J£J 8771

Bureau of Mines Information Circular/1978

Iron Oxide Pigments

(In Two Parts)

1. Fine-Particle Iron Oxides for Pigment,

Electronic, and Chemical Use

I UNITED STATES DEPARTMENT OF THE INTERIOR

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Information Circular 8771

Iron Oxide Pigments

(In Two Parts)

1. Fine-Particle Iron Oxides for Pigment,

Electronic, and Chemical Use

By Thomas S. Jones

UNITED STATES DEPARTMENT OF THE INTERIOR

Cecil D. Andrus, Secretary

BUREAU OF MINES
 As the Nation's principal conservation agency, the Department of the Interior
has responsibility for most of our nationally owned public lands and natural
resources. This includes fostering the wisest use of our land and water re-
sources, protecting our fish and wildlife, preserving the environmental and
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the enjoyment of life through outdoor recreation. The Department assesses
our energy and mineral resources and works to assure that their development is

in the best interests of all our people. The Department also has a major re-
sponsibility for American Indian reservation communities and for people who
live in Island Territories under U.S. administration.

lid

This publication has been cataloged as follows:

Jones, Thomas S
Iron oxide pigments (in two parts). 1. Fine-particle iron
oxides for pigment, electronic, and chemical use /by Thomas
S. Jones. [Washington] : U.S. Dept. of the Interior, Bureau
of Mines, 1978.

58 p. ; 27 cm. (Information circular - Bureau of Mines ; 8771)

Bibliography: p. 49*55"
1. Iron oxides. I„ United States. Bureau of Mines. II. Title.
III. Series: United States. Bureau of Mines. Information circular -

Bureau of Mines ; 8771.

TN23.U71 no. 8771 622.06173

U.S. Dept. of the Int. Library

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 CONTENTS
Page

Abstract 1
Introduction and background 1
Types and chemical forms of iron oxide pigments 2
Terminology 4
Specifications 5
Manufacture 6
Production of natural iron oxide pigments 7
Mines and mining methods 7
Size reduction 10
Production of synthetic iron oxide pigments 11
Thermal decomposition (dry process) 11
Solution methods (wet process) 12
Regenerator oxide 15
Aniline process 17
Operational factors in iron oxide production 17
Relationships between iron oxide producers and other materials
industries 18
End uses 21
Physical and chemical characteristics of iron oxide pigments 21
Chemical and physical stability 22
Particle size 22
Particle shape 22
Uses and applications 23
Paint 23
Building materials, drugs, and cosmetics 25
Ferrites 25
Catalysts gas absorption, and foundry sands
,
26
Transparent oxides 27
Magnetic recording 27
Copy machines and wastewater treatment 28
Micaceous iron oxide. 28
Iron oxides in relation to other pigments 28
Trends in production and foreign trade for the United States 30
Domestic shipments 30
Overall (natural versus synthetic oxides) 30
Individual oxides 36
Foreign trade 39
Imports of natural oxides 41
Imports of synthetic oxides 42
Apparent domes tic demand 45
Present and future s tatus of the industry , 47
References 49
Bureau of Mines publications on iron oxides 55
Appendix A. --Selected list of U.S. patents for wet -process manufacture of
synthetic iron oxide pigments 56
Appendix B. --Manufacture of synthetic iron oxide by the aniline process. 57
ii

ILLUSTRATIONS
Page

1. Relationships between oxides, oxyhydroxides , and hydroxides of iron 3

2. Open-air stockpiles of crude ocher 9
3. Settling tanks and mill for processing crude ocher 9
4. Cross section of Raymond ring -roller mill „ 10
5. Tank for storage of synthetic yellow iron oxide 14
6. Twin-tower hydrochloric acid pickling line with acid -reclaiming
unit. 16
7. Wastewater treatment facilities at pigment plant 19
8. Relationships between iron oxide producers and other materials
indus tries „ 20
9. Flow chart of ferrite preparation methods 26
10. Iron oxides in relation to the overall pigment industry 29
11. Quantity of domestic shipments of finished iron oxide pigments,
1955-76, by type 33
12. Value of domestic shipments of finished iron oxide pigments,
1955-76, by type 33
13. Average unit value of domestic shipments of finished iron oxide
pigments, 1955-76, historical basis 34
14. Average unit value of domestic shipments of finished iron oxide
pigments, 1955-76, constant -dollar basis 34
15. Price trends for synthetic yellow iron oxide, 1955-76 36
16. Quantity of domestic shipments of finished natural iron oxide pig-
ments, 1955-76, by kind 38
17. Quantity of domestic shipments of synthetic iron oxide pigments,
1955-76, by kind 38
18. U.S. foreign trade in iron oxide pigments, 1955-76 39
19. Imports of natural iron oxides, 1955-76 41
20. Quantity of imports of synthetic iron oxides, 1964-76, by chief
sources » 44
21. Value of imports of synthetic iron oxides, 1964-76, by chief
sources . 44
22. Apparent domestic demand for finished iron oxide pigments, 1964-76,
by quantity 46
23. Apparent domestic demand for finished iron oxide pigments, 1964-76,
by value 46

TABLES
1. Specifications pertaining to iron oxides 6
2 Uses of iron oxide pigments 24
3. U.S. producers of iron oxide pigments in 1976 31
4. Domestic shipments of finished iron oxide pigments, 1955-76, by
type 32
5. Price of synthetic yellow iron oxide, medium shade, 1955-76 35
6. Quantity of domestic shipments of finished iron oxide pigments,
1955 -76, by kind 37
7. U.S. foreign trade in iron oxide pigments, 1955-76 40
8. Tariff classifications for imports of iron oxide pigments 42
9. U.S. imports of synthetic iron oxides, 1964-76 43
10. Apparent domestic demand for finished iron oxide pigments, 1964-76. 45
 .

IRON OXIDE PIGMENTS

(In Two Parts)

1. Fine-Particle Iron Oxides for Pigment, Electronic, and Chemical Use

by

Thomas S. Jones 1

ABSTRACT

This Bureau of Mirues publication reviews characteristics, manufacture,

and uses of natural and synthetic iron oxide pigments. Supply and demand
trends within the domestic industry and in foreign trade are presented for
1955 through 1976. Iron oxides are expected to continue in demand for tradi-
tional uses, and if anything, to be favorably affected by technological
developments. Imports have been significant in relation to domestic produc-
tion, most notably for synthetic oxides from West Germany and Canada.

INTRODUCTION AND BACKGROUND

Man's use of mineral earths containing iron for coloring purposes pre-
dates written records. Mining of hematite for use as a pigment was carried
out in Swaziland in South Africa over 40,000 years ago (44) a Caves at Les
Eyzies in south -central France contain 20, 000 -year- old paintings by prehis-
toric man who used earth materials to make red, yellow, and black colors (35).
In the United States, Indians of the Southwest used ochers and similar pig"
ments beginning in ancient times (70) Until the late 19th century iron oxide
.

pigments were obtained wholly from natural materials, generally with little
alteration other than physical purification. In some cases roasting or calci-
nation was also carried out. However, beginning in the first part of the
20th century, chemical methods were developed for synthetic production of com-
mercial iron oxides. Synthetic production offered improved uniformity as well
as characteristics not obtainable with natural oxides, and consequently syn-
thetics displaced natural materials for many applications. Today the iron
oxide pigment industry produces a mix of synthetic oxides prepared to a range
of specifications plus a number of specific natural oxides still desired
because of lower cost or uniqueness of color.

This Bureau of Mines publication treats iron oxide pigments as a commod-

ity within the U.S. economy. The various pigments, methods of manufacture,

Physical scientist, Division of Ferrous Metals, Bureau of Mines, Washington,

D.C.
3 Underlined numbers in parentheses refer to items in the list of references
preceding the appendixes.
and uses are described, but not in great detail. Further technical informa-
tion is available from references cited in the text. Statistics pertinent to
the domestic industry over the interval from 1955 through 1976 are presented
and reviewed. The discussion essentially reflects industry status and outlook
as of the end of 1976. Part 2 of this study will cover the location of natu-
ral iron oxide pigment deposits worldwide, together with some geologic and
economic features. Therefore, these subjects are mentioned only briefly in
part 1.

The iron oxide industry is mature, with products matched to end uses
according to chemical and physical characteristics, outstanding among which
are stability and nontoxicity. Because of low cost and availability, iron
oxides constitute one of the most important groups of colored inorganic pig-
ments. Synthetic pigments, frequently produced from wastes or as a byproduct
of other industries, are now the more important portion of the iron oxide
industry.

Types and Chemical Forms of Iron Oxide Pigments

Development of color in iron oxides stems from the electronic structure

of the iron atom, which has the ability to exist in more than one valence
state. Valence states encountered in pigments are the divalent (ferrous ion)
and the trivalent (ferric ion). The trivalent state is more common and is
found in Fe s 3 , hematite, which is red, and in hydrated ferric oxide,
Fe 2 3 -H2 0, limonite or goethite, which is yellow. The divalent state occurs
along with the trivalent state in the magnetic oxide, magnetite, Fe 3 4 also
,

written as FeO-Fe 2 3 , which is black. Thus, iron oxides provide colors rang-
ing from yellow to red to black, as well as intermediate shades and browns
depending on method of preparation and impurities. Iron oxides do not give
blue or green colors, but pigments with these colors can be produced using
other iron -containing chemicals, as in iron blue, ferric ammonium ferrocyanide.

Oxides and hydrous oxides of iron occur or can be made in a variety of

forms and physical conditions, and this has resulted in the existence of a num-
ber of names for the various compounds, some with only poorly defined chemical
nature. However, for pigment purposes it is necessary to consider only five
of these compounds: Two forms of ferric oxide, two forms of ferric oxide
hydrate, and magnetite. The stable form of ferric oxide, hematite, designated
a-Fe 2 3 , alpha iron oxide, has a rhombohedral structure, is nonmagnetic, and
is the basis compound of red iron oxides. A metastable form of ferric oxide,
denoted Y _ F e 20 3 , gamma iron oxide, is a defect spinel which has the magnetic
property known as ferrimagnetism. Gamma iron oxide is important mainly for
application of its magnetic imaging characteristics in magnetic recording.
Heating gamma iron oxide to about 600° C causes permanent transformation to
stable alpha iron oxide. Goethite, commonly also called limonite, has the
formula o--Fe00H and is the basis compound of both natural (ochers, siennas,
and umbers) and synthetic yellow iron oxides. Ferric oxide monohydrate also
occurs in nature, or can be formed chemically, as y-F e 00H, which is known as
lepidocrocite. Its greatest significance is that it can be formed as an inter-
mediate in the preparation of magnetic gamma iron oxide. Magnetite, Fe 3 4 ,
has inverse spinel structure and, like gamma iron oxide, is ferrimagnetic.
However, to date it has not been as important in magnetic recording applica-
tions and is a relatively minor pigment. Both of the ferric oxide hydrates
and magnetite can be changed into hematite by heating; calcination of yellow
a -FeOOH is one of the main ways of producing synthetic red iron oxide.

The technical literature contains descriptions of the various oxides,

oxyhydroxides and hydroxides of iron, the relationships between them (J_) and
, ,

the way these relationships can be used in the production of synthetic pig-
ments (31 ) A schematic diagram of these relationships for the compounds of
.

main interest to iron oxide pigments is given in figure 1 (68 ) The compounds .

in this diagram can be classified in terms of two series, the alpha series for
or -FeOOH and a-Ye^0 3 and the gamma series for Y-Fp°°H and Y-Fe s 3 The stabil- .

ity of the compounds relative to one another, and the variety of ways in which
a-Fe 2 3 hematite, can be produced are indicated in the diagram. Also s^ ->wn
,

is the possibility of forming pigments beginning with either a ferrous or a

ferric salt. This type of diagram is mainly of interest in the preparation of
synthetic oxides, but it also helps in visualizing the natural processes
involved during formation of pigment ores.

Fe

Normal
Oxidizes rusting
while
washing -FeOOH
FeCI 2 + NH 4 OH Fe(OH) 2 ? -FeOOH -
o»

H. (goethite)
(
lepidocrocite)

Kept under
water

FeCI 3 + NH 4 OH Fe(OH) 3 Heat d -Fe20 3

hematite)
(gel or sol)

IS -Fe20 3
(maghemite

FIGURE 1. - Relationships between oxides, oxyhydroxides, and hydroxides of iron (68, p. 545).
 Terminology

Terminology for iron oxide pigments can be kept simple, on the basis of
color, except that a few of the natural colors have names that mostly reflect
the places where they were initially obtained. Thus, for synthetic oxides, it
suffices to speak of black, brown, red, and yellow pigments. Several types of
the synthetic pigments can be distinguished according to method of manufacture.
In its tabulations, the Bureau of Mines has differentiated synthetic reds into
copperas red, red manufactured by other chemical processes, and other manu-
factured red iron oxides. Copperas red is oxide produced by calcination of
the iron sulfate chemical known as copperas, "red manufactured by other chemi-
cal processes" refers to oxide prepared by calcination of precipitated oxide
(usually yellow), and "other manufactured red iron oxides" signifies red
obtained by direct precipitation.

