diet consisted of 90% ground wheat plus 10% of a
protein-mineral supplement. Total feces from these animals were col-
lected individually and daily for 13 days or were pooled for groups of
1. W.A. Schroeder, J.J. Balassa, and I.H. Tipton, op. cit., p. 61
2. loc. cit.
3. Ibid., p. 67
-58-
-------
five animals each for a period of seven days from days 6-13. All feces
samples were analyzed for Ti09 by a colorimetric method (modification of
Weller's Method). For all treated animals, the average recovery of titanium
dioxide over the 7-day period from days 6-13 was 92.0%. The rate of ex-
cretion was somewhat delayed since analyses of daily samples of feces for
the first six days showed that a constant and maximum excretion of TiO?
had not been attained. The authors concluded that it was unlikely that
TiO- was absorbed from the gastrointestinal tract, since, with progress-
ing time, the average digestion coefficients approach the values deter-
mined conventionally. The delayed excretion of TiO appeared to be due
(1)
to its accumulation in some part of the tract, possibly the cecum.
Another study investigated the passage of titanium dioxide through the
(2)
gastrointestinal tract. Rats were administered diets containing 0.42 gm
calcium carbonate together with 0.2, 1.0 and 2.0 gm titanium dioxide/100 gm
diet for seven days. At sacrifice, the ratios of the amounts of calcium to
titanium dioxide at various points along the length of the gastrointestinal
tract in these animals were not found to differ appreciably from that
present in the diet. This finding supports the view that titanium dioxide
is not absorbed. In addition, the blood, liver, kidneys or urine of rats
which had ingested 0.66 gm TiO /kg body weight daily for 15 days contained
(3)
no amounts of titanium that were detectable by an as=iay sensitive to 10 yg.
The absorption of titanium from the gastrointestinal tract may be dependent
upon the solubility of the salt employed. A study was made in which albino
mice administered a soluble titanium salt, potassium titanium oxylate, at
a dosage level of 5 ppm in drinking water from weaning throughout life span,
showed greater Ti concentrations in the lungs, spleen, kidneys, and liver
1. L.E. Lloyd, Elaine Rutherford, E.W. Crampton, "A Comparison of Titanic
Oxide and Chromic Oxide as Index Materials for Determining Apparent
Digestibility," Journal of Nutrition, _5j6 (1955) p. 265-71
2. P. Fournier, De 1'Emploi de 1'Oxyde de Titane Tour 1'Etude Quanti-
tative de 1'Absorption Intestinale, Coaptes Rendus des Seances de
1'Academie des Sciences, 231 (1950) p. 1343-5
3. loc. cit.
-59-
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than did control animals. These concentrations did not, apparently, affect
the mortality of the males and, as mentioned earlier (p.58), showed no
evidence of toxicity to the mice. Maximum precautions were taken in this
experiment against introducing titanium contamination from outside sources.
In rats, deposition of titanium dioxide has been demonstrated in the lungs
and lymph nodes following inhalation and intratracheal injection. ' '
Qualitative and quantitative analyses of lung tissue of three workers em-
ployed in a titanium dioxide processing factory in Finland also showed
considerable titanium content. The :
sented in detail below and on pp. 70-1.
considerable titanium content. The results of these studies are pre-
When TiO_ was used as a protective film on exposed parts of the body for
the prevention of flash burns during World War II, no adverse reactions
followed, indicating that it did not have the capacity to produce contact
dermatitis, allergic sensitization, or appreciable dermal absorption.
3. Transport and Distribution in Living Organisms
In a series of experiments, the rate of removal of titanium dioxide from
blood and its deposition in liver, spleen and celiac lymph nodes was studied
1. H.A. Schroeder, W.H. Vinton, Jr. and J.J. Balassa, "Effect of Chromium,
Cadmium and Other Trace Metals on the Growth and Survival of Mice,"
Journal of Nutrition, 80 (1963) p. 39-47
2. H. Christie, R.J. MacKay and A.M. Fisher, "Pulmonary Effects of Inhalation
of Titanium Dioxide by Rats," American Industrial Hygiene Association
Journal. 2k_ (1), (1963) p. 42-6
3. J. Ferin, "Papain-Induced Emphysema and the Elimination of Ti02 Particulates
from the Lungs," American Industrial Hygiene Association Journal
_32 (1971) p. 157-62
4. C.J. Gothe and A. Swensson, "Effect of BCG on Lymphatic Lung Clearance
of Dusts with Different Fibrogenicity, An Experimental Study in Rats,"
Archives of Environmental Health, _20_ (1970) p. 579-85
5. R.K. Elo, K. Maata, E. Uksila and A. Arstila, "Pulmonary Deposits of
Titanium Dioxide in Man," Arch. Path.. 94. (4), (1972) p. 417-24
6. Frank A. Patty, Editor, op. cit., p. 1157
-60-
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in rats following a single intravenous injection. In each study female
Sprague-Dawley rats 45-55 days of age and 145-155 gm in body weight were
used. The sample of TiO~, which had an anatase crystal structure and was
water-dispersible, was 99% pure with a lead content of Q.0016%. The
particle size was 0.2-0.4 microns. Dosages of TiO. were prepared as sus-
pensions in 5% dextrose (2.5 gm/100 ml) and injected intravenously into
the caudal vein. Ti09 tissue content was determined by a modification of
the technique of Hillebrand and Lundell, the limit of sensitivity of which
was about 1 yg/ml.
A single rat was injected intravenously with 250 mg TiO_/kg body weight
and blood samples taken at 5-minute intervals for TiO« determination.
The removal of TiO_ from the blood was found to occur at an exponential
rate with whole blood concentrations at +5, +10, and +30 minutes determined
as about 290, 90 and 25 yg TiO /cc, respectively.
In another series of experiments, eight rats/group received a single intra-
venous injection of 250 mg TiO_/kg body weight. Animals were killed at 0,
6, 12 and 24-hr intervals for determination of T±0n content in the liver,
L
spleen and celiac lymph nodes. Another animal was killed one year after
injection. In those rats killed immediately following injection, 69 and 78%
of the injected dose was found in the liver at 5 and 15 minutes, respectively.
Concentrations of Ti00 in the liver, spleen and celiac lymph nodes of animals
(2)
killed at 6 and 24 hrs, and 1 year are shown in Table XIX. In the 6-hpur
group highest concentration of TiO was found in the liver, and the next
highest in the spleen. Titanium was not concentrated in any of the lymph
nodes of the celiac group until 12 hours following injection, when the
average TiO- content was determined as 1.2 mg/gm. In contrast, the iliac
1. C.B. Huggins and J.P. Froelich, "High Concentration of Injected
Titanium Dioxide in Abnormal Lymph Nodes," Journal of Experimental
Medicine. 124 (6), (1966) p. 1099-1106
2. Ibid., p. 1102
-61-
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lymph nodes of the same animals contained 0.43 mg TiCL/gm. In the 24-hr
group, the relative TiO. concentrations in the three tissues were as folloWs;
"white celiacs" (those celiac lymph nodes with grossly-apparent high con-
centrations of TiO-) > liver > spleen.
In the single rat killed one year following titanium dioxide administration,
the highest TiO- concentration was found in the celiac lymph nodes, the
titanium content of which exceeded that of the mediastinal lymph nodes by
18 times. Decreasing TiO- concentrations were found in the mediastinal
lymph nodes, spleen and liver. Microscopic examination of the celiac lymph
nodes, which grossly did not appear enlarged, showed that the largest amount
of titanium dioxide was localized in the medulla.
In another series of experiments, the effect of splenectomy or partial
hepatectomy on celiac lymph node TiO,, content was examined. A TiO^ sus-
pension at the dosage level of 250 mg/kg was injected intravenously into
rats 24 hours following splenectomy or partial hepatectomy. Control rats
did not undergo surgical procedures. Tissues from all animals were col-
lected 24 hours following injection.
TABLE XIX
CONCENTRATION OF TITANIUM DIOXIDE IN LIVER, SPLEEN, AND LYMPH NODES
A Single intravenous injection of Ti02, 250 mg/kg, was given at 0 hr to
female rats age 45 to 50 days. There were 8 animals in each group.
Time of
harvest
Liver
Spleen
Lymph nodes
Celiac white Celiac
nonwhite
6 hr.
24 hr.
1 yr.
4.13+0.4
3.93lo.3
3.90±0.6
Ti02:mg/g
3.0+ 0.8
1.5± 0.4
18.2± 4
0.46
9.1+1.3
127.0
0.52
0.28
0.70
+, standard deviation
-62-
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The concentration of TiO^ in the liver of splenectomized rats, injected
1 to 21 days after removal of the spleen, was similar to that of normal
controls. Excision of the median and left lateral hepatic lobes, however,
had profound effects on the distribution of injected TiO- which were first
apparent 24 hours after surgery. The regenerating liver appeared intensely
white at 24 hours after surgery. As in the intact normal control, 80% of
the dose of TiO? was found in the regenerating hepatic lobes despite the
fact that the total amount of liver tissue was less than in the normal
controls. The number of "white celiacs" was reduced to two compared to
5-7 in control animals; these nodes were located only on the right side
of the abdomen around the epiploic foramen. There were no "white celiacs"
on the left side of the retroperitoneal space until day 7 after hepatectomy.
On day 21, the number and site of white celiac lymph nodes was similar to
that of the controls.
The authors concluded that the great accumulation of titanium dioxide in
the celiac nodes is attributed to their topography which results in pro-
gressive filtration of particulate matter from hepatic lymph rather than
any unusual chemical characteristics.
Deposition and clearance of titanium dioxide from the'lungs of rats follow-
ing exposure by inhalation has been studied. . In the former study
22 male Wistar rats, 245-360 gm in body weight, were exposed to TiO» dust
generated four times daily at 2-hour intervals five days/week for 10-13 months
by evaporation of an aqueous suspension of Ti09. Dust counts were in the
range of 42-328 mppcf (million particles/cubic foot) during the first hour
1. C.B. Huggins and J.P. Froehlich, op. cit., p. 1105
2. H. Christie, R.J. MacKay and A.M. Fisher, loc. cit.
3. J. Ferin, loc. cit.
-63-
-------
and 10-46 mppcf during the second hour. No particle size was given. A
comparable group of 23 rats served as controls.
No significant difference was observed between the wet weight of pairs
of lungs from treated and control animals after 9-13 exposure months,
although the lung ash content of the experimental group was substantially
greater than that of the control. Qualitative spectrographic analysis
of pooled lung ash from treated rats showed greater than 10% titanium
content.
Microscopic examination of the lungs showed aggregates of pigment in the
sump areas in the subpleural areas and in the regions of the alveolar
ducts after 9-13 exposure months. The pigment occurred intracellularly
within the macrophages and was associated with focal areas of emphysema.
The alveoli were for the most part free of pigmentation, although small
aggregates of macrophages containing pigments were apparent in the bron-
chial lymph nodes at 13 months. No enlargement of the mediastinal lymph
nodes was noted. The appearance of the lungs of rats exposed to dust for
10 months and then to fresh air for three months was identical with that
of animals exposed for 13 months. This finding suggests that the clearance
of titanium dioxide is delayed.
In the latter study, 10 male Long-Evans rats, about 200 gm in body weight,
3
per group were exposed to concentrations of 7.5 to 50 mg/m of anhydrous
(2)
TiO_ by inhalation for periods of minutes to 7 hours. Prior to exposure,
experimental emphysema was produced in two groups of animals by intra-
tracheal injection of 0.5 mg papain (two injections in 4 days) or by papain
aerosol (total exposure time 64 hours over two weeks and 48 hours over
two weeks). The median mass aerodynamic diameter of the particles was
1. H. Christie, R.J. MacKay and A.M. Fisher, loc. cit.
2. J. Ferin, loc. cit.
-64-
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1.48 ym (mean geometric standard deviation of 3.26); the mean specific
3 -10
surface area was 6.5 m /gm; and in vitro solubility was about 10 gm/
2
cm /day. Pulmonary TiCL retention was determined 25 days after exposure
by a photometric method using 4,4-diantipyrylmethane monohydrate.
The production of different lung burdens and the use of different exposure
time intervals permitted an evaluation of different clearance rates and
their relation to the localization of TiCL particles in the lung tissues.
In rats without experimental emphysema, the results showed (1) a direct
relationship between TiO^ concentrations following a 7-hour exposure and
absolute Ti09 deposition in the lungs, (2) a direct relationship between
3
exposure time and at a concentration of 54 mg TiO_/m and absolute TiO?
deposition in the lungs, and (3) a direct relationship between the lung
weight of five different species, including mouse, hamster, rat, guinea
pig and rabbit, following a '
TiO deposition in the lung.
3
pig and rabbit, following a 7-hour exposure to 15 mg TiO./m and absolute
The retention of TiO^ in the lung was studied for up to approximately
140 days postexposure. The biphasic retention half-times in three experi-
ments with average initial lung burdens of 60, 139 and 247 pg TiO_ were
about the same, "with 14 days applying to the first 8 days, and 88 days,
thereafter." The first phase of clearance included mainly, but not ex-
clusively, the particles deposited in the ciliated airways. After 30
minutes of exposure, phagocytosed Ti00 particles were apparent not only
(1)
within the alveoli, but also within macrophages on the ciliary "escalator."
In rats with papain-induced emphysema, a significant decrease in TiO_
clearance rates was apparent 25 days after exposure as shown in Table XX.
1. J. Ferin, op. cit., pp 160-1
-65-
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TABLE XX
(1)
TWENTY-FIVE-DAY RETENTION
Ex-
periment Treatment
1 Control
Papain aerosol
2 Control
Papain aerosol
3 Control
Papain, intratracheal
OF Ti00 IN
Initial
Lung
Burden
( g/lung)
376
438
326
293
326
164
PAPAIN-TREATED
Reten-
tion
(%)
49 ± 11
61 i 9
49 ± 7
66 ± 13
49 ± 13
82 ± 12
RATS
P <
0.05
0.01
0.001
In another study, treatment with BCG was also found to increase the retention
of TiO~ in the lungs of rats following administration by intratracheal
injection. Fifteen female Sprague-Dawley rats, 200 gm in initial body *
weight, were injected intratracheally with 1 ml of a TiO« suspension in
saline (20 mg/ml). The mean diameter of the particles was 0.6 y. An
intravenous injection of BCG (Gothenburg substrain), a cow-virulent strain
of bovine tubercle bacilli, preceded the intratracheal injections of dust
by two months. The substrain was supplied as a suspension with a con-
centration of 20 mg bacilli/ml. Each BCG-treated rat received 5 mg BCG
(1 mg contained about 3 x 10 "viable units"). The animals were sacri-
ficed 60 days after the dust injection. 'At autopsy, the TiO content of
the lymph nodes was determined spectrophotometrically while that of the
lungs was determined by spectralanalysis
(2)
1. J. Ferin, op. cit., p. 158
2. C.J. Gothe and A. Swensson, loc. cit.
-66-
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Intratracheal injection of the dust increased both the absolute and
relative lung weights, although the reaction was less pronounced than
that observed following injection with silica-containing dust. The re-
action from TiO_ in the hilar lymph nodes showed the same tendency as in
the lungs.
The TiO. content of the lungs was significantly higher in animals treated
with BCG and dust than in corresponding groups treated with TiO_ alone.
The tendency was quite the opposite in the hilar lymph nodes where the
TiC- content was significantly higher in the dust-treated control groups
than in corresponding experimental groups treated with both BCG and TiCL.
These results implied that significant amounts of inert dusts were trans-
ported from the lungs through the pulmonary lymphatics and that this
transport was retarded by BCG. Formerly, inert dusts had been consid-
ered to be mainly eliminated via the bronchi.
In guinea pigs and rabbits, intravenous or intra-tonsillar injection
of titanium dioxide has resulted in translocation of the particles to
tissues damaged by prior injection of cell-wall components of Strepto-
(2)
coccus, or tissue-damaging factor protein isolated from extracellular
products of group A streptococci or BCG. The results of the latter
study indicated that TiO- particles injected intraperitoneally in rab-
bits became localized within phagocytic cells in myocardial, hepatic
and diaphragmatic lesions induced by streptococcal toxin. It was also
1. C.J. Go'the and A. Swensson, loc. cit.
2. I. Ginsburg and R. Trost, "Localization of Group A Streptococci
and Particles of Titanium Dioxide in Arthritic Lesions in Rabbits,"
Journal of Infectious Diseases, 123 (3), (1971) p. 292-96
3. I. Ginsburg, H.A. Gallis, R.M. Cole, and I. Green, "Group A
Streptococci: Localization in Rabbits and Guinea Pigs Following
Tissue Injury," Science, 166 (1969) p. 1161-3
-67-
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shown that both streptococci and TiO_ particles were localized in
delayed hypersensitivity lesions induced in the skin of guinea pigs by
injections of tuberculin. It was suggested that the extent of localiza-
tion of particles in tissues depended upon the severity of the inflamma-
tory process.
4. Metabolic Effects
No data concerning metabolic effects of titanium were reported in the
literature reviewed.
5. Pharmacology
In other studies, an effect of titanium dioxide was observed on the level
(2)
of circulating thrombocytes following intravenous injection in rats.
Anesthesized albino rats, about 300 gm in average body weight, received
a single intravenous injection of 1, 2 or 4 mg TiO. suspended in saline.
The particles of TiO? were characterized as angular and had an average
size of 60 my. Blood samples were taken at 2, 4, 8, 16 and 32-minute
intervals up to 1 hour after injection. Control animals were treated in
a similar manner and injected with saline.
Doses of 1 and 2 mg TiO- produced no appreciable change in thrombocyte
count. A dose of 4 mg, however, was followed by a marked decrease in
platelet count which was first apparent 4 minutes after injection. This
effect lasted longer than 32 minutes. In comparison, injection of 1 mg of
amorphous synthetic silica (150 my) in suspension also produced a rapid
fall in the number of circulating thrombocytes. Maximum reduction was
achieved after 4 minutes. Similar results were obtained with a water-
soluble starch, but not with colloidal solutions of an iron preparation,
methylene blue or saline.
1. I. Ginsburg and R. Trost, loc. cit.
2. G. Bloom and A. Swensson, "The Reaction of Thrombocytes to Intra-
venously Injected Suspensions of Submicroscopic Particles,"
Acta Med. Scand., 162 (1958) p. 423-6
-68-
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6.,:. *•; Tissue Reaction
Compatibility of titanium with soft tissues and bones has been demonstrated
histologically following surgical implantation in dogs. In one
of the two studies, small discs of titanium (0.25 in. in diameter and
0.013 in. in thickness) were embedded into the rectus abdominus muscle,
left side, of dogs under surgical asepsis. Controls of tantalum (0.25 x
0.010 in.), a proven inert metal, were allowed to remain in situ for a
period of 7 months. The discs, with an adequate amount of surrounding
(3)
tissue, were then surgically removed and fixed for microscopic examination.
The gross specimens of titanium and tantalum gave no indication of irri-
tation, infection or inflammation. A fibrous capsule encased the metal in
each instance. The microscopic sections confirmed a negative inflammatory
and infectious response to both metals, but a fibroblastic response was
present. The tissue tolerance response appeared similar. The authors
concluded that titanium was well tolerated by living tissue of dogs.
In the second of the two studies, screws and plates (total of 11 plates
and 42 screws) of cast Vitallium, wrought Vitallium and Austanium, a
trademark for a titanium alloy, were surgically implanted in the body of
the mandible and the front and hind legs of anesthesized dogs. The plates
were placed over the cortical layer of bone, the screws inserted and the
periosteum sutured over both screws and plate. All animals were sacri-
ficed after a period of 2-17 months and were perfused with a 10% formalin
solution. Samples of tissue were taken for histological examination.
1. O.K. Beder and G. Bade, "An Investigation of Tissue Tolerance to
Titanium Metal Implants in Dogs," Surgery, J39 (1956) p. 470-3
2. P.P. Gross and L. Gold, "Compatibility of Vitallium and Austanium
in Completely Buried Implants in Dogs," Oral Surgery, 3X) (1957) p. 769-80
3. O.E. Beder and G. Eade, loc. cit.
4. P.P. Gross and L. Gold, loc. cit.
-69-
-------
Since no gross or histological differences were noted between the metals
or the length of time the metals were implanted, the findings were re-
ported as a composite. Only slight evidence of inflammatory reaction was
apparent histologically and was considered negligible. There was no acute
or chronic cellular or exudative response. Plasma cells or cells similar
in appearance to plasma cells were observed; these were possibly normal
hematopoietic elements or even osteoblasts. There was no evidence of
either osteoblastic or osteoclastic changes or periosteal proliferation.
There was no fibrous tissue barrier present in the long bones between the
screw and the bone at any point of contact along the metal path, except
where the screws penetrated the inner cortex and the periosteum into the
muscle tissue. In contrast, a fibrous capsule was present between the
apex of the screw and the medullary space of the mandible.
The authors concluded the cast and wrought Vitallium and Austanium plates
and screws, combined or separate, were compatible with soft tissues and
the bone, and did not cause any observable clinical or histologic injury.
C. Toxicity - Humans
1. Occupational Studies
Industrial exposure to dust of titanium and titanium dioxide has not been
linked with an unusual incidence of illness among workers and hence has
not received as extensive investigation as some other industrial compounds.
In Finland, lung samples from three men who had worked in a titanium
dioxide processing factory for 9-10 years, were examined with light and
(2)
electron microscopy. All three had displayed pulmonary symptoms incl
dyspnea, productive cough and recurrent bronchitis which were associated
1. P.P. Gross and L. Gold, loc. cit.
2. R.K. Elo, K. Maata, E. Uksila and A. Arstila, loc. cit.
-70-
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with their work. Radiologically, two of the patients showed changes of
pneumoconiosis. At thoracotomy, pleural and diaphramic adhesions were
found in one of the patients and both had green-colored patches on the
lung surface associated with carbon pigment. At autopsy (following un-
related drowning) the third worker also had green-colored patches of
pleural changes. Examination with light microscopy showed carbon-like,
but birefractive pigment aggregations; the nature of the pigment was not
determined. Two of the lungs showed some bronchiolar hyperplastic changes
and one emphysema and chronic bronchitis. Electron microscopy revealed
numerous phagocytizing cells in the alveolar lumen; the cytoplasm of these
cells was filled with electron-dense, single membrane-limited lysosomes
which contained numerous black particles. X-ray fluorescence analysis
indicated considerable amounts of titanium were present in all three lungs.
In two of the cases this was confirmed by optic emission spectrographic
analysis. Slight elevations of magnesium, aluminum and silica were seen
in two of the lungs; the third had a high concentration of nickel.
In contrast to the above study a study of 136 workers engaged in loading
or in extracting ilmenite failed to reveal any such possible effects.
The workers were submitted to 70 mm radiography of the chest, clinical
examination and interview about respiratory symptoms. Length of service
ranged from 1 to 12 years and averaged 4.4 years for all workers, 3.3 years
among the most exposed workers. Radiological lesions were observed in three
workers of whom only one had a high degree of exposure. All three were
asymptomatic. A similar incidence was found among controls. Six workers
had respiratory symptoms since starting work at the factory, but none had
1. C.G. Uragoda and U.R.M. Pinto, "An Investigation into the Health of
Workers in an Ilmenite Extracting Plant," Medical Journal of Australia,
1 (4), (1972) p. 167-9
-71-
-------
any abnormal physical signs or radiological lesions in the chest. The
symptoms were considered to be due to dust per se^ and not a specific
response to minerals.
In response to a request from an employee representative, the National
Institute for Occupational Safety and Health of the U.S. Department of
Health, Education and Welfare conducted a health hazard survey at the
Titanium Pigment Division of the NL Industries, Ltd. Among 15 randomly-
selected individuals who were interviewed, none had health complaints or
knew of anyone working in his area who had. Nine individuals who had
reported health complaints were interviewed. None of these suggested a
relationship to exposure to titanium dioxide although several indicated
effects (irritant contact dermatitis, plus one case of upper tract and
eye irritation) from exposure to monoisopropanolamine (MIPA). Until early
1973, MIPA had been metered into the grinding mills in small quantities to
reduce any caking tendency and to insure a final TiCL product ground to
exact specification. Triethanolamine (TEA) was then substituted for MIPA,
but was later eliminated prior to 31 May 1973. After the discontinuation
of MIPA, no new cases of irritation or dermatitis occurred.
Although monoisopropanolamine and its vapor are not regarded as toxic in
the usual industrial setting, MIPA on contact with the skin can cause
local effects up to a burn, depending on exposure. It is not, however,
considered to be a problem because of this and it is generally considered
low in toxicity by this route. Any vapor generated by MIPA should be
avoided. Similarly, a single short exposure to TEA can result in mild
skin irritation; prolonged or repeated exposure can provoke moderate irri-
tation or even a mild burn. However, TEA is not likely to be absorbed in
toxic amounts by the skin. In contact with the eye, MIPA can cause local
1. R.L. Hervin and J.B. Lucas, Health Hazard Evaluation/Toxicity Deter-
mination, NL Industries. NIOSH-TR-068-74, PB-229 604 (Springfield,
Virginia: NTIS, September 1973)
-72-
-------
effects up to a burn; TEA can cause moderate irritation and corneal injury.
The ML employees were exposed to MIPA (or to TiCK semi-saturated with MIPA)
during maintenance operations or when a leak occurred in the system. The
wearing of appropriate protective clothing by employees is recommended, if
either MIPA or TEA is reintroduced into the workplace.
The plant appeared to be rather dusty, but respirable levels of titanium
dioxide were below the standard permitted. It was concluded that no safety
recommendations need be made at the plant although the general housekeeping
could be improved to reduce the dust levels. Although there was no evidence
of actual or potential pulmonary or other hazard to employees from the Ti02
dust, respirators should be provided and used by the employees, whenever
airborne inert or nuisance dust is present in excessive amounts.
2. Epidemiology
No epidemiological studies were available for review. Titanium and its
compounds have been used in therapy of skin disorders and in surgical
(2)
appliances over the years with no reports of toxicity from such use.
3. Other Controlled Studies
There is very little data concerning controlled studies of the toxicity
to humans of titanium dioxide. In 1955, it was reported that the use of
1. R.L. Hervin and J.B. Lucas, loc. cit.
2. E. Browning, Toxicity of Industrial Metals, Second Edition
(New York: Appletion-Century-Crofts, (1969) p. 331-5
-73-
-------
titanium salts in ointment and powder preparations over a 3-year period in
some one hundred cases had shown therapeutic promise with no toxic effects.