For natural oxides, a variety of names has been assigned to materials

coming from particular sources. A still -prominent example is Spanish red,
which as the name implies is a natural red of particular characteristics com-
ing from Spain. Many of the other natural oxides having special names are no
longer produced or are of only occasional significance. Therefore, the follow-
ing terms are adequate to describe modern natural oxide products: Black
(magnetite) brown (includes the variety known as metallic brown) , Vandyke
,

brown, red, ocher, sienna, and umber. Metallic brown is an oxide obtained by
the calcination of siderite, iron carbonate. Vandyke brown is a carbonaceous
material containing only a minor amount of iron; it is included here because
of tradition and not because it can be clearly identified as an iron oxide
pigment.

Ocher, sienna, and umber can be thought of as a group of yellow to brown

pigments which more or less grade into each other on the basis of both chemi-
cal composition and color. The terms "ocher" and "sienna" appear to have been
used to describe similar material of both domestic and foreign origin. Use of
the term "umber" is more specific because of the manganese content and
greenish -brown natural shade of this pigment. In the natural state, the iron
coloring agent in all three of these pigments is hydrated ferric oxide, limo-
nite, which tends to give a yellow to brown color. Heating a limonitic mate-
rial sufficiently will produce a color change as water of hydration is driven
off and limonite is converted to hematite (red). Therefore, drying these
natural ores must be controlled, usually to temperatures below 115° C, if
color change is to be prevented. On the other hand, ores can be calcined
deliberately to produce darker shades. Ocher is prized for its natural yel-
low color and is not heated other than for drying. However, the option of
calcining results in there being two main types of both sienna and umber. The
term "raw" is used to designate material that has not been heated other than
for drying, and the term "burnt" signifies material that has been calcined to
produce a color change.
 As stated, the dividing line between ocher and sienna is not sharp.
General practice is to associate "ocher" with the lighter shades of ores,
which are also lower in iron; siennas are usually darker and higher in iron.
Siennas may also contain some manganese, because of their tendency to be
associated with umber deposits. To illustrate, the iron oxide content (Fe a 3 )
in a selection of pigments supplied domestically in 1970 was 20% to 57% for
ocher, 35% to 73% for raw sienna, and 23% to 58% for raw umber; the manganese
oxide (Mn02 ) in raw umber ranged from 6% to 25% (J7, p. 325).

Micaceous iron oxide is another natural form of iron oxide used as a

pigment (66). As suggested by the name, this material is a flaky hematite
whose platelike nature is physically similar to that of mica. Chemical
similarity does not exist, and micaceous iron oxide does not contain mica.
The particle form in micaceous iron oxide appears to give exceptional resist-
ance to weathering. This oxide therefore finds use in coatings for surface
protection, and it has been so employed outside the United States for many
years, as in painting of the Eiffel Tower in Paris. However, the predominant
use of domestic deposits of micaceous iron oxide in the United States has been
as ore for iron and steel production, and little, if any, has been used in
pigments.

Specifications

Specifications for iron oxide pigments have been developed by the Federal
Government. Table 1 lists the Federal specification numbers along with those
of the American Society for Testing and Materials (ASTM) (2). The few mili-
tary specifications indicated by the table are for iron oxides which in some
cases are too coarse to be considered as pigments. The U.S. statistical
number (Standard Industrial Classification or SIC No.) encompassing mining
of crude iron oxide is 1479, while that encompassing manufacture of synthetic
oxide is 2816 (21).
 TABLE 1 . - Specifications pertaining to iron oxides

Specification Date1 Title

No.
FEDERAL SPECIFICATIONS, GENERAL SERVICES ADMINISTRATION
TT-P-31D. . 7-6-73 Paint, Oil: Iron -Oxide, Ready -Mixed, Red and Brown
TT-P-57b.. 1-23-63; Paint, Zinc Yellow-Iron Oxide-Base, Ready-Mixed.
A 2-26-74
TT-P-86G. 3-19-74 Paint, Red -Lead -Base, Ready -Mixed.
TT-P-375.. 4-11-57 Pigment, Indian Red and Bright Red, Dry.
TT-P-381E. 10-13-70; Pigments -in -Oil, Tinting Color.
A 11-6-72
TT-P-390. , 12-15-58; Pigment, Iron Oxide; Black, Synthetic, Dry.
A 3-13-63
TT-P-395.. 1-15-58 Pigment, Iron Oxide; Brown, Synthetic, Dry.
TT-P-405.. 1-14-59 Pigment, Metallic -Brown, Dry.
TT-P-408.. 3-9-60 Pigment: Mineral -Red Natural: Dry.
TT-P-420a. 9-11-61 Pigment, Ocher; Yellow, Dry.
TT-P-435b. 2-6-68 Pigment, Sienna, Raw and Burnt, Dry.
TT-P-455.. 12-30-58 Pigment, Umber, Raw and Burnt, Dry.
TT-P-457.. 11-27-59 Pigment, Venetian -Red, Dry.
TT-P-458a, 1-11-62 Pigment, Yellow-Iron Oxide; Hydrated, Synthetic,

STANDARD SPECIFICATIONS, ASTM

1974 Red and Brown Iron Oxide Pigments.
1975 Ocher.
D763-48 1974 Raw and Burnt Umber.
1974 Raw and Burnt Sienna.
D767-65 3 1970 Venetian Red.
D768-47 1974 Yellow Iron Oxide Hydrated.
1974 Black Synthetic Iron Oxide.
MILITARY SPECIFICATIONS, DEFENSE SUPPLY AGENCY
MIL-I-275B. 5-6-69 Iron Oxide, Black, Technical.
MIL-I-706A. 8-23-62; Iron Oxide; Ferric, Red Dry (Natural and Synthetic)
A 9-20-68
1 A denotes amended; date of amendment follows,

discontinued in 1977.

MANUFACTURE

The term "pigment" usually carries with it the meaning that the particles
giving color are small enough that they cannot be detected individually. This
means that one of the objectives in pigment manufacturing is to produce mate-
rials with fine particle size. A convenient unit to use in measuring size of
pigment particles is the micrometer, which equals 10" 3 mm. In a modern pig-
ment, a particle with a dimension of 25 micrometers (about 1/1,000 inch) would
be relatively large. Some natural iron oxide pigments have average particle
sizes as great as 25 micrometers; synthetic oxides are much finer, most
particles being no larger than 1 micrometer and many particles being smaller.
These small sizes mean that only for natural oxides is there appreciable reten-
tion on a 325 -mesh sieve screen as used in powder work, inasmuch as the
openings for this screen will pass particles with diameters of less than
44 micrometers. Thus, manufacturers of synthetic oxide typically characterize
the size distribution of their product as "99.97 -325 mesh."

Accordingly, the task before a pigment manufacturer is either to appro-

priately reduce the particle size of starting materials that are too coarse
or to manufacture oxides having particle sizes that are fine enough to begin
with. As a rule, size reduction is necessary only for natural oxides, because
the processes used to manufacture synthetic oxides yield sufficiently fine
particles. The need to achieve small sizes leads to the differentiation of
pigment material into "crude" and "finished." Crude pigment is natural ore
which has been dug from the ground like other kinds of ore, but needs to be
further treated prior to final use, as in a paint. Washing alone does not
produce a finished pigment, but grinding will. Along with size reduction,
drying and/or calcining may be required. Finished pigments of iron oxide are
part of a larger pigment class termed "dry colors."

In the iron oxide pigment industry it is rare to find a completely inte-

grated company, in the sense that a single company begins with its own feed-
stock (natural ore or chemical raw materials) and eventually produces a
manufactured good such as paint or a ferrite body. More typically, companies
producing natural oxide will confine themselves to mining and selling crude
ore, to mining ore and processing it into finished pigments to be sold, to
buying ore and processing it into finished pigments, or to buying and process-
ing ore plus making paint to be sold. Similarly, a typical company producing
synthetic oxide mainly manufactures pigment. Such a manufacturer frequently
blends finished pigments of various kinds with other materials to produce multi-
component pigments meeting certain specifications . A pigment producer may
also make and sell dispersions, which are pigmented liquid vehicles whose form
may be convenient for paint manufacturing. Some firms in the pigment industry
simply buy finished pigments and do blending or dispersing, or perhaps both.

This review is concerned with the methods and materials used in producing
crude and finished iron oxide pigments and with the manufacturers who produce
such products. Blending is considered only within the context of pigment
manufacture. Dispersion and other operations and manufacturing carried out
using finished pigments are not discussed in any detail.

Production of Natural Iron Oxide Pigments

Mines and Mining Methods

Two classes of mines can be distinguished as sources of crude ore for

pigment production, "iron ore mines" and "pigment mines." Iron ore mines are
mines operated primarily to produce ore for smelting in the blast furnace. A
small amount of the production of these mines may be given additional benefi-
ciation to produce pigment raw material. Although the amount additionally
beneficiated is small in comparison to total mine output, this amount con-
stitutes the majority of U.S. crude ore production for pigments. Most of the
crude obtained as a coproduct of iron ore mining is red oxide, hematite.
Pigment mines are mines operated solely to produce crude for pigment
production; the character of this ore makes it unsuitable, or at best
uneconomic, for iron smelting. Production from pigment mines has tended to
be a relatively stable but lesser part of overall crude pigment production.

The most notable features of crude pigment mining are that mining is
underground in the case of ore produced from iron ore mines and is very
selective, even to the use of pick -and -shovel methods in pigment mines.
Pigment -grade crude ore is presently produced as an adjunct to iron ore mining
at two of the six underground iron ore mines in the United States. An earthy
hematite is produced at one of these mines; most of it is pelletized, but some
is processed as direct -shipping ore. About 1.57o of total production is
shipped directly from the mine for pigment purposes ( 60)
. Mining of this ore
is by block caving, and the ore is crushed and screened before being brought
to the surface. Until December 1977 magnetite ore was obtained at another
underground mine by a combination of sublevel stoping, pillar recovery, and
sublevel caving (20). The ore was crushed, first underground and then addi-
tionally on the surface, after which magnetic separation and flotation were
used to produce a concentrate. Most of the output was pelletized for smelting,
but a small amount was specially concentrated into a 71.5% iron-content prod-
uct sold for pigment-type applications (19).

In contrast to massive hematite and magnetite deposits, where the supply

of material usable for pigments far exceeds demand and where mass production
methods are used to obtain blast furnace feed, deposits of yellow and brown
ores suitable for pigments occur in spotty fashion and are mined on a much
smaller scale. Underground mining for ocher, sienna, and umber has been
practiced in the past, but operations at the two remaining mines are open pit.
Depending on the deposits being worked, mining is either by hand or by front-
end loader. At one location, a multiple -bench method is employed. Mined
material is stockpiled by grade (in the open by one producer as shown in fig-
ure 2) and then consumed at the milling plant in accordance with demand.

Ocher is still beneficiated by methods much like those described in

detail years ago ( 57) . Ore dumped at the top of an incline is disintegrated
into a slurry by a water spray. The slurry flows down into a log washer for
removal of coarse sand and rock particles. Further removal of clay and sand
particles occurs as the slurry passes successively through a separator tank
and a Dorr bowl rake, shown in an overall view of the plant in figure 3. The
ocher leaving the rake as an overflow goes to a settling tank, from which it
is withdrawn at a controlled solids content. The slurry is dried by being
spattered by an agitator onto a slowly rotating steam-heated drum; the speed
of the drum is regulated so that drying is complete in less than one drum
revolution. Product is removed by a knife edge located on the side of the
drum opposite that where fresh slurry is being added.
FIGURE 2. - Open-air stockpiles of crude ocheri (Courtesy, New Riverside Ocher Co.)

FIGURE 3. - Settling tanks and mill for processing crude ocher.

(Courtesy, New Riverside Ocher Co.)
10

Size Reduction

Size reduction of natural iron oxide pigments involves pulverizing and

classifying to eliminate agglomerates rather than shattering and crushing to
small average particle sizes. Lump ore may be crushed in a hammer mill. As
desired or necessary, the resulting powder can be dried or calcined, generally
in a rotary kiln. Steam heat can be used to dry ocher, sienna, and umber
without producing dehydration and color change; higher temperature calcining
yields burnt sienna and burnt umber but is not applied to ocher.