However, details are lacking as to how well controlled these studies were.
Preliminary results of efficacy of various agents for protection of the
skin from exposure to light suggest that titanium dioxide is an effective
agent.<2>
D. Toxicity - Birds and Mammals
1. Acute
The study of Gfithe and Swensson, which was discussed in detail (pp.67-8)
showed that rats receiving a single intratracheal injection of 1 ml of a
TiCL suspension in saline solution (20 mg/ml) and BCG, alone or in combi-
nation, did not show any retarded body weight increase in comparison with
the untreated controls. No c
toxicity of titanium dioxide.
the untreated controls. No other information was available on the acute
(3)
2., 3., 4., 5., and 6. Subacute, Sensitization from Repeated Doses,
Teratogenicity, Mutagenicity, and Carcinogenicity
The literature reviewed did not reveal any information or data on subacute
toxicity, sensitization from repeated doses, teratogenicity, or carcino-
genicity of titanium dioxide.
7. Other Chronic Studies
No evidence of any specific pathologic lesion produced by titanium dioxide
was observed in rats following inhalation of the dust for 9-13 exposure
1. L.P. Ereaux, "Clinical Observations on the Use of Titanium Salts in
Man," Canadian Medical Association Journal, 73 (1955) p. 47
2. T.M. MacLeod and W. Frain-Bell, "The Study of the Efficacy of Some
Agents Used for the Protection of the Skin From Exposure to Light,"
British Journal of Dermatology, J54 (1971) p. 266-81
3. C.J. Gothe and A. Swensson, op. cit., p. 579-85
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months in the study by Christie et al, which was discussed in detail
(pp. 64-5). No information on other chronic toxicity studies in
animals by any route was available.
8., 9., and 10. Behavioral Effects, Possible Synergisms, Other
No information.
E. Toxicity - Lower Animals
No information.
F. Toxicity - Plants
No information.
G. Toxicity - Microorganisms
No information.
H. Effects On Inanimate Objects and Structures
No information.
1. H. Christie, R.J. MacKay and A.M. Fisher, op_. cit.
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IV. REGULATIONS AND STANDARDS
A. Current Regulations
1. Food and Drug Authorities
Regulations appear to make a differentiation between "color additives"
and "food additives." The dyes or pigments, which are added to food, drugs
or cosmetics, are generally "color additives" and those which are used in
containers, films, coatings or other materials that are in contact with
but not transferred to food are generally "food additives."
Amendments to the Federal Food, Drug and Cosmetic Act, Part 8-Color Additives,
Subparts D and F, regarding titanium dioxide as a color additive state that
TiO- be free from admixture with other substances. Specifications stipulate
that TiO. conform to the following:^ '
Lead (as Pb), not more than 10 parts per million.
Arsenic (as As), not more than 1 part per million.
Antimony (as Sb), not more than 2 parts per million.
Mercury (as Hg), not more than 1 part per million.
Loss on ignition at 800°C. (after drying for 3 hours
at 105°C), not more than 0.5 percent.
Water soluble substances, not more than 0.3 percent.
Acid soluble substances, not more than 0.5 percent.
TiO- not less than 99.0 percent after drying for 3 hours at 105°C.
Lead, arsenic, and antimony shall be determined in the solution obtained
by boiling 10 grams of the titanium dioxide for 15 minutes in 50 milliliters
of 0.5N hydrochloric acid.
1. "Color Additives" — Part 8, Title 21, Federal Register, loc. cit.
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In coloring foods TiO is restricted for use:
(1) "The quantity of titanium dioxide does not exceed 1 percent
by weight of the food.
(2) It may not be used to color foods for which standards of
identity have been promulgated under section 401 of the act
unless added color is authorized by such standards."
In packaging materials such as paper, adhesives, textiles, cellophane,
resinous and polymeric coatings, which contain titanium dioxide, the use
of TiO_ is generally listed as authorized for use without any specified
limitations. Occasionally the limitations simply state that use be con-
sistent with good manufacturing practice.
2. and 3. Air, Water, and Ocean Dumping
In its Title 40 — Protection of the Environment, Chapter 1, EPA has issued
Ocean Dumping Criteria (Subchapter H, Part 227) in which titanium dioxide
wastes are classified under Section 227.41, entitled "Materials Requiring
Special Care," EPA stipulates that titanium dioxide wastes come under
the category of materials for which permits may be issued for its dumping,
if the applicant can demonstrate "(1) through the use of acceptable bio-
assay or other scientific data that dumping of the material in the proposed
quantities and qualities will have minimal adverse effects on the ocean
environment" and "(2) that the material proposed for dumping contains less
than the limiting permissible concentration of total pollutants" as stated
(2)
in Section 227.71 entitled "Limiting Permissible Concentrations."
4. Occupational Safety and Health Administration
Under the Occupational Safety and Health Standards, announced by OSHA in
mid-1974, TiO^ is listed in a table of air contaminants for which employee
exposure limits are given as 8-hour time weighted averages. Thus OSHA
has established that for any 8-hour work shift of a 40-hour week, an
1. "Color Additives" — Part 8, Title 21, Federal Register, loc. cit.
2. "Ocean Dumping Criteria," Federal Register, 38 (94), (16 May 1973) p. 12873
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employee's exposure to TiO. shall not exceed the 8-hour time weighted
^ n ^
average of 15 mg/M .v '
5. Department of Transportation
Titanium dioxide does not appear on the DOT's List of Hazardous Materials.
However, both titanium tetrachloride and titanium sulfate solution, con-
(2)
taining not more than 45 per cent sulfuric acid, are listed.
6. and 7. Other Federal and State Regulations
There were no additional regulations reported.
8. Foreign Countries
The Inter-Governmental Maritime Consultative Organization (IMCO) does not
list TiO, in its International Maritime Dangerous Goods Code although
(3)
titanium tetrachloride is listed.
B. Consensus and Similar Standards
1. and 2. Threshold limit Value (TLV) and Public Exposure Limits
The American Conference of Governmental Industrial Hygienists identifies
Ti02 as an "inert" or nuisance dust and, in accordance with their
general rule for substances in this category, they recommended a TLV of
10 mg/M3 for TiCy
1. "Occupational Safety and Health Standards," Federal Register, _39_ (125),
(27 June 1974) p. 23542
2. Code of Federal Regulations 49 Transportation. (Washington, B.C.: GPO
1972) p. 39
3. International Maritime Dangerous Goods Code, IMCQ. (London: Unwin
Brothers Ltd., n.d.)
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3. Other Regulations and Standards
a. American Industrial Hygiene Association
As part of their Hygienic Guide Series, The American Industrial Hygiene
Association reported on titanium dioxide summarizing: hygienic standards,
including recommended maximal atmospheric concentrations [(8 hours): 15 mg/m ]
exposure tolerances, and atmospheric concentration immediately hazardous
to life; toxic properties, including inhalation, skin contact, and ingestion;
industrial hygiene practice, including industrial uses, evaluation of ex-
posures, and hazards and their recommended control; and medical information.
Their concluding statement was that because of the chemical and physiolo-
gical inertness of TiO_, it is unlikely that an emergency could arise which
(1)
would require medical attention.
b. Joint Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP)
GESAMP is a joint group made up of IMCO, FAO, UNESCO, WHO, IAEA, UN experts.
In the list of marine pollutants and their relative harmfulness, which they
have developed, TiO_ wastes appear. The GESAMP evaluation of Ti07 wastes
indicates that they are of slight harm to living resources but no special
control action is indicated. Furthermore, their evaluation shows TiO~
wastes to be a negligible hazard to human health and a negligible hindrance
(2)
to maritime activities.
c. National Safety Council
Titanium dioxide is not listed per se on The National Safety Council's
(3)
list although the broader category titanium and its compounds does appear.
1. "Titanium Dioxide," American Industrial Hygiene Association Journal.
2]_ (2), (March-April 1966) pp. 206-7
2. Bernt I. Dybern, "Water Pollution — A Problem with Global Dimensions,"
Ambio, _3 (3-4), p. 143 (1974)
3. Chemical Safety References, Data Sheet 486, Revision A (Chicago:
National Safety Council, 1968) p. 14
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d. ASTM
Specifications for TiO? pigments are available inasmuch as manufacturers
of special pigments carefully control the composition and properties of
their products. Each pigment grade and its formulation is held within
close limits.
The ASTM's directions for testing TiO_ specifications include composition,
residue on a sieve test, oil absorption valve, color and tinting resistance,
matter volatile at 105°C, and matter soluble in water.
The corresponding ASTM designations include D 476-66, Titanium Dioxide
Pigments and D 1394-63, Chemical Analysis of White Titanium Dioxide
Pigments. ASTM BS 239, White Pigments for Paints, also incorporates
BS 1851.
1. Kirk-Othmer Encyclopedia of Chemical Technology, op. cit., p. 407
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V. EVALUATION AND COMMENTS
A. SUMMARY
The United States, with an estimated production capacity of 939,000 tons/yr
of titanium dioxide, now consumes approximately 800,000 tons annually.
Although TiO. ranked only 48th in the production list of the 50 biggest-
volume chemicals in 1972, it is industrially significant because of its
unique contribution to the manufacture of so many commonly-used products,
such as paint, paper and plastics.
Historically, titanium dioxide, per se, has been recognized as an in-
nocuous compound, primarily due to its chemical inertness and its in-
solubility in water and most organic solvents. It is, however, classified
as a nuisance dust and prolonged exposure to TiO_ dust, or exposure to
excessive amounts, has caused respiratory irritations. There is no indi-
cation, however, that the effects of TiO_ in any way resemble those attri-
buted to silica (silicosis), beryllium (berylliosis), or asbestos (asbestosis).
In fact, it is utilized beneficially in preparations for the treatment of
dermal irritations and has been used as a sunscreen.
Central to current environmental concern is the potential effect of and
the disposition of the waste products from Ti02 manufacture. By their very
nature, the gaseous emissions and the acidic effluents involved are cor-
rosive and capable of producing deleterious effects. Such characteristics
highlight the significance of effective control with its attendant engineering
problems and cost. In addition, environmental regulatory agencies are
pressing for the development of controls that will decrease the potential
environmental hazards.
B. CONCLUSIONS
Until recently, manufacturers of TiO_ faced no problems relative to the source
of the necessary raw materials. Now, there is developing concern about the
future availability of rutile ore to supply the increasing number of faci-
lities utilizing this ore in the chloride process. Consequently, these
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manufacturers must find ways of increasing supplies of a high titanium
dioxide-content raw material either by beneficiation of the lower-purity
ilmenite or by the use of mixed feeds. Although existing technology indi-
cates that this problem will be solved, the solution will bring with it a
continuation, or a magnification, of some of the environmental problems
that plague the industry at present, and may even introduce new problems.
The existing problems of TiO. processing waste disposal must be settled
soon in a manner satisfactory to industry and government. Along with the
development of new manufacturing technology, should go process innovations
for the recovery and use of waste materials.
Landfill is the presently accepted disposal method for the solid wastes
involved, but there is no record of research to determine the magnitude
and potential long-term hazards of the leaching out of trace toxic metals
from these wastes into the surrounding soil and waters. This issue, as
well as the determination of the magnitude and potential problems of waste
effluents from TiO. consuming industries, might become the subject for
other future studies.
The lack of literature in a number of pertinent areas necessary to deter-
mine the total health and environmental effects of TiCL, such as environ-
mental transport, bioconcentration and biomagnification, and toxicity,
hinders the completeness of analysis and evaluation, and suggests the need
for further studies.
In conclusion unless new findings from current research, not published,
or from future research contradict the prevailing views, it can be con-
cluded that TiO , per se, does not pose substantial environmental hazard.
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Chemical Week 112, 27 (28 March 1973)
2. AT SHERWIN-WILLIAMS, CHANGE IS MORE THAN LOGO DEEP
Chemical Week 116 (5), 34-5 (29 January 1975)
3. Barksdale, Jelks
TITANIUM, ITS OCCURRENCE, CHEMISTRY AND TECHNOLOGY, 2nd ed.
Ronald Press Co., New York City. 1966
4. Beder, O.K. and Eade, G.
AN INVESTIGATION OF TISSUE TOLERANCE TO TITANIUM METAL IMPLANTS IN
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Surgery 3£, 470-3 (1956)
5. Bloom, G. and Swensson, A.
THE REACTION OF THROMBOCYTES TO INTRAVENOUSLY INJECTED SUSPENSIONS
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Acta Medica Scandinavica 162, 423-6 (1958)
6. Browning, E.
TOXICITY OF INDUSTRIAL METALS, 2nd ed.