The several kinds of grinding units in use can be distinguished on the

basis of operating principle (71) One of the older units is the Raymond
ring -roller mill in which pigment agglomerates are broken down through the
crushing action of a roller
/ Product outlet rotating against a ring
(fig. 4). Classification
-Revolving
of the product may take
whizzers place through the action of
a "whizzer" mounted in
closed circuit on top of the
-Whizzer mill. More recently devel-
drive oped grinding units are high-
speed hammer and rotor mills
and fluid-energy mills (j5)
A hammer mill reduces size
„ ^Grinding ring
by impact of pigment parti-
~ Grinding roller
cles with very rapidly mov-
ing hammers wi thin a confined
circular space, followed by
-Feeder integral air classification.
Fluid -energy mills use steam
or compressed air to gener-
ate an autogenous grinding
action by impact of pigment
particles with each other as
they travel at high speed
about a circular path, with
classification occurring as
a consequence of machine
design. Introduction of
fluid energy mills has led
to the use of the terms
"micronizing" or "jet mill-
ing," one of the main advan-
tages of which is reduction
in the number of larger
particle agglomerates (32)
FIGURE 4. - Cross section of Raymond ring-roller mill.
(71, fig. 5-33, p. 5-29; copyright 1963; used Grinding alone or in
with permission of McGraw-Hill Book Co., combination with calcination
may be enough to produce a
Inc.)
 11

finished pigment containing only one component. In this case, ground material
can go directly to a bagging unit, generally automatic. However, intermediate
storage and handling steps are required if blending is to be done. Ribbon
blenders are commonly used to make mixtures; these mixtures may be passed
through a small centrifugal mill to break up any lumps formed during blending,
and then the mix can be bagged.

Production of Synthetic Iron Oxide Pigments

As evident from the foregoing, the methods used to produce natural iron
oxide pigments can all be considered "dry" methods. Processing steps for
natural pigments serve mainly to produce the desired physical characteristics
in dry solids, and chemical solutions are not involved. The sense in which
"dry" is being used here includes calcination, a step which is used also to
produce synthetic oxides from dry chemicals. However, the majority of syn-
thetic oxides are produced basically by manipulating chemical solutions,
suspensions, or slurries; and the term "wet process" can be used to refer to
synthetic oxides made in this way. In considering synthetic oxides, it is
well to recall that their color depends on the oxide formed, by whatever
process or sequence of steps: Hematite, ferric oxide, o -Fe2 3 , is red;
,

goethite, hydrated ferric oxide, a-FegOs'HgO, is yellow; and magnetite,

Fe 3 04, is black.

Thermal Decomposition (Dry Process)

Iron oxide can be produced from a number of iron salts by heating them
sufficiently in air. This procedure converts iron carbonate in siderite ore
into hematite; this is one of the older methods of producing iron oxide (so
called metallic brown) from natural materials. Oxide thus produced from
siderite and other natural materials, such as pyrite, is classed as natural
oxide because of the origin of the starting material. On the other hand,
oxide produced by calcination of iron salts is regarded as synthetic.

Iron oxide has been produced this way for many years from iron sulfate.
The iron sulfate commonly used is the heptahydrate of ferrous sulfate,
FeSO^VHgO, copperas, and the oxide so produced is referred to as copperas
red. A two-step process has been developed for calcination, in which the
heptahydrate is first dehydrated to the monohydrate and then decomposed at
temperatures in excess of 1,200° F to the oxide (J3; TJ_, pp. 346-347). This
process can be conducted so that the sulfurous offgases can be used to
generate sulfuric acid; the sulfuric acid is reacted with scrap iron to pro-
duce, with subsequent processing, more copperas. Oxide particles produced
by calcining copperas have a spheroidal shape.

Venetian red is a pigment obtained by methods similar to those used for

copperas red, a major difference being inclusion of a lime compound in the
furnace charge (50). This effectively introduces calcium oxide into the sys-
tem and causes the product to contain calcium sulfate (gypsum) as well as
iron oxide. The calcium sulfate forms by reaction between calcium oxide and
sulfur -containing gases generated by decomposition of the copperas. While
Venetian red has been produced for many years, today its production is quite
small in comparison with that of other synthetic red oxides.
12

Ferrite tans constitute another type of iron oxide pigment that is

obtained by forming a compound between iron oxide and another oxide. The
second oxide may be either magnesium or zinc oxide and is typically reacted at
an elevated temperature with ferric oxide hydrate (16-17) . This procedure can
be considered as a dry method and is similar to methods often followed in mak-
ing ferrites for magnetic applications. In the case of ferrite tans, reaction
between the two component oxides is expedited by including a small amount of
magnesium or zinc chloride, respectively, in the starting mixture as a reac-
tion catalyst. The advantage of the ferrite tans, which are nonmagnetic, is
that they provide a pigment with yellow shading that is heat stable.

Thermal decomposition methods are used also to prepare small quantities

of high-purity iron oxide, generally as Fe2 3 . Such oxide is made mainly for
chemical rather than for pigment purposes; one of its uses is in preparation
of specialty ferrites. Oxide is obtained by first preparing a highly pure
form of an only moderately stable compound, which is then heated to yield iron
oxide. For example, chemical -grade iron carbonate is readily decomposed into
iron oxide and gaseous carbon dioxide.

Solution Methods (Wet Process)

The solution methods most generally used in the domestic production of

synthetic iron oxides trace their origin to procedures disclosed by R. Penniman
and N. Zoph beginning in 1920 (48-49) . The use of their approach and subse-
quent modifications thereof is commonly referred to as the Penniman -Zoph
process. Alterations and variations of the original technology have made pos-
sible controlled production of oxides differing in color and physical specifi-
cations. A representative listing of relevant patents is given in appendix A;
the 1960 patent by Martin reviews the then -existing state of the art (42)
Also, at about the same date the diverse oxides and hydroxides of iron and
methods by which they can be produced synthetically were described in a German
article (31 )
. General features of the various synthetic processes can be
obtained from the patent and technical literature. However, a thorough
presentation of process chemistry and engineering does not appear to be avail-
able; this sort of information is looked upon as proprietary by producers.

The Penniman-Zoph process can be thought of as pigment production through

the controlled rusting of iron. Iron in the form of scrap is reacted with a
solution from which iron is simultaneously precipitated as iron oxide. Also,
by methods developed later, it is feasible to produce pigment by similar
chemistry but without the need for scrap iron. In commercial practice, both
kinds of processing, with and without the use of scrap iron, are employed. As
generally carried out, the Penniman-Zoph process is a two-step operation (28)
In the first step, a seed solution is prepared by precipitating fine nuclei of
ferrous hydroxide. Common practice for preparing this precipitate is to add
an alkali such as sodium hydroxide to a ferrous sulfate solution. The ferrous
sulfate solution can be obtained by making an aqueous solution of the same
chemical, copperas, which can be calcined to iron oxide by dry methodology.
Air injected into the seed solution oxidizes the nuclei to ferric oxide
hydroxide, Y -Fe 0°H or <* -Fe2 3 Hg
• , synthetic goethite. The process then
passes to a continuous -growth phase, in which the seed solution or a portion
 : .

13

of it is added to a reactor containing a ferrous sulfate solution in contact

with scrap iron. Circulation of the solution over the scrap iron along with
air injection causes iron to pass into solution at the same time that iron
oxide is depositing out of solution onto the growing nuclei. Product is
obtained by filtering the solution and washing the recovered precipitate.

The process described produces a yellow iron oxide whose particles are
acicular or needlelike. At the time of initial particle formation, the solu-
tion has a bluish -green color. As growth continues, this changes into a
yellow-brown color which gradually deepens with the development of reddish
shades. How long the operation is carried out depends on what shade is
desired. Some shades may be produced in a few days; in other instances the
run may last for several weeks. Even so, the average particle size of the
product remains quite small, generally less than 1 micrometer. The reaction
is usually carried out in large cylindrical tanks which typically may contain
15,000 gallons of solution, similar to that shown in figure 5. Construction
and design of the tanks vary, as does the method of placing the scrap iron.
The scrap iron used is clean low-carbon steel with high surface area, such as
punchings and trimmings

The chemical reactions taking place can be written as follows:

Nucleus or seed formation:

a. 4 NaOH + 2FeS0 4 = 2 Fe(0H) s + 2 NagS0 4

b. 2 Fe(0H) 2 + %02 = Fe 2 3 -H 2 + HgO

Growth

a. Solution of iron:

2Fe + 2HgS0 4 = 2FeS0 4 + 2H2

b. Precipitation onto seed:

2FeS0 4 + 3Hj,0 + %0 2 = Fe 2 3 -Hg0 + 2HgS0 4

The course of the reactions and nature of product depend on a number of vari-
ables, including rate of circulation of the solution, manner and quantity of
oxygen injection, type of precipitant, temperature, iron quality and quantity,
acidity, amount and character of seed particles, and presence of other ions in
solution, either accidentally or from deliberate addition. Zinc and aluminum
salts are prominent among additives that have been recommended for controlling
the character of the product.

An important variation of the process is elimination of use of metallic

iron, which can be accomplished by careful control of precipitation conditions
(56), including through use of gaseous ammonia (42) Also, it is possible to
.

use iron solutions other than those of the sulfate. An example is the use of
ferrous chloride solution, as described in a recent patent (5) In this
.
14

FIGURE 5i - Tank for storage of synthetic yellow iron oxide. (Courtesy, Pfizer, Inc.).

instance, conditions are maintained such that during both seed formation and
growth stages the iron compound formed is synthetic lepidocrocite, y-FeOOH.

As with its natural counterpart, synthetic yellow iron oxide can be

heated and its water of hydration driven off, thus yielding red oxide,
o/-Fe 3 3
. This is an important way of producing synthetic red iron oxide.
This introduces another consideration into control of preparation of synthetic
yellow, because procedures depend on whether the process is being used to pre-
pare yellow oxide as final product or yellow oxide that is to be calcined to
red. Red oxide produced by dehydrating synthetic yellow retains the needle -
like shape of the yellow, and this gives properties differing from those of
spheroidal copperas red.
 15

Precipitation methods can be used to prepare red, black, and brown pig-
ments directly, by careful control of factors such as temperature and extent
of reaction. Black oxides can also be produced from red and vice versa.
Hydrogen reduction of red hematite can be used to make black magnetite; con-
versely, calcination of magnetite will yield red iron oxide. Although brown
oxide can be made directly, the more usual procedure is to blend a mixture of
red, yellow, and black.

An important brown iron oxide produced for its magnetic rather than its
coloring properties is gamma iron oxide, Y-Fe;g0 3 .Gamma iron oxide has a
spinel type of crystal structure and is widely used in magnetic recording
applications. This oxide can be considered a derivative of the synthetic yellow
iron oxide industry and is usually produced by the following sequence of steps:
(1) Production of synthetic yellow, o/-Fe 2 3 'H 2 0; (2) dehydration of yellow to
red, o/-Fe20 3
; (3) reduction to magnetite, Fe 3 4 ; and (4) oxidation to gamma
iron oxide. This sequence produces magnetic particles whose shape and physi-
cal properties are both desirable. The synthetic yellow oxide produced as
starting material in step 1 has an acicular shape with a high ratio of length
to width, and this particle geometry is retained throughout the balance of
processing. In step 2 water is removed to give temperature -stable ferric
oxide. In the alpha form, however, the oxide is nonmagnetic (antiferromag-
netic). Reduction with hydrogen, step 3, produces magnetite, which has a
spinel lattice and itself finds use in magnetic applications although it is
deficient in chemical stability. In step 4, oxidation is conducted so as to
preserve the spinel structure of magnetite; the end result is an oxide with
desirable magnetic characteristics and good stability. Gamma iron oxide is
unstable with respect to alpha iron oxide, and heating to about 600° C can
cause a permanent reversion to the alpha form.

Precipitation techniques can be controlled so as to produce "trans-

parent" iron oxides. These oxides derive their insignificant hiding power
from very fine particle size, measured in hundredths of a micrometer, or an
order of magnitude finer in size than ordinary synthetic oxides. Trans-
parent oxides can be produced in yellow, red, and intermediate shades. They
constitute a relatively small portion of total synthetic production; the chief
applications are automotive finishes and plastics used in vinyl upholstery.

Regenerator Oxide

Regenerator oxide is byproduct iron oxide produced when hydrochloric acid

is regenerated from liquid waste from the pickling of steel. Pickling is a
chemical descaling process for cleaning the surface of steel sheets and other
intermediate shapes which have become covered with an oxide film, usually as a
result of heating or annealing. Formerly sulfuric acid was the main chemical
used for pickling, but now the majority of pickling is done with hydrochloric
acid. An estimated 40 million tons of steel per year are pickled with hydro-
chloric acid.

Spent pickle liquor containing ferrous chloride and some unused hydro-
chloric acid presents a pollution and disposal problem. A few steel plants
have installed facilities for treating spent liquor by "reversing" the
 .

16

pickling reaction. Hydrochloric acid is thereby regenerated for reuse in

pickling, and iron oxide is obtained as a byproduct. This oxide, which may
require further treatment to decrease residual chlorine, has found use
primarily as a raw material for production of hard ferrites used in permanent
magnets. Regenerator oxide produced in Canada has been particularly prominent
in U.S. consumption of this form of oxide. Most regenerator oxide has been
produced by a spray -roasting process (14, 58) A facility of this type oper-
.

ated by a U.S. steel company is shown in figure 6. However, other types of

regeneration processes have been installed, or are under development as
pollution control methods, and have potential for furnishing forms of oxide
suitable for traditional iron oxide markets (11, 55 67 ) ,

FIGURE 6. - Twin-tower hydrochloric acid pickling line with acid-reclaiming unit.