Appleton-Century-Crofts, New York City. 1969
7. CHEMICAL SAFETY REFERENCES
National Safety Council, Chicago. 1968
8. CLEANER UNITS FOR Ti02 STILL LEAVE DU PONT AT SEA
Chemical Week 116 (1), 26-7 (1 January 1975)
9. Christie, H., MacKay, R.J., and Fisher, A.M.
PULMONARY EFFECTS OF INHALATION OF TITANIUM DIOXIDE BY RATS
American Industrial Hygiene Association Journal ,24_ (1), 42-6 (1963)
10. CODE OF FEDERAL REGULATIONS. TITLE 49 ~ TRANSPORTATION
Government Printing Office, Washington, D.C. 1972
11. COLOR ADDITIVES — PART 8, TITLE 21
Federal Register _31 (18), 1065-6 (27 January 1966)
12. DIRECTORY OF CHEMICAL PRODUCERS
Chemical Information Services, Stanford Research Institute, Menlo Park,
California. 1974
A-l
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13. DOCUMENTATION OF THE THRESHOLD LIMIT VALUES FOR SUBSTANCES IN WORKROOM
AIR, 3rd ed.
American Conference of Governmental Industrial Hygienists, Cincinnati.
1971
14. du Pont de Nemours, E.I. & Co., Pigments Department
MATERIALS SAFETY DATA SHEET
Occupational Safety & Health Administration, U.S. Dept. of Labor
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16. Dybern, Bernt I.
WATER POLLUTION — A PROBLEM WITH GLOBAL DIMENSIONS
Ambio _3 (3-4), 139-45 (1974)
17. Elo, R.K., Maata, K., Uksila, E., and Arstila, A.
PULMONARY DEPOSITS OF TITANIUM DIOXIDE IN MAN
Archives of Pathology j)4 (4), 417-24 (1972)
18. Ereaux, L.P.
CLINICAL OBSERVATIONS ON THE USE OF TITANIUM SALTS IN MAN
Canadian Medical Association Journal 73, 47 (1955)
19. Fader, Samuel W.
BARGING INDUSTRIAL LIQUID WASTES TO THE SEA
Journal of the Water Pollution Control Federation 44 (2), 314-8
(February 1972)
20. Faith, W.L., Keyes, D.B., and Clark, R.L.
INDUSTRIAL CHEMICALS, 3rd ed.
John Wiley & Sons, Inc., New York City. 1965
21. Ferin, J.
PAPAIN-INDUCED EMPHYSEMA AND THE ELIMINATION OF TI02 PARTICULATES FROM
THE LUNGS
American Industrial Hygiene Association Journal 32. 157-62 (1971)
22. Fournier, P.
DE L'EMPLOI DE L'OXYDE DE TITANE POUR L1ETUDE QUANTITATIVE DE
L1ABSORPTION INTESTINALE
Comptes Rendus des Seances deL1Academic des Sciences 231, 1343-5 (1950)
23. GCA Corporation
EMISSIONS INVENTORY OF SOURCES AND EMISSIONS OF TITANIUM
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A-2
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24. Ginsburg, I. and Trost, R.
LOCALIZATION OF GROUP A STREPTOCOCCI AND PARTICLES OF TITANIUM DIOXIDE
IN ARTHRITIC LESIONS IN RABBITS
Journal of Infectious Diseases 123 (3), 292-6 (1971)
25. Ginsburg, I., Gallis, H.A., Cole, R.M., and Green, I.
GROUP A STREPTOCOCCI: LOCALIZATION IN RABBITS AND GUINEA PIGS FOLLOWING
TISSUE INJURY
Science 166, 1161-3 (1969)
26. Gb'the, C.J. and Swensson, A.
EFFECT OF BCG ON LYMPHATIC LUNG CLEARANCE OF DUSTS WITH DIFFERENT
FIBROGENICITY, AN EXPERIMENTAL STUDY IN RATS
Archives of Environmental Health 20, 579-85 (1970)
27. Gross, P.P. and Gold, L.
COMPATIBILITY OF VITALLIUM AND AUSTANIUM IN COMPLETELY BURIED IMPLANTS
IN DOGS
Oral Surgery J.O, 769-80 (1957)
28. HEAVY GOING AHEAD FOR WASTES DISCHARGING AT SEA ,
Chemical Week 112 (26), 45, 47 (27 June 1973)
29. Hervin, Raymond L. and Lucas, James B.
HEALTH HAZARD EVALUATION/TOXICITY DETERMINATION. N.L. INDUSTRIES, INC.
TITANIUM PIGMENT DIVISION, ST. LOUIS., MISSOURI
National Technical Information Service, U.S. Dept. of Commerce, Springfield,
Virginia. NIOSH-TR-068-74, PB-229 604, September 1973
30. Huggins, C.B. and Froelich, J.P.
HIGH CONCENTRATION OF INJECTED TITANIUM DIOXIDE IN ABNORMAL LYMPH NODES
Journal of Experimental Medicine 124 (6), 1099-1106 (1966)
31. Hyman, Harry
WORKING WITH THE VOLUME INORGANICS
Chemical Engineering/Deskbook Issue 80, 15-23 (8 October 1973)
32. lammartino, Nicholas R.
TROUBLED TIMES FOR TI02
Chemical Engineering _79_, 34-6 (1 May 1972)
33. INTERNATIONAL MARITIME DANGEROUS GOODS CODE, IMCO
Unwin Brothers Ltd., London, n.d.
34. Kamofer. W.A.
TITANIUM DIOXIDE
In Pigment Handbook, Volume 1, T.C. Patton, Editor, John Wiley & Sons, Inc.
1973
A-3
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35. Kerr-McGee Chemical Corporation
MATERIALS SAFETY DATA SHEET
Occupational Safety & Health Administration, U.S. Dept. of Labor
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U.S. INDUSTRY GIRDS FOR NO-GROWTH YEAR
Chemical & Engineering News 52, 18-20 (23 December 1974)
37. KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 2nd ed. (Revised).
VOLUME 20
John Wiley & Sons, Inc., New York City, 1969
38. Lloyd, L.E., Rutherford, Elaine, and Crampton, E.W.
A COMPARISON OF TITANIC OXIDE AND CHROMIC OXIDE AS INDEX MATERIALS FOR
DETERMINING APPARENT DIGESTIBILITY
Journal of Nutrition 56, 265-71 (1955)
39. MacLeod, T.M. and Frain-Bell, W.
THE STUDY OF THE EFFICACY OF SOME AGENTS USED FOR THE PROTECTION OF
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British Journal of Dermatology J34, 266-81 (1971)
40. MERCK INDEX, THE, 8th ed.
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MATERIALS SAFETY DATA SHEET
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Federal Register J39 (125), 23540-3 (27 June 1974)
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44. Patty, Frank A., Editor
INDUSTRIAL HYGIENE AND TOXICOLOGY, VOLUME II, TOXICOLOGY
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45. PIGMENTS
Rubber Age 107, 12 (March 1975)
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ESTIMATING POPULATION EXPOSURE TO SELECTED METALS — TITANIUM
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Chemical Week 115, 1 (20 November 1974)
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TROUBLE FOR THE MEDITERRANEAN
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ABNORMAL TRACE METALS IN MAN: TITANIUM
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EFFECT OF CHROMIUM, CADMIUM AND OTHER TRACE METALS ON THE GROWTH AND
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Rubber Age 107, 14 (February 1975)
54. TITANIUM DIOXIDE
Rubber Age 106, 12 (December 1974)
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American Industrial Hygiene Association Journal 27_ (2), 206-7
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DEVELOPMENT DOCUMENT FOR EFFLUENT LIMITATIONS GUIDELINES AND NEW SOURCE
PERFORMANCE STANDARDS FOR THE MAJOR INORGANIC PRODUCTS SEGMENT OF THE
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CHEMICAL AND PHYSICAL INVESTIGATIONS ON MARINE POLLUTION BY WASTES OF
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In Marine Pollution and Sea Life, Mario Ruivo, General Editor,
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A-6
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JAPCA 12 (7): 326-31 (July 1962)
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DEVELOPMENT AND EVALUATION OF LUBRICANT COMPOSITE MATERIALS
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Cardona, Manuel and Harbeke, Gunther
OPTICAL PROPERTIES AND BAND STRUCTURE OF WURTZITE-TYPE CRYSTALS AND RUTILE
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CLOUDING AGENTS FOR INCORPORATION INTO A DRY BEVERAGE MIX
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MINIMIZING CHEMICAL AND FINES BUILDUP IN WHITE WATER BY CHEMICAL MEANS
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Darley, E.F.
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Fumi Polveri (Milan) 6> (1): 274-81 (Oct. 1966) (In Italian)
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GLASSES AND GLASS-CERAMICS FROM ALKALI OXIDES-CALCIA-MAGNESIA-ALUMINA-
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Cent. Glass Ceram. Res. Inst. , Bull 17. W'• 99-104 (1972)
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NEW STUDIES ON AEROSOLS XXIV. DEPOSITION RATE OF VARIOUS MICROAEROSOLS
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ELECTRONIC AND RADIATION DAMAGE PROPERTIES OF RUTILE
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MEASUREMENTS OF ABSORPTION AND REFLECTANCE
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THE ANALYSIS OF TITANIUM DIOXIDE PIGMENTS BY.AUTOMATIC SIMULTANEOUS
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RATES OF REACTION OF S02 WITH METAL OXIDES
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DeVries, G.; and Meijer, A.E.F.H.
HISTOCHEMICAL METHOD FOR IDENTIFICATION OF TITANIUM AND IRON OXIDES IN
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HANDBOOK OF THE OPTICAL, THERMAL AND MECHANICAL PROPERTIES OF SIX
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Purdue Univ., Thermophysical Properties Research Center, Rept. for
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APPARENT TEMPERATURES MEASURED AT MELTING POINTS OF SOME METAL OXIDES IN
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HOW TO SELECT TITANIUM DIOXIDES FOR POLYOLEFINS
Plastics Technol.16 (6): 50 (June 1970)
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MICROSTRUCTURE AND INDENTATION HARDNESS OF A MAGNESIA-LITHIA-ALUMINA-
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THE ROLE OF PROMOTERS IN THE HYDROGENATION OF CARBON MONOXIDE OVER IRON
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INFLUENCE OF VERCORYL ON LIGHT AGING AND ITS PROTECTIVE EFFECT
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Dunn, J.L.; Heffner, M.H.
OUTDOOR WEATHERABILITY OF RIGID PVC
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COMPARISON OF CW (CONTINUOUS WAVE) ACOUSTOOPTICAL AND PULSE-ECHO
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IEEE Trans. Sonics Ultrason. 20 (3): 279-81 (1973)
Dyer, R. and Bach, H.W.
TITANIUM DIOXIDE PIGMENTS IN PLASTICS INTERACTIONS DESIRABLE AND
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SPE, 29th Ann. Tech. Conf., Washington, D.C. 17: 175-81 (10-13 May 1971)
Easteal, Allan J.; Udy, David J.
EXTRACTION OF TITANIUM DIOXIDE (TiO,) FROM ILMENITE AND TITANIFERROUS SLAG
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HEALTH HAZARDS FOR TEACHERS OF POTTERY, STUDENTS, AND AMATEUR POTTERS
Proc. Austr. Ceram. Conf., 4th, AB30/1-AB30/12, 1970
Egerton, G.S.
PHOTOSENSITIZING PROPERTIES OF DYES AND WHITE PIGMENTS
Nature 204 (4964): 1153-5 (1964)
Egerton, G.S. and Fisher, K.M.
USE OF THE SCANNING ELECTRON MICROSCOPE IN A STUDY OF THE ABRASIVE
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Text. Res. J. 40 (9): 784-8 (Sept. 1970)
Egerton, G.S. and Shah, K.M.
EFFECT OF TEMPERATURE ON THE PHOTOSENSITIZED DEGRADATION OF TEXTILE FIBERS
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Egerton, G.S. and Shah, K.M.
THE EFFECT OF TEMPERATURE ON THE PHOTOCHEMICAL DEGRADATION OF TEXTILE
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Text. Res. J. _38 (2): 130-5 (Feb. 1968)
Einbrodt, H.J.; and Liffers, R.
INVESTIGATIONS ON THE LYMPHATIC TRANSPORT OF TITANIUM DIOXIDE FROM THE
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Arch. Hyg. Bakteriol. 152 (1): 2-6 (1968) (In German)
Elik, E.E.; Rempel, S.I.
INFLUENCE OF FREEZING ON THE PROPERTIES OF PRECIPITATES IN ACID WASTE WATERS
Okhr. Prir. Vod. Urala 4: 69-73 (1971) (in Russian)
Elik, E.E.
PROCESSING OF TITANIUM DIOXIDE — MANUFACTURE WASTE WATERS FOR OBTAINING
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Sb. Nauch. Tr. Aspir. Soiskatelei, Ural. Lesotekh. Inst. No. 2, 106-10 (1969)
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STRENGTH OF TITANIA AND ALUMINUM SILICATE UNDER COMBINED STRESSES
J. Aroer. Ceram. Soc. 55 (7): 347-50 (1972)
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EXPERIMENTAL ADOPTION OF A SHOP FOR PRODUCING SULFURIC ACID FROM
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Tr., Nauch.-Issled. Inst. Udobr. Insektofungits. 70 (216): 50-3 (n.d.) (In Russian)
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COATING DEMANDS VERSATILITY IN HANDLING AND PREPARATION EQUIPMENT
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MODIFIED LACTALBUMIN HYDROLYZATE
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THE EFFECT OF S02 ON LUNG CLEARANCE OF T102 PARTICLES IN RATS
J. Am. Ind. Hyg. Assn. .34 (6): 260-3 (June 1973)
Ferin, J.
LUNG CLEARANCE OF T102 PARTICLES IN RATS
Toxicol. Appl. Pharmacol. 17 (1): 308 (1970)
Ferin, Juraj
PULMONARY CLEARANCE AFTER DEPOSITION OF AEROSOLS
(Bratislava) 5_ (1): 1-69 (1966)
Ferin, Juraj
OBSERVATIONS CONCERNING ALVEOLAR DUST CLEARANCE
Ann. N.Y. Acad. Sci. 200; 66-72 (1972)
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TITANIUM-DIMMED SILVERING ENAMEL INSTEAD OF TOXIC LEAD ARSENIC ENAMELS
Glas-Email-Keramo-Tech. 5: 89 (1954)
Figurovskaya, E.N.
INVESTIGATION OF THE EFFECT OF ADSORPTION OF WATER VAPORS ON THE WORK
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Kinet Catal 10 (2): pt.2, 374-7 (Mar-Apr. 1969)
Firle, Tomas E.; Flanagan, Terry M.
MECHANISMS OF DEGRADATION OF POLYMERIC THERMAL CONTROL COATINGS. PART II:
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Final Rept. GA-9853 1 Sept. 1968 - 30 Nov. 1969; Gulf General Atomic Inc.
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Fleischauer, Paul D.; Chase, Armond B.
COORDINATION CHEMISTRY AND KINETICS OF PREFERENTIAL ETCHING ON SURFACES
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U.S. NTIS, AD-759 259 (1973) 33 pp.
Frankle, W.E.; Penniman, John G., Jr.
ZETA POTENTIAL MEASURING BY LASER. KEY TO ONE-PASS RETENTION.
Pap. Trade J. 157 (32): 30-2, 38 (1973)
Franklin, M.J.B.; Goldbrough, K.; Pareltt, G.D.; and Peacock, J.
INFLUENCE OF PARTICLE CHARGE AND RESIN ADSORPTION ON THE OPACITY OF
ALKYD PAINT FILMS PIGMENTED WITH TITANIUM DIOXIDE
Amer. Chem. Soc.Div. Org. Coatings Plast. Chem. 30 (1): 427-33 (May 1970)
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Franklin, A.D.; Bennett, H.S.
ARPA-NBS PROGRAM OF RESEARCH ON HIGH TEMPERATURE MATERIALS AND LASER MATERIALS
Technical Note, 1 Jan. 1930 - June 1970; Inst. for Materials Research,
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USE OF CERAMIC MATERIALS IN PARTICLE ACCELERATORS AND AMPLIFIERS OPERATING
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Frensch, Heinz and Albrecht, Konrad
EVAPORATION-INHIBITING ADDITIVE TO PLANT PROTECTIVES
Ger. Offen. 2,205,590 (16 Aug. 1973)
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Fujita, Yutaka; Naruchi, Tatsuyuki| Yoshlsato, Elshln
REACTIVATION OF SPENT WASTE TITANIUM DIOXIDE-COPPER CATALYST USED IN
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Japan. Kokai Patent-No: 72, 33081 (18 Mar. 1971)
Gaertner, E. .
TITANIUM DIOXIDE AND ITS USE IN PLASTICS FOR PACKAGING
Kunststoffe 61 (8): 525-8 (1971)
Gass, J.L.; Juillet, F.; Teichner, J.
PREPARING METAL OXIDE AEROSOLS BY THERMAL DECOMPOSITION OF THEIR ALCO-
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Bull. Soc. Chira. (France) 2_ (Part 1): 429-35 (Feb. 1973)
Gluliano, C.R.; Hess, L.D.; Bliss, R.S.
DAMAGE THRESHOLD STUDIES IN LASER CRYSTALS
Air Force Cambridge Research Labs L G Hanscom Field Mass (011800)
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Gluliano, Concetto R.; DeBois, Donald F.; Hellwarth, Robert W.
DAMAGE THRESHOLD STUDIES IN LASER CRYSTALS
Hughes Research Labs, Malibu Calif.
Final Technical Rept. 16 June 1969 - 15 June 1972, AD-751 928 (Sept. 1972)
Glomme, John
AN EXPERIMENTAL EVALUATION OF THE RELATIVE FIBROGENETIC TENDENCY OF
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Securitas (Rome) _55 (11/12): 959-1108 (Nov./Dec. ' 1970)
Goethe, Carl-Johan; Swensson, Ake
INFLUENCE OF BCG ON LYMPHATIC LUNG CLEARANCE IN RATS
British Occupational Hygiene Society, London, England, Inhaled Particles
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Goodheart, B.A.; Birkett, G.C.L.
TITANIUM MINERALS AND PIGMENT PRODUCTION
Proc. Royal Aust. Chetn. Inst. 39. (8): 227-32 (1972)
Grabner, Ludwig H.; Wong, Eugene Y.
ZEEMAN EFFECT OF NO-PHONON QUARTET A2G-QUARTET T2G TRANSITION OF Cr(3+)
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National Bureau of Standards, Washington, D.C., Final Rept.
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Hamamura, Takuya; Yoshito, Onishi; and Yosuo, lizuka
THE CAYALYTIC OXIDATION OF CARBON MONOXIDE ON ZIRCONIUM DIOXIDE
Bull. Chem. Soc. Japan (Tokyo) 45 (5): 1288-91 (May 1972)
Han, Jae Sik and Kim, Jun Su
METALLIC TITANIUM PRODUCTION FROM KOREAN ILMENITE. III. PREPARATION OF
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Bull. Scl. Research Inst. (Korea) 4^ (1): 5-11 (1959)
Harman, George G.
ELECTROLUMINESCENCE FROM THE SURFACE LAYER OF BARIUM TITANATE, STRONTIUM .
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Phys. Rev. Ill; 27-33 (1958)
Harris, M.R. and Whitaker, G.
SURFACE PROPERTIES OF HYDROLYZED TITANIA. III. TITANIA PREPARED FROM
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Hass, George
PREPARATION, PROPERTIES, AND OPTICAL APPLICATIONS OF THIN FILMS OF TITANIUM
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Hasselberger, Francis X.; Allen, Billy; Paruchuri, E.K. et al
IMMOBILIZED ENZYMES: LACTASE BONDED TO STAINLESS STEEL AND OTHER DENSE
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Biochem. & Biophys. Res. Conm. 5_7 (4): 1054-62 (1974)
Haughey, Francis J. and Manganelli, Raymond M.
AN EXPERIMENTAL SYSTEM FOR AEROSOL RESEARCH
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Hiester, N.K.; Listen, E.M.; Goerz, D.
BENEFICIATION OF ILMENITE BY SULFIDIZATION
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Higbie, Kenneth B.; Stamper, John W.
THE PRODUCTION OF PRIMARY TITANIUM METAL
U.S. Atomic Energy Commission, DMIC-MEMO-234, 8-12, (1968)
Higgins, William A.
WEATHER-PROOF COATING
U.S. 3,247,011 (19 April 1966)
Hilfenhaus, J.; Schmitt, W.; and Einbrodt, H.J.
STUDIES ON THE ADSORPTION OF LIPIDS FROM ERYTHROCYTE MEMBRANE BY SILICONS
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Arch Hyg. 153 (1): 9-13 (1969) (In German)
Hill, P.M.; Greener, W.A.
ANALYSIS AND CONTROL OF A ROTARY WASHING FILTER HANDLING TITANIUM DIOXIDE
Filtr. Separ. £ (D' 71-3, 96 (1972)
Hoffman, Clarence Anthony
RECOVERY OF INORGANIC FILLER MATERIALS FROM PAPER MILL WASTE SLUDGE
Ger. Offen. 2,256,581 (30 May 1973)
Homsy, Charles A.
CURRENT RESEARCH ON THE IN VITRO STABILIZATION OF SKELETAL PROSTHETIC
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Proc. Semin.-Workshop Biomater. 135-55 (1969) (Pub. 1971)
Hoogerbeets, J.G.
EFFICIENT USE OF TITANIUM DIOXIDE PIGMENTS IN ORGANIC COATINGS
J. Oil Colour Chem. Ass. 54 (12): 1162-77 (1971)
Hottel, H.C.; Sarofim, A.F.; Dalzell, W.H.; Vasalos, I.A.
OPTICAL PROPERTIES OF COATINGS. EFFECT OF PIGMENT CONCENTRATION
AIAAJ. £ (10): 1895-8 (1971)
Huang, Chin-Pao and Ghadirian, Mehdi
PHYSICAL-CHEMICAL TREATMENT OF PAINT INDUSTRY WASTEWATER
Journal of the Water Pollution Control Federation 4£ (10): 2340-6 (1974)
Hughes, D.A.
METHODS OF OBTAINING THE OPTICAL PROPERTIES OF PAPERS CONTAINING
TITANIUM DIOXIDE AND OTHER FILLERS
Tappi 45_ (2): 159A-163A (1962)
Hulbert, S.F.; King, F.M. Jr.; Klaw^tter, J.J.
INITIAL SURFACE INTERACTION OF BLOOD AND BLOOD COMPONENTS WITH ALUMINUM
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Biomed. Mater. Symp. (2) (Pt. 1), 69-89 (1&71)
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Hulbert, Samuel F.; Pain, C.Clifford; Eltel, Michael J.;
DESIGN OF A WATER-DISPOSABLE GLASS PACKAGING CONTAINER. PART I:
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PART II: MECHANICAL PROPERTIES OF WATER-SOLUBLE SODIUM SILICATE GLASSES.
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Interim Rept. Clemson Univ., S.C. Div. of Interdisciplinary Studies.
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Imai, Kiyoshi; Doi, Mitsuru
PHYSICAL AND CHEMICAL PROPERTIES OF FIBERS IN RELATION TO RESIN
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Sen-i Kogyo Shikensho Iho 35.: 68-77 (1955)
Inoue, Yoshinori; Wadachi, Yoshiki; Yamaoka, Yoshito
SKIN CONTAMINATION BY 137CS AND ITS DECONTAMINATION
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A COMPARISON OF THE RATES OF PASSAGE OF CR203, TI02, AND FE203 USED
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Gen. Comp. Endocrinol. .4 (3): 264-70 (1964)
Ito, Fumio; Hirao, Kazushlge
QUANTITATIVE DIFFERENTIAL THERMAL ANALYSIS WITH SPECIAL REFERENCE TO
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Yogyo Kyokai Shi 65: 84-8 (1957)
Ivanov, N.; Schneider, R.
SURFACE DAMAGE ON PIGMENTED RAYON-ACETATE FABRICS BY THE ACTION OF
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Reyon, Zellwolle u. Chemlefasern ]_• 556-9 (1957)
Jansch, H.; Mayer, F.X.
LUNG ASH IN CASES OF SUSPECTED SILICOSIS
Beitr. Gerichtl. Med. 20,: 49-55 (1955)
Jayme, Georg; Reimann, Karl
DISTURBING INFLUENCES OF STARCH AND TITANIUM OXIDE ON THE DETERMINATION
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CALCIUM CARBONATE IN FLAT WALL PAINT
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DEGRADATION PROCESSES IN Ti02-PIGMENTED PAINT FILMS ON EXPOSURE TO
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J. Paint Technol. 46_ (598): 56 (Nov. 1974)
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A HYGIENIC ASSESSMENT OF PLASTIC ARTICLES USED FOR MEDICAL PURPOSES
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METHOD FOR REGENERATING COOKING LIQUOR FROM ALKALI PULP WASTE LIQUOR
Japan 7238,443 (28 Sept. 1972)
KERR-MCGEE CHEMICAL CORPORATION ANNOUNCES $100-MILLION TiOo PLANT IN MOBILE'
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COMPARISON OF SURFACTANT ADSORPTION ON TITANIUM DIOXIDE PIGMENT BY TEN-
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TREATMENT OF WASTE LIQUOR.FROM TITANIUM DIOXIDE MANUFACTURING
Ryusan 17 (1): 5-12 (1964) (In Japanese)
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THERMAL CONDUCTIVITY. XII. TEMPERATURE DEPENDENCE OF CONDUCTIVITY
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ELIMINATION OF DUST FROM THE LUNGS INTO THE REGIONAL LYMPH NODES
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RETENTION, PENETRATION AND ELIMINATION OF INHALED DUSTS i
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SUNSCREENS AND THEIR USEFULNESS j
Amer. Perfumer Aromat. 75. (8): 42-4 (1960) !
Komolova, T.I.; Nasledov, D.N.
ELECTRICAL PROPERTIES OF RECTIFIERS ON THE BASIS OF TK>2 '
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ETIOLOGY OF MALIGNANT TUMOURS OF THE NASOPHARYNX: A CONTRIBUTION '
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Kopp, R.J.; Grannemann, W.W.
INVESTIGATIONS OF METAL-BURIED SILICIDE-SILICON STRUCTURES AND METAL- I
TITANIUM OXIDE-SILICON STRUCTURES
U.S. NTIS, AD-760 009 (May 1973) 178 pp.
i
I
Komblum, Saul S.; Lopez, Benito ;
TITANIUM DIOXIDE LAKES I: PREPARED FROM CERTIFIED WATER-SOLUBLE DYES
AND EMPLOYED IN COLOR-COATING TABLETS
J. Pharmaceutical Sci. 59_ (7): 1016-8 (Jul. 1970) ]
Koshi, Kimiko; Hiryouki, Sakabe
EFFECTS OF ASBESTOS OR QUARTZ PARTICLES ON THE MIXED CULTURES OF i
MACROPHAGE AND 3T6 CELL
Ind. Health (Japan) 10 (3-4): 125-7 (Dec. 1972)
B-10
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Koshi, K.; Kawai, K.; Sakabe, H.