(Courtesy, Republic Steel Corp.)
 . .

17

,
Aniline Process

The aniline process has not yet been used commercially in the United
3
States. Its use to make iron oxide pigments has been unique to Germany,
where it has been employed for many years as the main method used by a major
maker of synthetic pigments. The process entails reduction of an aromatic
nitro compound to an amine in the presence of iron and acid (69) The reaction,
.

known as Be*champ reduction, when applied to production of aniline from nitro-

benzene is nominally

4 C 6 H B N0 2 + 9 Fe + 4 HgO = 4 CeHgNHg + 3 Fe 3 4 .

While this reaction was originally utilized to manufacture aniline, the

process can be conducted so that byproduct oxide sludge yields valuable
pigments

The technology for making pigments by the aniline process was developed
by I. G. Farbenindustrie A. -G. not many years after the Penniman-Zoph process
was introduced in the United States (34) The aniline process is practiced at
.

Uerdingen in North Rhine -Westphalia, West Germany, by Bayer A. -G. a successor,

of I. G. Farbenindustrie, and accounts for most of Bayer's large output of syn-

thetic pigments. Iron chips of controlled size are used; they may be of cast
iron. To produce yellow pigments, the reaction is carried out in the presence
of aluminum chloride; ferrous chloride is added when black pigments are
desired. Red pigments may be obtained by calcining either yellow or black
products. A description of the aniline process as practiced at the end of
World War II is given in appendix B (38)

Operational Factors in Iron Oxide Production

Because of relatively low product prices, natural oxides cannot carry a

large cost component for transportation of raw material. Therefore, milling
operations are located close to mines for natural pigment, and additional
crude sources are sought in the immediate vicinity. On the other hand, crude
material from iron ore mines is shipped considerable distances to existing
mills, rather than being ground at plants sited nearby. As ocean freight
rates rise, processing and use of foreign natural oxides can be expected to
encounter increasing competition from domestic material.

Blending is a secondary operation carried out both by crude processors

and by other firms handling only finished pigments. In blending, pigments,
and perhaps additives, are combined to achieve a particular shade or physical
property. Blends may be mixtures of wholly natural or synthetic pigments or
mixtures of the two kinds of pigments. For example, a small amount of syn-
thetic oxide may be blended with predominantly natural oxide to obtain a

3 InMarch 1977, Mobay Chemical Corp., a subsidiary of Bayer A.-G., announced

that a major iron oxide production facility was to be added to a plant at
New Martinsville, W. Va., that already produces aniline. Aniline -process
pigments are eventually to be manufactured at this new facility, the first
stage of which was scheduled to come on-stream in 1978.
 .

18

brighter shade. Blending is used to manufacture synthetic brown pigments from

mixtures of synthetic reds, yellows, and blacks. Some blends are rather com-
plex with as many as a dozen constituents, none of which is dominant in the
mixture.

Iron oxides are usually produced in batch or intermittent fashion,

although the processing and milling of natural oxide could be carried out
continuously. Milling can be readily started and stopped, and therefore can
be done conveniently on a single-shift basis. However, calcining and carrying
out wet -process methods require a prolonged period of continuous operation.
Also, energy inputs for heating are needed for both of these operations.
Therefore, it is desirable to conduct calcining and synthetic oxide manufac-
ture for extended periods, or else to shut the plant down, rather than to run
on a stop-and-start basis.

As with many other industries, iron oxide producers have had to take
steps in recent years to limit air and water pollution. Problems with pollu-
tion have been least for dry operations such as grinding of natural oxide.
For the natural oxides, relatively simple equipment suffices to keep airborne
emissions within acceptable amounts. However, care and some expense are also
involved in avoiding pollution of adjoining waterways by runoff from mill
property. More extensive facilities are required to cope with potential water
pollution from wet -process production of synthetic oxides. This technology
requires handling of acid solutions containing solid fine particles. Meeting
environmental standards has meant extra expense for installation of water
treatment facilities mainly designed to control suspended solids and iron
levels in effluent. Waste water treatment facilities at a major U.S. producer
of synthetic pigments are shown in figure 7. The iron oxide industry has been
included in a study of waterborne wastes of the inorganic pigments industries
(4) but has not been deemed of sufficient concern by the U.S. Environmental
Protection Agency to warrant a specific investigation. One producer has
funded study of uses for iron oxide plant wastes containing gypsum (12)

Relationships Between Iron Oxide Producers

and Other Materials Industries

The majority of iron oxide production ties in at least indirectly with

some other industry or form of minerals processing, as shown schematically in
figure 8. Only the portion of iron oxide production derived from natural pig-
ment mines can be thought of as completely independent of other mineral- and
materials -producing industries.
 19

FIGURE 7. - Wastewater treatment facilities at pigment plant. (Courtesy, Pfizer, Inc.)

 .

20

INPUTS PRODUCTS END USES

MINING CALCINE

PIGMENT 1 1

IRON ORE
\
A?
PYRITE
ROAST
V " CINOEH
COLORANTS
PAINTS
MANUFACTURING STAINS
BUILDING MATERIALS
RUBBER
Ti02 PLASTICS
INDUSTRY
ELECTRONICS
WASTEWATER HARD FERRITES(Ba, Sr)
TREATMENT
SOFT FERRITES |Mn. Ni, Zn)
GARNETS
MAGNETIC TAPE

OTHERS
STEEL
INDUSTRY CATALYSTS
ANIMAL FEED
FOUNDRY SANDS
GLASSMAKING
STEELMAKING DUST

ANILINE PROCESS
(GERMANY)

FIGURE 8t - Relationships between iron oxide producers and other materials industries.

Both the titanium pigment and the steel industry play a very important
role in providing iron -containing materials from which iron oxides are pro-
duced. Various possible interactions between these industries and the iron
oxide pigment industry are shown in figure 8. Not all the interactions are
practiced currently. The sulfate -process portion of the titanium pigment
industry is a key source of copperas, FeS0 4 -7 H2 0, which can either be cal-
cined directly to iron oxide or used in solution methods for production of
precipitated forms of iron oxide. Wastes from newer chloride processes for
titanium pigments also are potential starting material for iron oxide
production (53)

The steel industry, which processes and produces iron-bearing materials

in a variety of forms, is also a significant source of feed materials for iron
oxide production. Light steel scrap with high surface area is used in produc-
ing synthetic oxide according to the process originated by Penniman and Zoph.
Acid pickle liquor from cleaning steel surfaces has been used to prepare fer-
rous sulfate, which when roasted has been an important* source of oxide used as
polishing rouge (30) Within the past decade the steel industry has turned at
.

many plants to hydrochloric acid instead of sulfuric acid for pickling steel.
Several processes have been developed for regenerating hydrochloric acid
pickle liquor, and in them a byproduct iron oxide is produced. Some of this
so-called regenerator oxide has found application outside the steel plant,
particularly for manufacture of hard ferrites used in making permanent magnets.
The steel industry produces a great quantity of dusts; those collected from
certain steelmaking operations can be used in some low-grade pigment
applications.
 .

21

The steel industry has a potential for being a much larger source of iron
oxide powder and in the future could conceivably produce a volume much greater
than the market is capable of absorbing. This can be seen by projecting the
total amount of regenerator oxide that would be produced if all pickle liquor
were processed for recycle. However, even if regeneration technology were
applied universally, it is unlikely that this would significantly displace
established methods of manufacturing iron oxides, because oxides from steel
plants would not possess the characteristics required by end applications.
More likely, these oxides will eventually be recycled via the blast furnace.

Figure 8 also indicates that sulfate and chloride wastes from the tita-
nium pigment and steel industries are usable as agents for treating wastewaters
(26, 59 )
. This is a market for bulk chemicals that has been projected to grow
at about 7% annually (13) .Thus, wastewater applications may prove able to
absorb sulfate and chloride wastes, only a small portion of which can be con-
sumed in manufacturing iron oxides

Production of natural iron oxides has less interdependency with other

industries. Production of oxides using crude from pigment mines relates to
other industries only to the extent that other materials, such as synthetic
iron oxides, are blended with natural oxides. The same is largely true for
pigment material derived from crude from iron ore mines. However, it should
be noted that mining for iron ore is, to a very great extent, intended to pro-
vide feed for blast furnaces, and therefore production from such mines is
scheduled with that as the major objective. Similarly, iron oxide from pyrite
is a byproduct of an operation whose major function is to produce other mate-
rials, such as sulfuric acid.

Another industry in figure 8 relates to iron oxide production in Europe.

This is the organic chemical intermediates industry, one portion of which, via
the aniline process, makes iron oxides as a coproduct in West Germany. This
technology has not been used in the United States, but is scheduled to be
applied within the next few years at a new facility.

END USES

Physical and Chemical Characteristics of Iron Oxide Pigments

Uses of iron oxide pigments depend on properties of the pigment particles,

individually and in relation to the medium in which they are used. Ordinarily,
pigment particles can be considered insoluble in, and unreactive chemically or
physically with, the vehicle into which they are dispersed. Among the proper-
ties or characteristics that can affect selection of a pigment and the manner
in which it is used are mass color (color at full pigment strength) , tinting
strength, hiding power, oil absorption, particle size and shape, particle size
distribution, and cost. Selection of a pigment further depends on optical,
magnetic, and chemical properties. In what follows, properties of iron oxide
pigments will be discussed in general terms and their main areas of applica-
tion indicated. Published literature (23-24, 27, 2J9, 36-37, 39-41) and data
from pigment manufacturers should be consulted for specifics on pigment
properties.
22

Chemical and Physical Stability

Chemical and physical stability along with relatively low cost are
important advantages of iron oxide pigments. Both natural and synthetic
oxides are generally characterized by resistance to alkaline and acid environ-
ments. This helps impart high bleed resistance; that is, resistance to attack
from solvents in coatings applied over coatings pigmented with iron oxides.
Natural and synthetic oxides are both lightfast and nontoxic; the latter is
especially a property of synthetics. Red oxides and calcined natural oxides
deriving their color from ferric oxide (Fe 3 3 ) are heat stable. Other oxides
in which coloration is based on hydrated ferric oxide (Fe 2 3 'HgO) or on ferro-
soferric oxide (Fe 3 4 ) are stable under normal ambient conditions but can with-
stand only a limited amount of heating. Thus, natural yellow oxide, ocher,
raw sienna, and raw umber are subject to color change on heating above 220° F,
natural black oxide (magnetite) is not color stable above 300° F, and syn-
thetic yellow and black do not withstand heating above 350° F.

Particle Size

The particle size of iron oxide pigments depends on the origin or method
of preparation and on whether size reduction procedures were used. The
largest particle sizes are found in natural pigments, which may contain
agglomerates as coarse as 30 to 100 micrometers (about 1/1,000 to 4/1,000
inch). Pulverized natural pigments and synthetic pigments are finer, typ-
ically having particle sizes of 1 micrometer or less on down to particle sizes
of only hundredths of a micrometer in the case of transparent oxides. Thus,
iron oxide pigments span the size range normally associated with all kinds of
pigments from relatively coarse down to colloidal dimensions. 4 Particle size
can be used to control shade, because development of a stronger red shade is
favored as particle size decreases (33) . Smaller particle size also gives
increased hiding power, provided pigment particles are not so small that
hiding power disappears, as in transparent pigments. The range of particle
sizes in a pigment, that is, the particle size distribution, is also important
because a tighter size distribution gives greater color purity and brilliance.

Particle Shape

Pigment properties are also dependent upon shape of pigment particles.

This is perhaps most evident for synthetic oxides and micaceous iron oxide.
In large measure, synthetic yellow iron oxides have an acicular or needlelike
shape as precipitated. Such oxides and the reds prepared from them tend to be
higher in oil absorption than oxides having particles with more regular shapes.
On the other hand, an elongated shape is more desirable in oxides for magnetic
applications. All types of synthetic pigments except yellow are available in
varieties whose particles have a spheroidal or cubic shape rather than an
acicular shape. Red oxide from calcination of copperas is spheroidal, and
this is significant in determining powder and sintering characteristics when

4 Dispersions of colloidal iron oxides, mainly as magnetite, can be produced

for use as magnetic fluids ("ferrof luids") , which have the unusual property
of apparently changing density in response to changes in an applied mag-
netic field (51-52).
 . -

23

this oxide is used in preparation of ferrites. Particle shape of natural

oxides is not controllable beyond the effects of size reduction and calcina-
tion treatments. Micaceous iron oxide particles have a relatively large plate
like or wafer shape which can be utilized to give a coating with enhanced
protective properties. In general, with the exception of micaceous oxide,
particles of natural oxide have irregular shapes but are not highly asymmetric.