STUDIES ON THE PATHOGENESIS OF SILICOSIS (EFFECT OF SILICA DUSTED ON
THE PHAGOCYTIC CELLS IN VITRO)
Bull. Nat. Inst. Ind. Health (Kawasaki, Japan) _2: 29-39 (1959)
Kosikowski, Frank V.; Brown, David P.
APPLICATION OF TITANIUM DIOXIDE TO WHITEN MOZZARELLA CHEESE
J. Dairy Sci. 52. (7): 96.8-70 (1969)
Kotb, A.R.; Luckey, T.D.
MARKER IN NUTRITION
Nutrition Abstracts and Reviews 42 (3): 813-45 (Jul. 1972)
Kunin, V.Ya.; Polonskii, Yu.A.; Tsikin, A.N.
AGING OF RUTILE CERAMICS
Izvest. Vysshikh Ucheb. Zavedenii, Fiz. No. 2: 85-9 (1960)
Le Bouffant, L.
EFFECT OF THE NATURE OF DUSTS AND THE PULMONARY CHARGE ON CLEARANCE
Inhaled Particles and Vapours III, Proc. Intern. Symp.III., 1970,
227-37 (Pub. 1971)
Le Bouffant, L.
QUANTITATIVE STUDY OF PULMONARY ELIMINATION IN THE RAT. COMPARISON
BETWEEN INERT AND HARMFUL DUSTS
Inhaled Particles and Vapours I, Proc. Intern. Symp. I, 1960, 369-83
(Pub. 1961) (In French)
Leone, Joseph L.
COLLABORATIVE STUDY OF THE QUANTITATIVE DETERMINATION OF TITANIUM
DIOXIDE IN CHEESE
J. Aes. Off. Anal. Chem. 5£ (3): 535-7 (1973)
Lock, Leona M. and Frank, Grace C.
A STUDY OF SOME FACTORS AFFECTING THE PHOTODEGRADATION OF TEXTILE YARNS.
PART II. NYLON 66 AND POLYETHYLENE TEREPHTHALATE YARNS.
Guelph Univ. (Ontario), Dept. of Consumer Studies, AD-772 587 (18 Oct. 1972)
Lomovtseva, S.B.; Savinkova, E.I.; Ellk, E.E.
BINDING PROPERTIES OF GYPSUM OBTAINED FROM WASTE WATERS OF A TITANIUM
DIOXIDE SHOP
Okhr. Prir. Vod. Urala _5: 87-9 (1972) (In Russian)
Lendergan, M.C. and Spengeman, W.F.
MODERN TITANIUM DIOXIDE PIGMENTS
J. Paint Technol 42_ (543): 260-4 (Apr. 1970)
Lorenz, K.; Maga, J.
FUNCTIONAL AND SENSORY PROPERTIES OF TITANIUM DIOXIDE AS A FLOUR AND
BREAD ADDITIVE
Food Prod. Develop. 7^ (5): 93-4, 96, 98 (1973)
Low, David Nicholson
REMOVAL OF SOLID, LIQUID, AND GASEOUS IMPURITIES FROM WASTE GASES
DuPont de Nemours, E.I., and Co., Ger. Offen. 2,222,561 (16 Nov. 1972)
Lukacs, Stefan: Braun-Falco, Otto
BEHAVIOR OF DITHRANOL (CIGNOLIN) IN PASTES AND SOLUTIONS AND A MODIFI-
CATION IN ITS STABILITY BY ADDITION OF SALICYLIC ACID
Hautarzt. 24_ (7): 304-9 (1973)
B-ll
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Lundgren, Karl D.; Swensson, Ake
EXPERIMENTAL INVESTIGATION USING THE METHOD OF MILLER AND SAYERS ON THE
EFFECT UPON ANIMALS OF CEMENTED TUNGSTEN CARBIDES, AND THE POWDERS USED AS
RAW MATERIAL
Acta Med. Scand. 145; 20-7 (1953)
Luttropp, H.
VACUUM-FORMING OF MIXTURES OF POLY(VINYL CHLORIDE) AND MIXED POLYMERS OF
VINYL ACETATE
Plaste u. Kautschuk .5: 87-93 (1958)
Mack, Heinz I
DISTRIBUTION AND RETENTION OF FILLERS IN PAPER i
Papier 13_: 459-69 (1959) ,
Magllevskaya, O.Ya
ACTION OF AEROSOLS OF TITANIUM AND ITS DIOXIDE j
Glglena 1 Sanlt. 21 (3): 20-3 (1956)
i
Makarov, I.A.; Kallnlichuk, E.M.; et al !
PURIFICATION OF WASTE WATERS OF PETROLEUM REFINING PLANTS BY WASTES OF
TITANIUM DIOXIDE PRODUCTION WITH THE REGENERATION OF COAGULANT SLUDGE 1
Neftepererab. Neftekhim.. (Kiev) _7: 56-63 (1972) (In Russian) j
Makarov, V.K. ;
INDUSTRIAL HYGIENE DURING PRODUCTION OF TITANIUM DIOXIDE i
Toksikol. Gig. Prod. Neftekhim. Proizvod., pp. 139-43 (1972)
Manghnanl, Murli H. :
PRESSURE AND TEMPERATURE DEPENDENCE OF THE ELASTIC MODULI OF SODIUM OXIDE- :
TITANIUM DIOXIDE-SILICON DIOXIDE GLASSES
J. Amer. Ceram. Soc. 55 (7): 360-5 (1972)
Mannara, Giuseppe '
TOOTH PASTE ;
Ger. Offen. 2,242,099 (24 May 1973) '
McTaggart, F.K. and Bear, Joy
PHOTOTROPIC EFFECTS IN OXIDES. I. TITANIUM DIOXIDE. ,
J. Appl. Chem. (London) 5_: 643-53 (1955)
Mellish, C.E.; Payne, J.A.
FILTRATION CAPACITY OF ION-EXCHANGE COLUMNS '
Nature 198; 283 (1963) i
i
Merritt, R.R.; Hyde, B.C.; Bursill, L.A.; Philip, O.K.
THERMODYNAMICS OF THE TITANIUM + OXYGEN SYSTEM. ISOTHERMAL GRAVIMETRIC
STUDY OF THE COMPOSITION RANGE TITANIUM PENTOXIDE TO TITANIUM DIOXIDE
AT 13048K
Phil. Trans. Roy. Soc., London, Ser. A. 274 (1245): 627-61 (1973)
Mezentseva, N.V.; Mel'nikova, E.A.; and Mogilevskaya, 0. Ya.
EFFECT ON THE ORGANISM OF RARE, DISPERSED, AND OTHER METALS AND THEIR
COMPOUNDS USED IN INDUSTRY: TITANIUM
Toksikol. Redkikh Metal. 58-71 (1963)
Millar, N.S.C.
COLOR STABILITY OF FRITTED-IN COLORED ENAMELS
Metal Finishing J. 1.: 483-8 (1955)
Minematsu, Yoichi
ACTION OF LIGHT ON POLY(VINYL CHLORIDE). VII. ETHER EXTRACTION OF
PLASTICIZED POLY(VINYL CHLORIDE) FILM AND OUTFLOW OF SOAP STABILIZER.
Nippon Gomu Kyokaishi 32_: 18-20 (1959)
B-12
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Minomura, S. and Drickamer, H.G.
EFFECT OF PRESSURE ON THE ELECTRICAL RESISTANCE OF SOME TRANSITION METAL
OXIDES AND SULFIDES
J. Appl. Phys. 34 (10): 3043-8 (1963)
Mitsui, Takeo; Fukushima, Shoji; and Takada, Susumu
EVALUATION OF POWDER SURFACE PROPERTIES BY AN ADSORPTION METHOD
J. Soc. Cosmet. Chem. 23: 525-31 (17 Aug. 1972)
Mltton, Parker B.; Richards, Dick P.
MODEL FOR OBJECTIVE DEVELOPMENT OF ACCELERATED WEATHERING TESTS
J. Paint Technol. 43_ (563): 107-14 (1971)
Mogilevskaya, O.Ya.
ACTION ON THE ORGANISM OF INDUSTRIAL DUSTS OF MIXED COMPOSITION CONTAINING
RARE AND COMMON METALS AND THEIR COMPOUNDS: INDUSTRIAL ORE CONCENTRATE DUSTS
Toksikol. Redkikh Metal. 209-26 (1963)
Mogilevskaya, O.Ya.
EFFECT ON THE BODY OF ARTIFICIAL DUST MIXTURES (RARE EARTH METAL OXIDES
MIXED WITH SILICON DIOXIDE)
Gigiena i Sanit. 26 (9): 18-23 (1961)
Mogilevskaya, 0. Ya.
ACTION OF RARE METAL ORE DUST ON THE RESPIRATORY ORGANS
Gigiena i Sanit. 25 (4): 30-5 (1960)
Mogilevskaya,.0. Ya.
THE EFFECT OF TITANIUM AND TITANIUM DIOXIDE AEROSOL
Gigiena i Sanit. 21 (3), (1956) (In Russian)
U.S.S.R. Lit. on Air Pollut. & Relat. Occup. Din. £: 191-95 (March 1960)
(English Translation)
Mogilevskaya, 0. Ya.; Mel'nikova, E.A.; and Mezentseva, N.V.
TOXICITY OF TITANIUM AND ITS COMPOUNDS
Tsvetnya Metal. _3JD (4): 51-5 (1956)
Momota, Tsuneo and Matsukura, Yasuo
EFFICIENCY OF SOLAR THERMOELECTRIC GENERATORS COMPOSED OF SEMICONDUCTORS
Trans. Conf. Use Solar Energy, Tucson, 1955 5_: 21-30 (Pub. 1958)
Mueller, Rudolf; Schlemmer, Peter
REDUCTION OF HEALTH-AFFECTING TOBACCO SMOKE COMPONENTS WITH PARTICULAR
REFERENCE TO THE INFLUENCE OF RECONSTITUTED TOBACCO
Ber. Inst. Tabakforsch., Dresden 19: 22-34 (1972) (In German)
Muhler, Joseph C.
ZIRCONIUM SILICATE IN PROPHYLACTIC DENTAL PASTE
U.S. 3,257, 282 (21 June 1966)
Munechika, Kaichi; Tajiri, Hiromi
TITANIUM OXIDE WASTE LIQUOR TREATMENT
Japan. Kokai 7304,397 (19 Jan. 1973)
Murayama, Susumu; Kyogoku, Kazuaki; and Sayama, Yoshikatsu
INSECTICIDAL RESIN COMPOSITIONS CONTAINING DDVP CAPABLE OF BEING
MOLDED AT LOW TEMPERATURES
Jap 72 45,096 (14 Nov. 1972)
B-13
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Nair, K.V.; Narayanamurthy, J.
PROCESS DEVELOPMENT AND PILOT PLANT STUDIES ON THE RECOVERY OF THE WASTE
SULPHURIC ACID FROM A TITANIUM DIOXIDE PLANT
Chem. Age India 21 (2): 102-12 (Feb. 1970)
Naruo, Ota, Shigeki, Yamada, Toshihiko, Shimado, et al
EFFECTIVE TREATMENT OF T102 WASTE ACID
Kogyo Kagaku Zasshi 62:. 346-50 (1959)
Negas, T.; Roth, R.S.; Parker, H.S.; Minor, D.
SUBSOLIDUS PHASE RELATIONS IN THE BaT103-T102 SYSTEM
National Bureau of Standards, Washington, D.C. Final Rept.
Pub. in: J. of Solid State Chem. 9; 297-307 (1974)
NJaa, L.R.
DETERMINATION OF PROTEIN DIGESTIBILITY WITH TITANIUM DIOXIDE AS INDI-
CATOR SUBSTANCE
Acta Agr. Scand. U. (3-4): 227-41 (1961)
Noguchi, Masayasu; Saeki, Masanobu; et al
LIFETIME SPECTRA OF POSITRONS IN TRANSITION-METAL MONOXIDES
J. Phys. Soc. Jap. 32 (5): 1439 (1972)
Novoderezhkin, P.I.
MODIFICATION OF BRIGHTNESS OF SYNTHETIC FIBERS
Izvest. Vysshikh Ucheb. Zavedenii, Tekhnol. Tekstil. Prom. No. 4,
32-8 (1959)
Nuernberg, Eberhard; Rettig, Eberhard; Aye, Rolf D.; et al
SHAPED DRUGS WITH A METALLIC OR PEARLY LUSTER
Merck Patent G.m.b.H., Ger. Offen. 2,045,749 (16 Sept. 1970)
Nugey, Anthony L.
NEUTRALIZING ACID INDUSTRIAL WASTES
U.S. 2,642,334 (16 Jun. 1953)
Nwoko, V.O.; Shreir, L.L.
ELECTRON MICROGRAPHIC EXAMINATION OF ELECTRODEPOSITED DISPERSION-HARDENED
NICKEL
J. Appl. Electrochem. _3 (2): 137-41 (1973)
O'Keeffe, M.; Kibble, T.J.
INTERDIFFUSION AND THE SOLUBILITY LIMITS OF CHROMIUM-(III) OXIDE IN THE
RUTILE PHASE OF TITANIUM DIOXIDE
J. Solid State Chem. 4^ (3): 351-6 (1972)
Onishi, Yoshito
THE CATALYTIC DECOMPOSITION OF NITROUS OXIDE ON TITANIUM DIOXIDE; ANATASE
AND RUTILE
Bull. Chem. Soc. Japan (Tokyo) 4.5. (3) : 922-3 (Mar. 1972)
Orfila, Jeanne; Lepinay, Agnes; Vasseur, Monique et al
EFFECT OF QUARTZ, COAL, TITANIUM OXIDE, AND ASBESTOS DUSTS ON EXPERIMENTAL
CHALAMYDIA PSITTACI INFECTION IN MICE
C.R. Acad. Sci., Ser. D, 274 (9), 1434-7 (1972) (In French)
Orlov, M.A.; Osminkina, V.A.; Shvartsshtein, Ya.V.; Sergeeva, L.A.
RECIRCULATION PROCESS FOR THE COMPLEX CONVERSION OF TITANIUM DIOXIDE
MANUFACTURE WASTES
Tr. Nauch.-Issled. Inst. Udobr. Insektofungits No. 216: 35-42 (1970)
Othmer, D.F.; Nowak, R.
TITANIUM DIOXIDE AND TITANIUM METAL THROUGH CHLORINATION OF ILMENITE
Chem. Eng. Progr. 6£ (6): 113-4 (1973)
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Panush, Sol
METALLIC-NONMETALLIC CONCEPT FOR NEW EFFECT. HIGH CHROMA, DURABLE COLORS.
J. Paint Technol. 45 (581): 39-43 (1973)
Parker, James W.; Peck, Garnet.E.; Banker, Gilbert S.
EFFECTS OF SOLIDS-LOADING ON MOISTURE PERMEABILITY COEFFICIENTS OF FREE
FILMS
J. Phann. Scl. 63 (1): 119-25 (Jan. 1974)
Pelsakhov, I.L.
USE OF SLEEVE FILTERS FOR DUST COLLECTING AT RARE-METAL INDUSTRY PLANTS
Tsvet. Metal. (5): 60-3 (1973) (In Russian)
Peschlera, Lincoln; Freiherr, Frank H.
DISPOSAL OF TITANIUM PIGMENT PROCESS WASTES
J. Water Pollut. Contr. Fed. 40 (1): 127-31 (1968)
Petrova, T.T.; Shutova, A.I.; Aleksandrova, E.M.
EFFECT OF ELECTROLYTES ON THE COLLOIDAL PROPERTIES OF TITANIUM DIOXIDE
PIGMENT PASTES
Colloid. J. (USSR) 31 (5): 592-4 (Sept.-Oct. 1969)
Pings, W.B.
TITANIUM. 2.
Colo. Sch. Mines, Miner. Ind. Bull. JL5. (5): 16 pp. (1972)
Powell, Robert
TITANIUM DIOXIDE AND TITANIUM TETRACHLORIDE
Chemical Process Review No. 18, Noyes Development Corp., Park Ridge, N.J.
(1968) 306 pp.
Predecki, Paul; Aualaender, B.A.; Stephen, J.E.; et al
ATTACHMENT OF BONE TO THREADED IMPLANTS BY INGROWTH AND MECHANICAL
INTERLOCKING
J. Biomed. Mater. Res. .6: 401-12 (1972)
Predecki, Paul; Stephan, J.E.; Auslaender, B.A.; et al
KINETICS OF BONE GROWTH INTO CYLINDRICAL CHANNELS IN ALUMINUM OXIDE
AND TITANIUM
J. Biomed. Mater. Res. 6>: 375-400 (1972)
Preston, Jerome A.
DENTAL STONE COMPOSITIONS
U.S. 3,083,110 (26 Mar. 1963)
Pursglove, J., Jr.
FLY ASH IN 1980
Coal Age 72_ (8): 84-5 (Aug. 1967)
Rackham, J.M.
EASE OF DISPERSION OF TITANIUM DIOXIDE
Pigment Resin Technology 1^ (4) : 7-11 (1972)
Rao, T.V. Subba; Rao, G. Gopala
PHOTODECOLORIZATION AND RANCIDITY OF VEGETABLE OILS. II. PHOTOSENSI-
TIZED DECOLORIZATION OF PEANUT OIL
Grasas y aceites (Seville, Spain) 10; 92-6 (1959)
B-15
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Rechmann, Heinz
TITANIUM AND ITS DAILY TECHNICAL IMPORTANCE
Chem.-Ztg. 97. (6): 320-4 (1973) (In German)
Rice, R.W.
EFFECT OF GRINDING DIRECTION ON THE STRENGTH OF CERAMICS
U.S. National Bureau of Standards, Spec. Publ. No. 348: 365-76 (1972)
Robinson, F.D.; Tear, B.J.
MICROELECTROPHORETIC EXAMINATION OF EMULSION PAINT STABILITY
Chin. Peintures .35 (2): 43-55 (1972)
Robinson, F.D.; Tear, B.J.
MICROELECTROPHORETIC EXAMINATION OF EMULSION PAINT STABILITY
Polym., Paint Colour J. 161 (3816): 390-6 (1972)
Rubin, Alan J.; Haberkost, Donald C.
COAGULATION AND FLOTATION OF COLLOIDAL TITANIUM DIOXIDE
Separ. Sci. S (3): 363-73 (1973)
Rubin, Alan J.
REMOVAL OF SURFACE INACTIVE SUBSTANCES BY FOAM SEPARATION PROCESSES
Ohio State Univ., Columbus. Water Resources Center, Completion Rept.
PB-214-510, 57 pages (Nov. 1972)
Rupprecht, H.; Biedermann, M.
EFFECT OF SURFACE REACTION OF TITANIUM DIOXIDE ON THE UTILIZATION VALUE
OF PHARMACEUTICAL PREPARATIONS. II. BINDING OF INVERT SOAPS ON COLLOI-
DAL TITANIUM DIOXIDE IN THE PRESENCE OF INORGANIC ANIONS AND CATIONS.
Pharm. Ind. 35. (6): 353-6 (1973)
Sakabe, H.; Koshi, K.; Shima, I.; Mastushima, K.
STUDIES ON THE PATHOGENESIS OF SILICOSIS. (EFFECT OF DISSOLVED SILICA
ON THE RESPIRATORY SYSTEM OF CELLS)
Bull. Nat'l Inst. Ind. Health (Kawasaki, Japan) I: 14-25 (1958)
Sarver, James F.
THERMAL-EXPANSION DATA FOR RUTILE-TYPE Ge02
J. Amer. Ceram. Soc. .46.: 195-6 (1963)
Sazonova, I.S.; Keyer, N.P.; Khokhlova, T.P.; Mikhailova, I.L.
ON THE IMPORTANCE OF LOCAL AND COLLECTIVE ELECTRONIC PROPERTIES OF
MODIFIED TI02 IN THE OXIDATION OF CARBON MONOXIDE AND IN THE DECOM-
POSITION OF ISOPROPYL ALCOHOL AND FORMIC ACID
Kinetika I Kataliz 11 (2): 447-54 (1970)
Schaner, B.E.
FABRICATION OF HIGH-DENSITY URANIUM FUEL PLATELETS
Amer. Ceram. Soc. Bull. 38.: 494-8 (1959)
Scheve, J.; Scheve, E.
SEMICONDUCTION AND CATALYSIS. IV. QUANTUM ASPECTS OF CATALYSIS, ELU-
CIDATED THROUGH INVESTIGATIONS ON MIXED OXIDE CATALYSIS
Z. Anorg. Allgem. Chem. 133; 143-53 (1964) (In German)
Schlipkoeter, H.W.; Hilscher, W.; Pott, F.; Beck, Ernst Gerhard
INVESTIGATIONS ON THE ETIOLOGY OF COAL WORKERS' PNEUMOCONIOSIS WITH THE
USE OF POLY(VINYLPYRIDINE N-OXIDE)
Inhaled Particles and Vapours III, Proc. Intern. Symp. III., 1970),
379-90 (Pub. 1971)
Schmitz-Moormann, P.; Hoerlein, H.; Hanefeld, F.
LUNG CHANGES FOLLOWING EXPOSURE TO TITANIUM DIOXIDE DUST
Beitr. Silikose-Forsch. 80: 1-17 (1964)
Sethi, S.; Hilscher, W.; Flasbeck, R.
TISSUE RESPONSE TO A SINGLE INTRAPERITONEAL INJECTION OF VARIOUS SUB-
STANCES IN RATS
Zentralbl. Bakteriol. Parasitenk., Infektionskr. Hyg., Abt. 1: Orig., Reihe B
157 (2-3): 131-44 (1973)
B-16
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Shimizu, Takashi; Hiroshi, Hara; Kooji, Shimada; et al
CATALYTIC OXIDATION OF CARBON MONOXIDE ON SEMICONDUCTIVE BARIUM TITANATE
Kogyo Kagaku Zasshi (J. Chem. Soc. Japan) M. (5): 825-8 (May '1971)
Shultz, J.I.; Bell, R.K.; Rains, T.C.; Menis, 0.
STANDARD REFERENCE MATERIALS: METHODS OF ANALYSIS OF NBS CLAY STANDARDS
National Bureau of Standards, Washington, D.C. Analytical Chemistry Div.
Special Pub. (Final), Rept. No." NBS-SP-260-37, 88 pages '(jiin. 1972)
Shvartsshtein, Ya.V.; Osminkina, V.A.; Orlov, M.A.; et al
PROCESSING OF TITANIUM DIOXIDE-PRODUCTION WASTES WITHOUT RECYCLE
Tf. Nauch.-Issled. Inst. Udobr. Insektofungits No. 216, 43-9 (1970) (In Russian)
Siddle, G.R.
TITANIUM DIOXIDE PIGMENTS
Paint Technol. 35 (9): 6-11 (1971)
Siddle, G.R.
TITANIUM DIOXIDE PIGMENTS. 3. FORMULATING FOR STABILITY. CHLORIDE
TITANIUM DIOXIDE IN EMULSION PAINTS
Paint Technology 35_ (12): 6, 8-9, 11, 13 (1971)
Simensen, Terje; Liseth, Paul ' ,
DISPOSAL OF TITANIUM DIOXIDE WASTE IN A STRATIFIED ESTUARY
Purdue Univ., Eng. Bull., Ext. Ser. No. 129 (Pt. 2): 950-67 (1967)
Sitnikov, I.S.; Skomorokha, V.N.; Zhovanik, P.J.
PURIFICATION OF WASTE WATERS WITH THE EXTRACTION OF COMMERCIAL PIGMENT
IN TITANIUM DIOXIDE PRODUCTION AT THE SUMY CHEMICAL CONCERN
Lakokrasoch. Mater. Ikh Primen. 7£ (5): 80-1 (In Russian)
Slepetys, Richard A.
PARTICLE SIZE DISTRIBUTION OF TITANIUM DIOXIDE PIGMENTS FROM LIGHT SCAT-
TERING MEASUREMENTS ' - '
J. Paint Technol. 44 (568) : 91-6 (1972)
Small, James E.; Jeffries, Sampson F.
TABLET-COATING COMPOSITION ' '
U.S. 3,751,277 (7 Aug. 1973)
Smirnov, E.M.; Ogorodova, N.P.
SELECTION OF SYSTEMS FOR NEUTRALIZING WASTE WATERS FROM TITANIUM DI-
OXIDE PRODUCTION ...
Lakokrasoch. Mater. Ikk Primen. (1);. 73-5 (1973)
Smyth, Harold T.
ROLE OF TRANSVERSE OXYGEN VIBRATIONS IN THERMAL EXPANSION BEHAVIOR OF
GLASSES AND CRYSTALS
Amer. Inst. Phys., Conf. Proc. No. 3, 244-56 (1972)
Soerbye, Oeyvlnd; Kruse, Inger ..
COAGULATION OF CHICKEN BLOOD. VII. USE OF NICKEL OXALATE, BISMUTH .
OXALATE, CADMIUM PHOSPHATE, AND BISMUTH PHOSPHATE FOR DIFFERENTIATION AND
ASSAY OF STRONTIUM CARBONATE NON-ADSORBABLE LABILE FACTORS
Acta Chem. Scand. 16: 1662-74 (1962)
Sperry, P.R.; Mercurio, A.
EXTERIOR DURABILITY OF TIO. PIGMENTED ACRYLIC COATINGS
Amer. Chem. Soc., Div. Crg. Coatings Plast. Chem. JO (1): 400-17 (May 1970)
Toronto, Ont.
Sprague, R.H.; Keller, J.H.
DYE SENSITIZATION OF PHOTOSENSITIVE TITANIUM DIOXIDE
Photogr. Sci. Eng. 14 (6): 401-6 (Nov.-Dec. 1970)
Stadler, Henry L.; Tien, Tseng-Ying; Esper, Michael; Romine, Donald J.