Uses and Applications

The variety of uses to which iron oxides are put is indicated in table 2,
which is based mainly on information given in volumes I and II of the Pigment
Handbook (23-24, 36-37 41 47 )
, , . Coloring applications cover a wide range of
materials, such as paint, plastics, and rubber. Iron oxides are chosen in cer-
tain instances because of the particular shades which they provide, as in
stains for wood. Detailed information on relative amounts going to various
end uses is not available. For synthetic oxides in 1971 in the United States,
it has been estimated that one -half went into paint, paper, plastics, and
rubber applications; one -fourth into magnetic tape and ferrites; one -eighth
into roofing granules and cement; and the remaining one-eighth into catalysts,
rouge, drugs, cosmetics, and miscellaneous uses (24 p. 336).
, By comparison,
a distribution of consumption for coloring purposes only as reported in a
German publication in the early 1960's was as follows: Lacquer, emulsion, and
glue colors, 217*; linoleum, tile, and wall and floor coverings, 21%; cement
building materials, 207=,; stone and hard plaster, 177,; polishing agents, 137c,;
and asbestos slate, enamel, and rubber, 87, (25 p. 799).
,

Paint

Paint is a major area of application for iron oxides because of their

attributes, with limitations as given, of high hiding power, high tinting
strength, color fastness, heat resistance, bleed and chemical resistance,
ease of dispersion in all vehicles, high infrared reflectance, high ultra-
violet absorption, and low price. The mass colors available are red, purple,
yellow, brown, and black. Within this range of colors, the main reason for
selecting a pigment other than iron oxide is that iron oxides do not have high
chroma or color purity, which means that an organic pigment may offer greater
brightness or richness of color.

With the growing trend towards water -reducible paints to minimize solvent
emissions, the question arises as to whether iron oxides will prove satisfac-
tory for use in aqueous paint systems. If not, this major end use will be
taken by some other appropriate pigment, and iron oxide consumption will be
depressed. It appears that most synthetic oxides function as well in water as
in solvent paint systems but that use of natural oxides will be more limited
in water -reducible paints. Tests of aqueous industrial paint systems for
primer and top coat applications indicated that synthetic oxides and those
natural oxides with high iron content and low water soluble salts can be
expected to have wide use, with certain limitations (72) .Oxides such as
siennas and umbers are likely to be restricted to use in particular
applications
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 . . . -

25

Building Materials, Drugs, and Cosmetics

The high stability and the nontoxic nature of iron oxides make them
obvious candidates for coloring purposes in building materials and in drug
and cosmetic applications. Red, yellow, brown, and black oxides all show
good fastness to light, cement, and lime, and red oxide has high temperature
resistance; these features have caused these pigments to be the most important
for producing the respective colors in building materials (33) Both syn-
.

thetic and natural iron oxides are used in construction materials. Because of
their nontoxicity, synthetic oxides can be used without certification in drugs,
cosmetics, and pet food and in plastics for food packaging; raw sienna and
burnt umber also may be used in food packaging (18)

Ferrites

The use of iron oxides in ferrites is an important end use and one in
which color has no more than an incidental role. Rather, the interest in iron
oxides for this application is due to the magnetic and electronic properties
of the compounds or bodies produced. Ferrites are manmade mixed oxide compo-
sitions containing iron and one or more other cationic elements and can be
classified into four main groups:

1. Soft ferrites, also known as linear ferrites, are chiefly manganese

zinc and nickel -zinc ferrites corresponding to the general formula M0-Fe 2 3 .

They are an important part of the ferrite industry, comprising television

deflection yokes, high-frequency transformer cores, antenna rods, and record-
ing heads

2. Magnetic memories and switches, also known as square-loop ferrites

and structurally similar to linear ferrites, are mainly magnesium -manganese
and copper -manganese ferrites.

3. Microwave ferrites, used in telecommunication devices in small quan-

tities but at high unit value, include nickel -copper and manganese -magnesium
ferrites, garnets, and some hexagonal ferrites.

4. Hard ferrites, mostly barium and strontium ferrites according to the

general formula M0'6Fe 2 3 , are used as permanent magnet materials in loud-
speakers, motors, generators, and flexible magnets

Commercialization of ferrites is a post -World War II development which

by 1974 grew into a market of over $100 million for soft ferrites (including
memory cores) and to about $40 million for hard ferrites (61) .Strongest
future growth is expected in hard ferrites, because the trend is for gradual
displacement of ferrite memories by silicon devices and other technology.

The vast majority and the greatest volume of ferrites are prepared by
powder methods similar to those used in powder metallurgy and ceramics. Heat-
ing causes intimate mixtures of the component oxides to react and form ferrite
grains, which are shaped, usually by pressing, and then densified in another
heating operation. The result is a polycrystalline body which is never
 . - .

26

perfectly uniform because of variations in grain size and porosity that cannot
be eliminated. While certain intrinsic properties of ferrites have little to
do with microstructural details, such other properties as mechanical strength,
initial permeability, and coercive force depend on microstructure and there-
fore may occasion considerable quality control and development efforts to
insure reproducible attainment of optimum properties (10)

A generalized diagram of the steps involved in making ferrites is shown

in figure 9 (62) In the preparation of ferrites from oxides, particle size
.

and shape are important in determining which oxides are the most suitable (64)
In the less demanding applications, regenerator oxide from steel plant pickle
liquor and natural magnetite containing silica impurity are satisfactory, low-
cost raw materials. Copperas red oxide is used at higher cost when circum-
stances require. As
DRY METHOD WET METHOD indicated in the diagram,
mixtures other than oxides,
such as carbonates, hydrox-
Weigh and mix Weigh and dissolve
ides, or oxalates, may also
STARTING STARTING
MATERIALS MATERIALS be used as starting mate-
rials. Another approach by
CARBONATES, which intimate mixtures of
OXIDES OXALATES,
two or more components may
ETC.
be prepared in specified
proportions is to precipi-
I
Decompose
tate or otherwise cause to
separate from a multi-
PRECIPITATE
by heat component solution fine
particles of the constitu-
I entsI As with carbonates or
.

oxalates, heating converts

Filter, dry, and
MIX, USUALLY MILL these mixtures into oxide
powder as necessary
ferrites. For specialized

I J
applications and research
purposes, a small quantity
I of ferrites is made in the
form of single crystals by
PRESINTER
such techniques as flame
fusion, gradient solidifica-

Mill, add
I binder,
tion, and flux melt.
and
lubricate if necessary
Catalysts, Gas Absorption,
and Foundry Sands

Besides ferrites, other

PRESS, SINTER, noncoloring uses to which
and FINISH pigment -quality iron oxides
are put because of their
FIGURE 9. - Flow chart of ferrite preparation methods chemical nature are cata-
(63, fig. 2.1, p. 14). lysts, gas absorption, and
foundry sands. Catalytic
properties of iron in oxides
 ,

27

come about because iron is a transition element of variable valence, usually

2 or 3, which also forms defect oxides. Many oxide catalysts have been
developed containing iron, chromium, aluminum, and other elements; they are
used in several petroleum-refining reactions. Iron oxides have an affinity
for sulfur -containing gases such as hydrogen sulfide (H2 S). In the form
known as "iron sponge" they were used to purify manufactured gas prior to the
popular usage of natural gas (45) . More recently, iron oxides have shown
promise for removing hydrogen sulfide from hot gases generated in coal gasifi-
cation ( 1_)
. In foundry sands, it has long been known that small additions of
iron oxide improve hot strength, for example, in core sand mixes for heavy
sections (54 ) . Natural iron oxide is used as an additive in foundry sand,
in which reaction between iron oxide and impurities takes place when the sand
is subjected to the heat of iron and steel casting. This action helps avoid
a variety of casting defects. Additions of 0.57o to 0.8% are the rule,
although as little as 0.25% is effective in eliminating porosity defects in
iron castings made using ure thane -bonded sands (46). The amount of iron oxide
consumed annually in the United States for these purposes, as well as to
color-code certain sand mixes, is estimated as about 2,000 tons.

Transparent Oxides

Because of the very fine particle size, about 0.01 micrometer, transpar-
ent iron oxides can provide both color and transparency. Particularly notable
use of this combination of optical properties has been made in recent years in
finishes for automobiles. Utilization of the additional property of absorbing
ultraviolet radiation is being investigated to determine the potential of
transparent oxides in containers and packaging for food and wherever else
durability, transparency, and ultraviolet absorption are desired in a pig-
ment (22, 43).

Magnetic Recording

The most important application of iron oxides based on magnetic and

electrical properties is in magnetic tape in the form of gamma iron oxide
Y-Fe2 3. Production of gamma iron oxide typically begins with synthetic
production of yellow iron oxide, which is converted to the red oxide,
hematite (o/ -Fe 2 3 ) by heating and then under carefully controlled conditions
,

reduced to magnetite (Fe 3 4 ) and finally reoxidized, while retaining the

spinel crystal arrangement of magnetite, to gamma iron oxide. Gamma iron
oxide is metastable with respect to hematite and transforms irreversibly to
hematite when sufficiently heated. However, under normal conditions of use,
gamma iron oxide remains unchanged and functions as the key component in
recording apparatus whose value is many times that of the oxide itself. An
advantage of preparing gamma iron oxide as described is that this method
automatically gives elongated particles, which have much better recording
characteristics than regularly shaped particles of the same oxide. Only a few
companies produce synthetic oxide for magnetic recording purposes; it is mar-
keted either as finished gamma iron oxide or as the yellow oxide precursor.
The amount of oxide produced for this use is not known, but it is a signifi-
cant part of total synthetic production.
 s

28

Copy Machines and Wastewater Treatment

The magnetic properties of iron oxides also lend themselves to certain

applications in copy machines and in filtering for water treatment. Iron
oxides in the form of ferrites can be used as the carrier for toner particles
in electrostatographic copiers (6}. Soft ferrites such as nickel -zinc and
manganese -zinc varieties are preferred, because they are magnetically attract-
able but easily magnetized and demagnetized. Ferrites produced for this use
are prepared with a particle size somewhat larger than that normally encoun-
tered in pigments. Potential use of iron oxide to facilitate filtering of
waste waters is under development. High -gradient magnetic separation tech-
niques are being applied, especially for removing fine particles. In this
application, seeding with a magnetic material and a flocculant are used to
enhance removal of nonmagnetic or diamagnetic particles (15) . Also, improved
filtering characteristics have been obtained by incorporating iron oxide with
polymer particles as a filter aid (9) . Magnetite is the oxide used both for
magnetic seeding and as a filter aid; in both applications the process is
operated so that oxide is recovered and recycled.

Micaceous Iron Oxide

Micaceous iron oxide is a pigment material whose good protective coating

properties relate to the flaky shape of the oxide particles, most of which are
only a micrometer or so thick but from 10 to 60 micrometers long (66,
pp. 52-53). This shape, when utilized properly in a coating, helps confer
outstanding durability. Micaceous oxide is specular hematite, that is,
ferric oxide, the same as in red iron oxide, and therefore is both chemi-
cally inert and high in heat resistance. However, micaceous oxide is dark
gray and not red. The main source has been Austria, where in the 1970'
"eisenglimmer" has been mined at the rate of about 9,000 tons per year.
Because of the lack of suitable domestic deposits, micaceous oxide has not
seen much use in the United States. Recently the Japanese have developed a
wet -process method of manufacturing a synthetic micaceous iron oxide, using
byproduct copperas as feed ( 65). Applications similar to those of natural
micaceous oxide are visualized, but apparently are still being tested.

Iron Oxides in Relation to Other Pigments

In today's technologically based society, market and application niches

of iron oxide pigments depend on their attributes compared with those of other
pigments. The position of iron oxides in the overall pigment industry is
shown in figure 10, on the basis of 1974 data (63) . In that year, iron oxides
accounted for 127o of the volume and over 5% of the value of production of all
pigments. The most important pigment was white titanium dioxide, which
accounted for 67% of the volume and 54% of the value of production. Among
inorganic pigments, iron oxides and chromates followed titanium dioxide in
order of importance ahead of zinc oxide. Iron oxides do not compete with
titanium dioxide because all iron oxides are colored. Of the colored
inorganic synthetic pigments, oxides and chromates comprised the greatest
amount. Oxides were produced in greater volume than chromates but at lower
value. Iron oxides were the only representatives of colored inorganic pig-
ments of natural origin. The data presented in figure 10 illustrate the
 29

Organic Synthetic

105.7
$23.2 £ Natural

Black Black
110 5 i— Synthetic 4.8
$26.1 $2.9

Inorganic

48
$29 Magnetite

N.A.

•— Natural —

Organic Synthetic

359
S273 4 £ Natural

Chromate
52.5
$638
TOTAL PIGMENTS Colored

11803 248
$993 $4137 Synthetic Iron Oxides

1400 71.8
$1249 $41.8

Inorganic

2121 Brown
$1403 19 3
$61

Natural Red
63.3 Iron Oxides 35.9
$95 $3.3

Yellow

81
$1.1

Titanium
White
dioxide
8218 Inorganic Synthetic Titanium
786.7
$563 2
$532.1

-> Zinc — Zinc oxide

29.5
$18.3

Metalic
Inorganic Synthetic
NA

FIGURE 10. - Iron oxides

in relation to the overall pigment industry (63), Pro-

duction thousands of short tons and millions of dollars. Dotted

in

lines denote data omitted for clarity.

30

relatively low unit value of iron oxide pigments, especially for natural
oxides, and the relatively high cost of colored organics.

TRENDS IN PRODUCTION AND FOREIGN TRADE FOR THE UNITED STATES

Collection and compilation of iron oxide pigments data by the Bureau of

Mines began during World War II, so that this portion of the Bureau's program
on mineral commodities currently spans some 30 years. Shipment figures for
crude and finished pigments are a major part of the annual tabulations. The
list of companies participating in the Bureau's canvass in 1976 is given in
table 3; only a few companies produced crude material, but a number produced
finished pigments, either natural or synthetic or both.

The discussion that follows considers trends for finished pigments only.
Shipments are treated as equal to production; data are not collected on produc-
tion directly or on stocks held by either producers or consumers. For long-
term trends, data will be utilized only as far back as 1955; data for earlier
years do not appear to be sufficiently comparable. Furthermore, for direct
comparison with modern industry, only data from 1964 and later years can be
considered. In 1964, producer reclassification of reporting base occurred,
affecting primarily red oxide; that product, formerly reported as manufactured
oxide, was henceforth reported as natural oxide. This change is consistent
with modern concepts of what constitutes "natural" and "synthetic" pigments.
Unfortunately, 1955-63 data cannot be revised to the same base as has applied
since 1964.

Domestic Shipments

Overall (Natural Versus Synthetic Oxides)

Data for 1955-76 for overall domestic shipments of finished iron oxide
pigments are given in table 4 and presented graphically in figures 11 to 14.
Data were obtained from the 2 -year table of shipments data in the Iron Oxide
Pigments chapters of the Bureau of Mines Minerals Yearbook. Revised data were
selected whenever they appeared in the chapter for the year following original
publication. The listing in table 4 and the graphs based on it contain an
adjustment made in order to redistribute values for the "Mixtures and Other"
category as listed in the Yearbook chapters into simplified totals for only
natural and synthetic pigments. This adjustment was made by assigning one-
third of the quantity and one -seventh of the value in the "Mixtures and Other"
category to "Natural," with the balance assigned to "Synthetic."
 . . .

31

TABLE 3 . - U.S. producers of iron oxide pigments in 1976

Producer |
Mailing address | Plant location
FINISHED PIGMENTS
100 Cherry Hill Rd. Wyandotte, Mich.
Parsippany, N.J. 07054
Box 39 Henry, Va.
Henry, Va. 24102
Box 350 Bryn Mawr, Pa.
Bryn Mawr, Pa. 19101
Chemetron Corp., Chemetron Pigments 491 Columbia Ave. Huntington, W. Va.
Div. Holland, Mich. 49423
Cities Service Co., Columbian Div.. Box 5373 St. Louis, Mo ., Monmouth Junction, N.J.,
Akron, Ohio 44313 Trenton, N.J.
Combustion Engineering, Inc., 901 East 8th Ave. Camden , N.J.
CE Minerals Div. King of Prussia, Pa. 19406
1050 East Bay St. Milwaukee, Wis.
Milwaukee, Wis. 53207
E . I . du Pont de Nemours & Co . , Inc Pigments Dept. Newark, N.J.
Wilmington, Del. 19898
Ferro Corp., Ottawa Chemical Div... 700 North Wheeling St. Toledo, Ohio
Toledo, Ohio 43605
Route 100 Exton, Pa.
Exton, Pa. 19341
Greenback Industries, Inc., Route 2, Box 63 Greenback, Tenn.
Greenback Ferrite Div. Greenback, Tenn. 37742
720 Commerce St. Pulaski, Va.
Pulaski, Va. 24301
Box 218 Hiwassee, Va.
Hiwassee, Va. 24347
7011 Muirkirk Rd. Beltsville, Md.
Beltsville, Md. 20705
Box 387 Cartersville, Ga.
Cartersville, Ga. 30120
Pfizer Inc., Minerals, Pigments & 235 East 42d St. Emeryville, Calif. , East St. Louis, 111.,
Me ta 1 s Di v New York, N.Y. 10017 Easton, Pa.
700 Lehigh St. Quincy, 111., Bowmanstown, Pa.
Bowmanstown, Pa. 18030
15 East 26th St. Bethlehem, Pa.
New York, N.Y. 10010
George B. Smith Chemical Works, Inc. 1 Center St Maple Park, 111.
Maple Park, 111. 60151
Box 1766 Springfield, 111.
Springfield, 111. 62705
Sterling Drug, Inc., Hilton-Davis 2235 Langdon Farm Rd. Cincinnati, Ohio
Chemicals Div. Cincinnati, Ohio 45237
Sterling Drug, Inc., Thomassett 120 Lister Ave. Newark , N.J.
Color Div. Newark, N.J. 07105
CRUDE PIGMENTS
Cleveland Cliffs Iron Co. , Mather 1460 Union Commerce Bldg. Negaunee, Mich.
Mine & Pioneer Plant. Cleveland, Ohio 44115
Box 218 Hiwassee, Va.
Hiwassee, Va. 24347
Martin Towers, Room 1836
Bethlehem, Pa. 18016
Box 387 Cartersville, Ga.
Cartersville, Ga. 30120
 ,

32

1
TABLE 4. - Domestic shipments of finished iron oxide pigments, 1955-76, by type

Quantity Value
Year Natural, Synthetic, Total, Ratio: Natural, Synthetic, Total, Ratio:
short short tons short synthetic thousand thousand thousand synthetic
tons tons to natural dollars dollars dollars to natural
1955 41,156 74,146 115,302 1.80 3,031 14,441 17,472 4.76
1956 43,296 70,565 113,861 1.63 3,091 14,013 17,104 4.53
1957 35,345 69,520 104,865 1.97 2,727 13,678 16,405 5.02
1958 33,182 65,240 98,422 1.97 2,655 13,167 15,822 4.96
1959 41,238 76,366 117,604 1.85 3,185 15,852 19,037 4.98
1960 36,238 69,784 106,022 1.93 2,961 14,987 17,948 5.06
1961 35,457 71,045 106,502 2.00 2,927 15,418 18,345 5.27
1962 37,482 75,483 112,965 2.01 3,220 16,578 19,798 5.15
1963 37,489 81,358 118,847 2.17 3,296 17,839 21,135 5.41
1964 56,060 63,479 119,539 1.13 5,553 17,438 22,991 3.14
1965 65,111 62,429 127,540 0.96 6,101 17,448 23,549 2.86
1966 66,601 64,057 130,658 0.96 6,505 18,336 24,841 2.82
1967 60,121 67,217 127,338 1.12 6,133 20,587 26,720 3.36
1968 59,296 73,087 132,383 1.23 6,623 24,053 30,676 3.63
1969 66,953 75,940 142,893 1.13 7,220 25,069 32,289 3.47
1970 53,124 70,864 123,988 1.33 6,378 21,819 28,197 3.42
1971 60,111 68,197 128,308 1.14 8,416 22,921 31,337 2.72
1972 72,212 80,200 152,412 1.11 9,585 28,088 37,673 2.93
1973 66,283 82,519 148,802 1.25 10,000 33,514 43,514 3.35
1974 67,599 79,945 147,544 1.18 10,667 49,945 60,612 4.68
1975 53,022 51,818 104,840 0.98 8,513 37,693 46,206 4.43
1976 70,356 65,559 135,915 0.93 11,374 53,132 64,506 4.67
Ave rage uni t value per pound
Historical basis Constant -dollar basis 8 Ratio:
Natural, Synthetic, Total, Natural Synthetic j
-
synthetic
cents cents cents cents cents to natural
1955 3.682 9.738 7.577 8.08 21.36 2.64
1956 3.570 9.929 7.511 7.59 21.11 2.78
1957 3.858 9.838 7.822 7.94 20.24 2.55
1958 4.001 10.091 8.038 8.11 20.43 2.52
1959 3.862 10.379 8.094 7.65 20.56 2.69
1960 4.086 10.738 8.464 7.96 20.92 2.63
1961 4.128 10.851 8.613 7.97 20.95 2.63
1962 4.295 10.981 8.763 8.14 20.82 2.56
1963 4.396 10.963 8.892 8.21 20.48 2.49
1964 4.953 13.735 9.617 9.11 25.27 2.77
1965 4.685 13.974 9.232 8.43 25.15 2.98
1966 4.884 14.312 9.506 8.51 24.94 2.93
1967 5.101 15.314 10.492 8.63 25.92 3.00
1968 5.585 16.455 11.586 9.05 26.65 2.95
1969 5.392 16.506 11.298 8.32 25.46 3.06
1970 6.003 15.395 11.371 8.79 22.54 2.56
1971 7.000 16.805 12.212 9.75 23.41 2.40
1972 6.637 17.511 12.359 8.88 23.42 2.64
1973 7.543 20.307 14.621 9.54 25.67 2.69
1974 7.890 31.237 20.540 9.06 35.89 3.96
1975 8.028 36.371 22.036 8.44 38.23 4.53
1976 8.083 40.522 23.730 8.08 40.52 5.01
1
Figures for "Natural" and "Synthetic" include those classed as "Mixtures
and Other" in Minerals Yearbook tabulations. Quantities of "Mixtures
and Other" apportioned 1/3 to "Natural" and 2/3 to "Synthetic"; values of
"Mixtures and Other" apportioned 1/7 to "Natural" and 6/7 to "Synthetic."
2
1976 dollar = 1.00.
 33

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34

As shown in figure 11,

total shipments grew nearly
8. 507o from an annual total
near 100,000 tons in the
mid-1950' s to about 150,000
tons in the mid-1970' s.
Shipments growth has been
particularly uneven in the
1970' s, with recovery in
1976 not enough to compen-
sate for a steep decline in
1975. Synthetic pigments
have been responsible for
most of the growth trend;
natural pigments have fluc-
tuated without much long-
s term progression or
£*
1980 recession. Synthetics have
accounted for both greater
volume and value; the volume
FIGURE 13; Average unit value of domestic shipments
of synthetics since 1964 has
of finished iron oxide pigments, 1955-76,
been about 11% greater than
historical basis.
that of naturals. It can be
surmised that the disparity
50 between the amounts of syn-
thetics and naturals shipped
has averaged about the same
as this since World War II.
40 Change of
reporting base
Synthetic oxides have
CO
dominated over natural
oxides in value. This is
evident in figures 12
through 14 for both total
value of shipments and aver-
r-B u a a
age unit value. Since 1964
20
the synthetic -to -natural
ratio for both total value
and average unit value has
Natural
been about 3:1, and since

_ <>-cr-u o u e o o
o o —o o o ^D 1974 this ratio has been
markedly higher. Value of
RATIO, synthetic to natural
LU A fl A A A A A A A A A 6 a
ft
***** domestic shipments of iron
i i j
oxides, which more than
tripled over the past two
Si 1955 1960 1965 1970 1975 1980 decades to around $60 mil-
lion annually in the mid-
FIGURE 14. - Average unit value of domestic shipments 1970' s, has increased more
of finished iron oxide pigments, 1955-76, rapidly than volume of ship-
constant-dollar basis; ments , mainly because of
inflation. On a historical basis, average unit value has been steadily
 -

35

increasing for both natural and synthetic oxides. However, on a constant

dollar basis, it appears that little or no change in average unit value has
taken place for natural oxides as far back as 1955. The same holds for
synthetic oxides, except for unusual value increases beginning about 1974, on
both a historical and a constant -dollar basis. This is a reflection of price
trends, as given in table 5 and shown in figure 15 for synthetic yellow iron
oxide, medium shade. 5 On a constant -dollar basis, the price of synthetic yel-
low declined gradually by about 107o from 1955 through 1972. However, price
increased significantly in 1973 and 1974, mostly between October 1973 and July
1974. In this 9 -month interval, actual prices increased nearly 1007o in
several steps.

TABLE 5 . - Price of synthetic yellow iron oxide, medium shade, 1955-76

Year Price at yearend, cents per pound

Historical Constant -dollar basis 1
1955 11.0 24.1
1956 11.5 24.5
1957 12.0 24.7
1958 12.0 24.3
1959 12.0 23.8
1960 12.0 23.4
1961 12.0 23.2
1962 12.0 22.8
1963 12.0 22.4
1964 12.5 23.0
1965 12.5 22.5
1966 13.5 23.5
1967 13.5 22.9
1968 13.5 21.9
1969 14.0 21.6
1970 15.0 22.0
1971 16.0 22.3
1972 16.75 22.4
1973 21.5 27.2
1974 36.5 41.9
1975 36.5 38.4
37.5 37.5

Source: Compilations by A. Banov in American Paint Journal Convention Daily,

issues of Nov. 2, 1963, p. 30; Nov. 13, 1973, p. 28; Oct. 25, 1977,
p. 54.