SENSOR FOR THE CONTINUOUS SUPERVISION OF THE AIR-GASOLINE MIXING RATIO
IN INTERNAL COMBUSTION ENGINES
Ger. Offen. 730-524 (24 May 1973)
B-17
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Steig, Fred B.
TITANIUM DIOXIDE, OR IS IT
J. Paint Technol. 43. (561): 36, 43 (1971)
Stleg, F.B.
WEATHERING AND TITANIUM DIOXIDE
J. Paint Technol. 43 (553): 82-9 (Feb. 1971)
Stelger, K.; Beuttner, W.
CRUDE TITANIUM DIOXIDE
Schwelz. Apoth.-Ztg. 94: 85-90 (1956) (In German)
Stoess, H.A., Jr.
HANDLING CHEMICALS IN PULP AND PAPER MILLS
Paper Mill News 28 (4): 64-7 (1955)
Styhr, K.H., Jr.; Beals, M.D.
USE OF TITANIUM DIOXIDE IN SELF-OPACIFYING GLAZES
Amer. Ceram. Soc. Bull. ,37.: 480^5 (1958)
Sukach, S.P.; Antonchuk, Kh.I.; et al
CONDITIONS OF USE OF A COAGULATING AGENT OBTAINED IN THE PRODUCTION OF
TITANIUM DIOXIDE FOR PURIFICATION OF INDUSTRIAL WASTE WATERS
Issled. Obi. Vod. Probl. (1969-1970): 156-8 (Pub. 1973) (In Russian)
Sukach, S.P.; Antonchuk, Zh. I.
FERRIC .SULFATE PRODUCED FROM THE WASTES OF TITANIUM DIOpDE MANUFACTURE
AS A COAGULANT IN WATER TREATMENT
Vodosnabzh., Kanaliz., Gidrotekh. Sooruzh. Mezhvedom. Respub. Nauch.
-Tekh. Sb. 71 (13): 8-12 (1971) (In Russian)
Suleebka, P.; Suleebka, K.P.
COAXIAL CAPACITANCE VOLTAGE DIVIDER FOR OSCILLOSCOPIC RECORDING OF
NANOSECOND HIGH-VOLTAGE PULSES
J. Phys. E. 5. (5): 407-9 (1972)
Suriani, Ernesto
DEIONIZATION OF LIQUID ACID WASTES
French 1,550,213 (20 Dec. 1968)
Swensson, A.
EXPERIMENTAL EVALUATION OF THE FIBROGENETIC POWER OF MINERAL DUSTS
Stud. Laborls Salutls No. 10: 86-97 (1971)
Tavernier, Paul
THERMOCHEMICAL DATA RELATIVE TO THE CONSTITUENTS OF PROPELLANTS
Mem. Poudres 38: 301-36 (1956)
Taylor, H.A.; Tlncher, W.C.; and Hamner, W.F.
PHOTODEGRADATION OF NYLON 66. I. PHOTOTENDERING BY TiO,
J. Appl. Polym. Scl. 14 (1): 141-6 (Jan. 1970)
Trap, I.H.J.L. and Stevels, J.M.
CONVENTIONAL AND INVERT GLASSES CONTAINING TITANIA
Phys. and Chem. Glasses i_: 107-18 (1960)
Tsujlno, Takao
TREATMENTS OF FLUE GAS FROM T102 FIRED FURNACES
Netsu Kanri (Heat Management: Energy and Pollution Control) 24 (6):
34-8 (June 1972) ~~
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Van Der Smissen, Carl Ernst
LOADING CAPACITY OF AEROSOL FILTERS FOR RESPIRATORS
Staub, Reinhaltung Luft 31 (9): 1-5 (Eng. trans, of Staub. 31 (9):
355-9 (1971)
Veber, A.
ATMOSPHERIC POLLUTION AS A FACTOR IN THE AGING OF ELASTOMERS
Comparee (Paris) 67_ (784): 21-4 (Jan. 1967)
Vcnkatu, D.A.
ANALYSIS OF SINTERING EQUATIONS PERTAINING TO CONSTANT RATES OF HEATING
Mater. Sci. Eng. J5 (6): 339-40 (1971)
Vergnon, P.; Astler, M.; Telchner, S.J.
SINTERING OF SUBMICRONIC PARTICLES OF METALLIC OXIDES
Mater. Sci. Res. 6: 301-10 (1972)
Veroeven, Wilbur M.
CASTABLE ELASTOMERS AND PLASTICS FOR WEAPON SYSTEM COMPONENTS
U.S. NTIS, AD-731 187, (1971) 18 pp. :
Viens, G.E.; Campbell, R.A.; and Rogers, R.R.
EXPERIMENTAL ELECTRIC SMELTING OF ILMENITA TO PRODUCE HIGH-TITANIA
SLAG AND PIG IRON '
Trans. Can. Inst. Mining Met. 60 (543): 405-10 (1957)
Von Maessenhausen, Walter H.
TREATMENT OF WASTE WATERS FROM MANUFACTURE OF TITANIUM DIOXIDE PIGMENTS
Ger. Offen. 2,124,593 (Dec. 1972)
Waitkins, George R.; De Luca, Carmine V.; Miller, Harold A.; and
Wilcox, Forrest S.
TITANIUM DIOXIDE-MOTHER-OF-PEARL COSMETIC PIGMENT
Ger. Offen. 2,337,094 (31 Jan. 1974)
Warner, George S.
WHAT AN INDUSTRY CAN DO IN CONTROLLING WASTES
Proc. Ann. Conf., Maryland-Delaware Water and Sewage Assoc. 33; 10-5 (I960)
Weber, H.H.
MEASURES AGAINST WATER POLLUTION IN INDUSTRIES PRODUCING BASIC INORGANIC
CHEMICALS INCLUDING FERTILIZERS
Pure & Applied Chemistry ^9_ (1-3) : 67-73 (1972)
White, Harry J. ,
RESISTIVITY PROBLEMS IN ELECTROSTATIC PRECIPITATION
JAPCA 24 (4): 314-38 (Apr. 1974)
Wilder, David R. and Dodd, C.M.
SOME EFFECTS OF TITANIA ON REFRACTORY CLAYS
J. Amer. Ceram. Soc. JI6: 400-3 (1953)
Wilks, P.H.; Thorpe, M.L.
PLASMA TORCHES IN INDUSTRIAL CHEMISTRY
Chem. Technol. 31-7 (Jan. 1972)
Williams, Philip C.
THE USE OF TITANIUM DIOXIDE AS A CATALYST FOR LARGE-SCALE KJELDAHL
DETERMINATION OF THE TOTAL NITROGEN CONTENT OF CEREAL GRAINS
J. Sci. Food Agric. U (3): 343-8 (1973)
Wood, G.C.; Hodgkiess, T.
HARDNESS OF OXIDES AT AMBIENT TEMPERATURES
Werkst. Korros. 23 (9): 766-73 (1972)
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Williams, Philip C.
THE USE OF TITANIUM DIOXIDE AS A CATALYST:FOR LARGE-SCALE KJELDAHL
DETERMINATION OF THE TOTAL NITROGEN CONTENT OF CEREAL GRAINS
J. Sci. Food Agric. 24 (3): 343-48 (1973)
Wood, G.C.; Hodgkieas, T.
HARDNESS OF OXIDES AT AMBIENT TEMPERATURES
Werkst. Korros. 23. (9): 766-73 (1972)
Yee, Tin Boo and Andrews, A.I.
RELATION OF VISCOSITY, NUCLEI FORMATION, AND CRYSTAL GROWTH IN TITANIA-
OPACIFIED ENAMEL
J. Amer. Ceram. Soc. 3£: 188-95 (1956)
Yoshida, Koji and Kawamura, Takao
TITANIUM OXIDE RECTIFIER
Bull. Univ. Osaka Prefect. Ser. A. 6: 75-84 (1958)
Young, G.J. and Chessick, J.J.
THE FORMATION AND STABILITY ON NONSOAP LUBRICATING GREASES. I. FACTORS
RESPONSIBLE FOR GEL FORMATION
J. Colloid Sci. 13: 358-71 (1958)
Zajusz, Kazimiers; Paradowski, Zbigniew; Dudziak, Zenon
HEMOLYTIC ACTIVITY OF SILICA AND..OTHER DUSTS
Med. Pr. 19 (1): 26-31 (1968) (in Polish) .'
Zeronian, S.H.; Tomioka, M.K.; and Pangborn, J.
SURFACE DAMAGE OF DELUSTERED NYLON 66 FIBERS EXPOSED TO LIGHT
Proc. Electron Microsc. Soc. Amer. 31.: 58-9 (1973)
Zorin, L.L. and Babashkina, T.I.
RECOVERY OF TITANIUM DIOXIDE FROM FLUE GASES WITH METAL CERAMIC FILTERS
Lakokroasochn Mater. Ikh Primenen. 4^ 82-4 (1971)
Zurlo, Nicola
SCARLINO CASE. WASTES FROM TITANIUM DIOXIDE PRODUCTION
Ecologia 2_ (4) : 21-5 (1972) (In Italian)
ANONYMOUS PUBLICATIONS
AMERICAN CYANAMID HAS RAISED TITANIUM DIOXIDE TABS, EFFECTIVE APRIL 16
Chem. Wk. 112 (13): 27 (28 Mar. 1973)
ARTIFICIAL TEETH COMPOSITION
Neth. 302,657 (25 Oct. 1965)
BIG SUCCESS NO SURPRISE FOR POLKADOTS
Chem. Wk. 115 (15): 45-6 (9 Oct. 1974)
COATING OBJECTS WITH LIGHT-ABSORBING TRANSPARENT OR TRANSLUCENT COLOR
LAYERS
Brit. 962,868 (8 July 1964)
COLOR ADDITIVES: MISCELLANEOUS AMENDMENTS
Fed. Reg. .33: 8812-6 (18 June 1968)
CORSICA ERUPTS OVER MONTEDISON'S POLLUTION OF MEDITERRANEAN
Marine Pollution Bulletin .4 (3): 40 (1973)
CPI GIVES SURGEONS NEW TOOLS
Chem. Wk. 115 (22): 41 (27 Nov. 1974)
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DU PONT IS LOOKING FOR A TITANIUM DIOXIDE PLANT SITE IN EUROPE
Chem. Wk. 112 (9): 23 (28 Feb. 1973)
DU PONT TO BUILD T102 PLANT ON GULF COAST SITE IN MISSISSIPPI
J. Paint Technol. 46 (596): 117 (Sept. 1974)
ELECTROPHOTOGRAPHIC-CHEMICAL REACTION SYSTEM FOR MULTIPLE IMAGES
Neth. 6,504,797 (18 Oct. 1965)
EXCIPIENT FOR FLUORINATED TOOTHPASTES
Belg. 651,124 (13 Nov. 1964)
FOOD ADDITIVES. CELLOPHANE
Fed. Reg. Z]_: 11640 (27 Nov. 1962)
HE KNOWS WHEN TO LET OTHERS CARRY THE BALL
Chem. Wk. 115 (16): 52 (16 Oct. 1974)
HYGIENIC GUIDE SERIES. TITANIUM
Amer. Ind. Hyg. Assoc. J. .34 (6): 275-7 (June 1973)
INDIAN STANDARDS
Chem. Age India 20 (6): 547 (6 June 1969)
INTERNATIONAL NOTES
C&EN 51 (23): 7 (4 June 1973)
KRONOS GUIDE — FUNDAMENTALS AND USE OF KRONOS TITANIUM DIOXIDE
Translation from German by D.G. Cole
Kronos Titanium Companies, Western Germany (1968)
MATERIAL SUPPLIES FOR COATINGS LESS SCARCE
C&EN 52 (40): 9 (7 Oct. 1974)
MEAT INSPECTION REGULATIONS
Fed. Reg. 30: 8673-4 (9 July 1965)
MOLDING POLYURETHANE GOLF BALL COVERS
Brit. 968,987 (9 Sept. 1964)
MONTEDISON'S CAMPAIGN TO SELL TO COMMUNIST COUNTRIES
C&EN .51 (31): 4 (30 July 1973)
NYLON YARN
Neth. 6,514,993 (20 May 1966)
PIGMENT BIND WILL NOT END SOON
Chem. Wk. USX(7): 24, 29 (14 Aug. 1974)
/"
REQUIREMENT TO USE TITANIUM DIOXIDE IN ISOLATED SOY PROTEIN
Fed. Reg. ^5 (75): 6255 (17 Apr. 1970)
SHERWIN-WILLIAMS WILL SELL ITS TITANIUM DIOXIDE BUSINESS TO SCM CORPORATION
C&EN 52 (40): 6 (7 Oct. 1974)
Ti02 AND A POSSIBLE GUIDE TO PAST OCEANIC SPREADING RATES
Nature 246 (5434): 468-70 (21/28 Dec. 1973)
TOXICOLOGY OF TITANIUM DIOXIDE, THE
\ Food and Cosmet. Toxic. J.: 95-6 (1963)
1
U.S. CHEMICAL INDUSTRY - THE PRODUCTS IT MAKES
C&EN 51 (23): 12-3 (4 June 1973)
WE'RE SPENDING $17,000,000 TO PROVE WE MEAN WHAT WE SAY
J. Paint Technol. 46 (596): 38 (Sept. 1974)
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