B
Synthetic yellow has become the iron oxide listed by the Bureau of Labor
Statistics, U.S. Department of Labor, in its monthly publication, "Whole-
sale Price and Price Indexes." A price listing for synthetic yellow,
Code 06220205 in table 6 of that publication, began appearing in July 1976
on the basis of information obtained from producers. Formerly, a price
based on published quotations for (synthetic) red iron oxide, code 06220111,
was listed.
 .

36

FIGURE 15. - Price trends for synthetic yellow

iron oxide, 1955-76.

Individual Oxides

Trends in shipments of the various natural and synthetic pigments during

1955-76 are listed in table 6 and plotted in figures 16 and 17; it can be seen
that the most significant effect of the 1964 change in reporting basis was for
red oxides. While red oxides have been shipped in largest quantity in both
natural and synthetic varieties, little, if any, growth has taken place for at
least the last 10 and possibly the last 20 years. Shipments of natural brown
oxides also appear to have reached a plateau. Growth in shipments of natural
oxides has been confined to umbers, ocher, and siennas, although the amount of
these three oxides taken together is still only about half that of natural red
oxide. Among synthetics, growth trends can be noted for all shades except red.
Shipments of yellow oxides have advanced especially and in the past few years
have drawn even with those of red oxides
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38

FIGURE 16; - Quantity of domestic shipments of finished natural iron oxide pigments, 1955-76,
by kind.

FIGURE 17. - Quantity of domestic shipments of synthetic iron oxide pigments, 1955-76,
by kind;
 39

Foreign Trade

U.S. foreign trade in iron oxide pigments for 1955-76 is tabulated in

table 7 and plotted in figure 18, taking imports of natural oxides as the sum
of those for crude and refined material. Both forms eventually find their way
into use, and data for making a distinction between ground and unground
material are not readily available for the years prior to 1963. On this basis,
the historical record shows that during 1955-63 annual imports of both natural
and synthetic pigments each fluctuated about an average of 6,500 tons, while
exports of pigment -grade oxides were running about 4,000 tons annually. As of
approximately 1964, the rate of importation began increasing, with growth in
imports concentrated in synthetic oxides. Between 1964 and 1974 the volume of
imports increased nearly sixfold for synthetics and doubled for naturals,
giving an overall fourfold increase. Value of imports rose overall by a
factor of nearly 8. In the same period, volume of exports showed no gain
until 1973, when exports approximately doubled abruptly in both volume and
value. Imports of both synthetic and natural oxides fell sharply in 1975 and
^then rebounded, but not fully, in 1976.

£ 40
-
FIGURE 18. - U.Si foreign trade in iron oxide
pigments, 1955-76.

s 30

1965 1970 1975 1980

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 41

Imports of Natural Oxides

The classification
scheme for imports of iron
oxides according to kind
under the present Tariff
Schedules of the United
States (TSUSA) is given in
table 8. It can be seen that
details on imports of the
various natural iron oxides
are available, and these
have been listed in table 7
and plotted in figure 19.
Of the natural oxides,
umbers have been imported in
greatest quantity and have
shown the strongest import
growth trend. The "not
specifically provided for"
category, which by elimina-
tion and by country of
origin chiefly corresponds
to natural red oxide, has
been second to umbers in
import volume but has
declined significantly.
Of pigments imported in
lesser amounts, in the past
decade imports of siennas
have grown moderately, those
of Vandyke brown have shown
strong growth, and those of
ochers have nearly ceased.
In recent years the main
sources of imports of natu-
ral pigments have been
Cyprus for umber, Spain for
natural red oxide (n.s.p.f.),
Italy for Sienna, West
Germany for Vandyke brown,
1955 1960 1965 and the Republic of South
Africa for ocher.
FIGURE 19. - Imports of natural iron oxides, 1955-76.
42

TABLE 8. - Tariff classifications for imports of iron oxide pigments

(TSUSA numbers)

Natural
Pigment Crude (crude or washed Refined (ground) Synthetic
but not ground)
472.40 473.32 "

472.42 473.36
472.44

472.46 473.80
472.48

472.50 473.40 -

473.86

x Not specifically provided for.

— -
473.30

Imports of Synthetic Oxides

Data are not similarly available on kinds of synthetic oxides imported,

because under the tariff schedule all imports of synthetics are lumped into a
single reporting category. Therefore, the amounts of imports of synthetics
which have been red, yellow, brown, or black oxides are not known. Available
information relates to country of origin, as given in table 9 and graphed in
figures 20 and 21, commencing with 1964. West Germany and Canada have been
the first and second most important sources of synthetic imports, and have
accounted for the majority of such imports. The United Kingdom and Japan have
also been relatively significant sources of foreign oxides. However, imports
from West Germany and Canada have obviously been largely responsible for
growth in imports in the past decade or so. From the structure of the iron
oxide industry in West Germany, it is evident that most of the oxide from West
Germany has been produced by the aniline process. Most of that from Canada
has been obtained as a byproduct from regeneration of steel plant pickle liquor
and has been consumed domestically by the ferrite industry.
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 45

Apparent Domestic Demand

Apparent domestic demand for finished iron oxide pigments in the United
States is listed in table 10 and is presented in graphical form in figures 22
and 23. This estimation of apparent demand 6 makes no allowance for stocks and
stock changes in the absence of appropriate data, and includes only the
refined or ground portion of imports of natural pigments. Apparent domestic
demand has trended upwards since 1964 except for distinct setbacks in 1970 and
1975, of which the 1975 reversal was much more pronounced.

TABLE 10. - Apparent domestic demand for finished irbn oxide pigments,
1964-761

Quantity, short tons

Year Domestic Imports Apparent
shipments Natural Synthetic Total Exports domestic
demand
1964 119 ,539 3,386 8,829 12,215 5,097 126,657
1965, 127 ,540 3,726 10,071 13,797 4,656 136,681
1966, 130 ,658 4,478 15,234 19,712 4,753 145,617
1967, 127 ,338 4,099 14,034 18,133 3,123 142,348
1968 132 ,383 5,407 18,596 24,003 3,321 153,065
1969. 142 ,893 3,830 22,555 26,385 3,992 165,286
1970, 123 ,988 2,956 24,138 27,094 4,565 146,517
1971 128 ,308 2,539 28,236 30,775 3,984 155,099
1972, 152 ,412 4,379 34,274 38,653 4,268 186,797
1973, 148 ,802 3,983 37,436 41,419 9,888 180,333
1974, 147 ,544 4,083 41,943 46,026 9,666 183,904
1975, 104 ,840 1,638 21,867 23,505 8,780 119,565
1976, 135 ,915 2,857 40,547 43,404 5,805 173,514
Value, thousand dollars
Domestic Imports Apparent
shipments Natural Synthetic Total Exports domestic
demand
1964. 22 ,991 206 1,426 ,632 1,816 22,807
1965. 23 ,549 229 1,748 ,977 1,380 24,146
1966. 24 ,841 291 2,626 ,917 1,307 26,451
1967. 26 ,720 316 2,626 ,942 1,312 28,350
1968. 30 ,676 347 3,455 ,802 1,257 33,221
1969. 32 ,289 318 4,390 ,708 1,439 35,558
1970. 28 ,197 252 5,264 ,516 1,621 32,092
1971. 31 ,337 260 5,592 ,852 1,680 35,509
1972. 37 ,673 456 7,602 ,058 1,926 43,805
1973. 43 ,514 656 10,700 ,356 3,101 51,769
1974. 60 ,612 718 14,969 ,687 3,466 72,833
1975. 46 ,206 307 9,184 ,491 2,523 53,174
1976. 64 ,506 516 15,523 ,039 3,353 77,192
1 Apparent domestic demand = domestic shipments + imports - exports,

6 Apparent domestic demand = domestic shipments + imports (natural + synthetic)

- exports.
 1

46

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 47

From 1964 through 1974, apparent demand grew from 127,000 to 184,000 tons
per year, an increase of 45% that corresponds to a moderate annual growth rate
of 3.6%. This was about the same growth rate in that period as for U.S. pro-
duction of titanium dioxide pigment, 857 of that for the Federal Reserve Board
industrial production index (FRBIPI) for total production, and about 50% of
the FRBIPI for chemicals and products. By comparison, population increased 1%
annually. The quantity of domestic shipments and of imports of iron oxides
both increased by about 30,000 tons. The rate of growth was higher for
imports, however; annual growth rates for imports were 20% for synthetic
oxides and -0.3% for finished natural oxides, whereas growth rates for domes-
tic shipments were 1.1% for natural oxides, 2.77, for synthetic oxides, and
1.9% overall. Value of domestic demand rose from $23 million to $73 million.
Average unit value grew more rapidly for imports than for domestic shipments,
but because of lower unit values, imports increased in value by less than half
the amount that value of doiiestic shipments increased.

Both quantity and value of apparent demand decreased markedly in 1975,

and neither returned to the trend level in 1976. The extent to which apparent
demand and domestic shipments recovered in 1976 from the reverses of 1975 can
be judged by comparison of 1976 actual quantities with those projected from
the 1964-74 trend. Demand, shipments, and imports all approached 90% of pro-
jections, which is about the same as noted in trends for titanium dioxide pro-
duction but about 7% below FRBIPI performance both for total production and
for chemicals and products. Continued recovery is required to fully offset
the 1975 decline; average annual growth rates for apparent demand and for
domestic shipments decreased to 1.9% and 0.6%, respectively, when calculated
for 1964-76.

PRESENT AND FUTURE STATUS OF THE INDUSTRY

The iron oxide pigments industry is a mature industry. Its ancient roots
continue to nourish production of oxides from natural sources, but chemical
methods developed in the 20th century have made synthetic oxides the dominant
part of the industry. Iron oxides constitute a small but important portion of
the overall pigment industry, representing perhaps one -tenth of the total
market. Low cost and good chemical and physical stability would seem to
guarantee that iron oxides will remain in demand for pigment purposes. Annual
domestic use of iron oxides has grown to well over 100,000 tons at a value of
around $50 million. Growth in usage has been modest, 3.67> annually in recent
years. While this rate exceeds that of population growth, it lags that of the
chemical sector generally. Imports have grown more rapidly than domestic
shipments of pigments during the last decade and now correspond to about one-
fourth of domestic demand.

Present trends in natural oxides are for a continuation of demand for

certain oxides whose characteristics are desired and otherwise unattainable at
comparable cost. There is some indication that the trend to aqueous paint
systems may retard rather than enhance the use of natural pigments. Deposits
at mines operated solely to produce pigments appear to be in no danger of
exhaustion. However, mining of black magnetite has just recently been stopped,
and radical curtailment of supply of natural red oxide within a few years
 . .

48

appears possible due to the impending cessation of operations at the iron ore
mine that is presently the sole domestic source. Should production of natural
red oxide cease and no substitute source be available, production of pigment
oxide from domestic sources would be confined to relatively small amounts
mined by only two companies. Foreign red oxide is not a direct substitute for
domestic material and is unlikely to be imported in a quantity comparable to
the amount that has been produced domestically. Also foreign sources of
natural pigment are subject to uncertainty because of political, labor, and
management factors

The future of synthetic oxides seems more secure. No real raw materials
problems are evident, although costs may increase because of technological
change in the industries that have traditionally provided feed material.
Methods used to manufacture iron oxides will be expanded when the aniline
process is introduced from Germany into the United States. This development
is expected to have a significant effect on foreign trade in synthetics,
because West Germany has been the main source of imports. As with any
synthetic product, it is possible that some new discovery or advance could
cause a major change in the industry. New sources could arise through
application of technical innovation, leading to marketing of iron oxides as
a desirable byproduct as has already occurred with the aniline process

Synthetic oxides can be expected to remain competitive with other pig-

ments because of continuing sophistication in control over manufacture and
properties of the products. A possible area for large future growth is yellow
oxide in combination with organic pigments as a substitute for pigments such
as chrome yellow that have environmental or ecological disadvantages. Use of
iron oxides in ferrite permanent magnets appears likely to grow in the future,
but declining use of oxides for square -loop ferrites in memory devices is fore-
seen. Transparent iron oxides are a small part of overall iron oxide produc-
tion and consumption; however, these oxides possess a number of unique
properties favoring future growth. In a technological world, nonpigment
uses of iron, oxides are most susceptible to change, because new developments
may cause demand to increase dramatically or drop abruptly. However, low
cost and ready availability are important advantages that should cause iron
oxides to be considered for any application where their properties may be
useful.
 49

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50

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 51

27. Hancock, K. R. Mineral Pigments. Ch. in Industrial Minerals and Rocks,

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32. Kresse, P. Micronised Iron Oxide Pigments. Pigment and Resin Technol.,
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40. Love, C. H. and J. W. Ayers

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52

41. Love, C. H. and J. W. Ayers

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 53

55. Rupay, G. H., and C. J. Jewell. The Regeneration of Hydrochloric Acid

From Waste Pickle Liquor Using the Keramchemie/Lurgi Fluidized-Bed
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56. Ryan, L. W. and H. L. Sanders (assigned to Interchemical Corp., New

,

York). Manufacture of Pigments. U.S. Pat. 2,388,659, Nov. 6, 1945.

57. Santmyers, R. M. Ocher and Ochery Earths. BuMines IC 6132, 1929,

pp. 5-7.

58. Schuldt, A. A. Regeneration of Hydrochloric Acid Pickle Liquor at

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, Mather Iron Ore Mine Marks Production of
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England, 2d ed., 1972, pp. 8-22.

63. Stanford Research Institute. Pigments --Production and Value in 1974.

Sec. in Chemical Economics Handbook. Menlo Park, Calif., January 1977,
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Magnetic Ferrites. Bull. Am. Ceramic Soc, v. 38, No. 3, 1959,
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Iron Oxide (MI0) Chem. Econ. Eng. Rev., v. 7, May 1975, pp. 28-31,
.

43.

66. Treade, M. 316 Micaceous Iron Oxide. Am. Paint J., v. 59, Sept. 23,
1974, pp. 52-53, 56, 62-63.

67. Wade, J. W. Hydrochloric Acid Regeneration With Ferric Oxide Recovery.

Pres at Nat. Conf. on Management and Disposal of Residues From the
.

Treatment of Industrial Wastewaters, Information Transfer, Inc.,

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68. Wells, A. F. Structural Inorganic Chemistry. Clarendon Press, Oxford,

England, 3d ed., 1962, pp. 544-546.
54

69. Werner, J., and P. H. Groggins . Amination by Reduction. Ch. in Unit

Processes in Organic Synthesis, ed. by P. H. Groggins. McGraw-Hill
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70. Wilson, H. Iron Oxide Mineral Pigments of the United States. BuMines
Bull. 370, 1933, p. 72.

71. Work, L. T., and A. L. Stern. Size Reduction and Size Enlargement. Ch.
in Chemical Engineers' Handbook, ed. by R. H. Perry, C. H. Chilton, and
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72. Young, D. S. The Suitability of Iron Oxides and Extender Pigments for
Use in Aqueous Industrial Paint Systems. Pres. at Houston Soc. Coat-
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available for consultation at Division of Ferrous Metals, Bureau of
Mines, Washington, D.C.
 55

BUREAU OF MINES PUBLICATIONS ON IRON OXIDES

Note: All items listed are out of print and no longer obtainable from
the Superintendent of Documents. However, except for the report by Barton and
Johnson, copies may be examined at those depository libraries that maintain
complete files of Bureau publications, and microfiche copies may be obtained
from UPDATA Publications Inc., 1756 Westwood Blvd., Los Angeles, Calif. 90024.

1. Barton, W. R. Jr., and V. Z. Johnson.

, Natural Iron Oxide Pigments in New
England and New York. Report for the Mineral Resources Study and Report
Group of the New England and New York Inter -Agency Committee, October
1954, 11 pp.

2. Harness, C. L. Marketing Mineral Pigments. BuMines IC 7217, 1942, 27 pp.

3. Santmyers, R. M. Iron Oxide Pigments and Mortar Colors. BuMines IC 6627,

1932, 26 pp.

4. . Ocher and Ochery Earths. BuMines IC 6132, 1929, 20 pp.

5. . Umber, Sienna, and Other Brown Earth Pigments. BuMines IC 6504,

1931, 19 pp.

6. Tufft, H. E. Ocher, Umber, and Sienna. BuMines RI 2139, 1920, 6 pp.

7. Wilson, H. Iron Oxide Mineral Pigments of the United States. BuMines

Bull. 370, 1933, 198 pp.

8. . Ochers and Mineral Pigments of the Pacific Northwest. BuMines

Bull. 304, 1929, 74 pp.
 . .

56

APPENDIX A. --SELECTED LIST OF U.S. PATENTS FOR WET -PROCESS MANUFACTURE

OF SYNTHETIC IRON OXIDE PIGMENTS

No. |
Issue date :
InvenCor and title Assignee
YELLOW OXIDE
1,327,061 Jan. 6, 1920 Penniman, R. S., Jr., and N. M. Zoph, West Coast Kalsomine Co.
Process of Manufacturing Iron Compounds.
1,368,748 Feb. 15, 1921 Penniman, R. S., Jr., and N. M. Zoph, National Ferrite Co.
Process of Manufacturing Iron Compounds
and Product.
1,392,925 Oct. 11, 1921 Fireman, P., Pigment and Method of Magnetic Pigment Co.
Producing the Same.
2,111,726 Mar. 22, 1938 Plews, G. , Method of Producing Iron Oxide C. K. Williams & Co.
Pigments.
2,111,727 Mar. 22, 1938 Do.
2,388,659 Nov. 6, 1945 Ryan, L. W. ,and H. L. Sanders, Manufacture Interchemical Corp.
of Pigments.
2,939,767 June 7, 1960 Martin, J., Manufacture of Iron Oxides Columbian Carbon Co.
RED OXIDE (BY DIRECT PRECIPITATION)
2,618,532 Nov. 18, 1952 Atkins, P. J., and J. B. Peel, Method of Imperial Chemical
Making Red Iron Oxide. Industries Ltd.
2,620,261 Dec. 2, 1952 Toxby, T., Method of Making Iron Oxide C. K. Williams & Co.
Pigment.
2,633,407 Mar. 31, 1953 Marsh, D. W. Process for Producing Red
, Mineral Pigments Corp.
Unhydrated Iron Oxide.
2,716,595 Aug. 30, 1955 Marsh, B. H. Manufacture of Red Hydrous
, C. K. Williams & Co.
Ferric Oxide.
2,785,991 Mar. 19, 1957 Bennetch, L. M. , Preparation of Red Oxide Do.
of Iron.
2,937,927 May 24, 1960 Ayers J. W., Production of Red Oxide of
, Do.
Iron Pigments.
BLACK OXIDE
802,928 Oct. 24, 1905 Fireman, P., Manufacture of Printing-ink One -half to E. G. Portner
Pigments.
2,133,267 Oct. 18, 1938 Ayers, J. W. , Black Oxide of Iron and C. K. Williams & Co.
Process for Making the Same.
BROWN OXIDE
1,392,926 Oct. 11, 1921 Fireman, P., Pigment and Method of Magnetic Pigment Co.
Producing the Same.
2,090,476 Aug. 17, 1937 Fireman, P., Pigment and Methods of Do.
Preparing the Same.
OXIDE FOR MAGNETIC RECORDING (Y-FegOa)
2,694,656 Nov. 16, 1954 Camras, M. , Magnetic Impulse Record Member, Armour Research Founda-
Magnetic Material, and Method of Making tion of 111. Inst, of
Magnetic Material. Technology.
3,015,627 Jan. 2, 1962 Ayers, J. W., and R. A. Stephens, Gamma C. K. Williams & Co.
Ferric Oxide for Magnetic Impulse Record
Members
3,904,540 Sept. 9, 1975 Bennetch, L. M. , H. S. Greiner, Pfizer Inc.
K. R. Hancock, and M. Hoffman, Magnetic
Impulse Record Member.
3,931,025 Jan. 6, 1976 Woditsch, P., G. Buxbaum, F. Hund, and Bayer A -G.
. (W . Germany)
V. Hahnkamm, Magnetic Iron Oxides With
Improved Orientability and a Process
for Their Production.
TRANSPARENT OXIDE
2,357,096 Aug. 29, 1944 Fireman, P., Transparent Iron Oxide Columbian Carbon Co.
Pigments.
2,558,302 June 26, 1951 Marcot, G. C, W. J. Cauwenberg, and American Cyanamid Co.
S. A. Lamanna, Powdered Transparent
Iron Oxide Pigments.
 57

APPENDIX B. --MANUFACTURE OF SYNTHETIC IRON OXIDE BY THE ANILINE PROCESS

The description of the manufacture of synthetic iron oxide by the aniline

process that follows is an abridgment of Love's report, pp. 7-16. 1 The tech-
nology described is that used by I. G. Farbenindustrie, A. -G. Uerdingen, West
,

Germany, as of the end of World War II for preparation of their yellow grade
No. 415. Such yellow oxides were produced by iron reduction of nitrobenzene
to aniline using aluminum chloride (AlCl 3 ) and an excess of nitrobenzene.
AlCl 3 was produced by circulating hydrochloric acid over clay containing 177o
to 207o aluminum to give an AlCl 3 with a specific gravity of 1.26, an aluminum
content of 7%, and 0.5% free and 28.5% combined hydrochloric acid. Nitro-
benzene was water -containing nitrobenzene from the aniline -producing plant
or aniline -containing nitrobenzene from washing. Aniline water, the other
liquid raw material, was water remaining from steam distillation of aniline
and contained 3% to 4% aniline.

Iron used in manufacture of yellow 415 was medium-ground cast iron powder
with an iron content of 967 to 97% and a specific gravity of about 7.0. This
powder was prepared by screening and grinding cast iron chips so as to produce
a size fraction of material falling in the 0.6- to 1.75 -mm size range, which
corresponds to about minus 12 plus 30 mesh (U.S. Series).

The equipment and procedure used in oxide manufacture were described as

follows:

Twelve autoclaves of 20 cubic meters capacity are available

for the reduction process. They are lined with acid-proof brick,
have a 3 -arm agitator (of 12 percent Si steel), and the following
inlets at the top: Manhole, distillate outlet, nitrobenzene inlet,
return flow pipe, metallic iron screw feed, sampling tube, oil dis-
charge pipe, and steam inlet. Automatic weighing and measuring
devices are provided for all raw materials. The iron is fed by a
worm screw with interchanging gears so that the rate of feed may be
controlled. As aniline is formed, it distils and is condensed on a
cooler with a surface of 60 to 100 square meters. The proper
safety devices such as bleeding pipes, overflow pipes, etc., are
connected to the vessel.

The sequence of additions of chemicals to produce 415 Yellow

follows: First, 1,980 liters of water and 1,763 liters of AlCl 3
solution are heated in a separate vessel and pumped into the auto-
clave simultaneously with the introduction of 5,000 kg. nitro-
benzene. Then add 5,300 kg. of medium ground cast iron over a
period of 10-12 hours. The aniline starts distilling after 2-3
hours, and the agitator, at 35 RPM, shows an increase in power con-
sumption to 85-90 amperes after 6-8 hours. This power consumption
is maintained for the full period of 10-12 hours by admitting

•"Love, C. H. German Production of Some of the More Important Inorganic Pig-

ments. Office of Military Government for Germany (U.S.), FIAT Final
Report 814, June 24, 1946, 79 pp.
 .

3,500-4,000 liters of aniline water. The resulting aniline is

pumped to the neutralizing tank of 15 -cubic -meter capacity where
the aniline oil separates from the aniline water. Here, after
24 hours, the water is drained off and the oil distilled for 9
hours in the usual commercial manner. The residue of iron oxide
and liquid is steamed for 6-8 hours, and the autoclave filled with
water. It is then forced by 3 -atmosphere air to the iron oxide
refining plant...

In the refining plant, aniline process oxides were purified, dried, and
pulverized. Purifying consisted of removing any remaining metallic iron and
washing free of salts. Removal of metallic iron took place in a "spitzkessel,"
a narrow brick-lined cylindrical iron tank provided with a conical bottom
having a volume of 65 cubic meters and equipped with an arm agitator to which
hanging chains were attached. At a gravity of 40° to 50° Baume (Be), iron
oxide paste from aniline production was run into the tank, diluted with water
to 15° to 20° Be, and agitated. After stirring was stopped, iron was allowed
to settle and was drawn off at the bottom, a process that was repeated several
times

Because of the slow settling properties of yellow oxides they were washed
by means of a system of Dorr thickeners. The pigment slurry in the
"spitzkessel" was diluted to about 10° Be and pumped through a rake classi-
fier for removal of oversize and foreign matter. From there the slurry passed
to a hydroseparator where water was added to give a 5° Be paste. The hydro-
separator overflowed to the first of three Dorr thickeners, which produced a •

15° to 20° Be slurry which was pumped to a second thickener. This process
was continued through a third thickener, additional water being added in
agitated tanks at each stage in amounts regulated so as to produce a maximum
chloride content of 0.017o to 0.027o in the final product.

Collection and drying of the aniline yellows included a brightening

process involving heating to 160° to 180° C, without which the product would
be colored a dirty greenish yellow. Slurry from the thickeners was pumped to
a rotating filter to give a filter cake containing 40% to 507o water, which
was conveyed by screw feed to an inclined revolving heating drum. The drum
was fitted with a gas burner at the charging end and operated so as to produce
an outlet temperature of 160° to 180° C. Filter cake, flowing concurrently
with hot combustion gases was crushed in the center of the drum by steel balls
held in place by a grid across the diameter. Dried yellow product was finally
screened, disintegrated, blended where necessary, and packed.

frU.S. GOVERNMENT PRINTING OFFICE: 1978-259-058/2339

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