Color technology

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Color technology
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Fraga, Robert
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College of Architecure, University of Florida
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AFA HP document 87

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N~O


Color Technology









By
Robert Fraga












AE 681
November 28, 1976


'AC;




















INDEX


INTRODUCTION . . . . .

COLOR THEORY . . . . .

ORIGIN & CLASSIFICATION OF PIGMENTS . .

NOMENCLATURE OF COLORS . . .

HISTORICAL DEVELOPMENT OF COLOR TECHNOLOGY .

Pre-Historic Times . . .

From Early Times to the Fall of the Roman
Empire . . . . .

Middle Ages, Mediterranean Civilizations

Renaissance to thelndustrial Revolution

Industrial Revolution to the Present .

New Synthetic Pigments . . .


. 1

. 2

. 4

. 7

. 10

. 10


. 10

. 14

19

. 24

. 28


CHARTS


Historical Development of Pigments .

Synthetic Organic Pigments of Acceptable
Permanency . . . .

BIBLIOGRAPHY . . . . .














Introduction


From time immemorial men have been exposed to colors.

The colors found in nature have inspired men to create and

use colors. There is evidence that as early as 150,000 years

ago man was using colors. This fact has been documented by

an archeological discovery of bone tubes that carried grease

paint made from red and yellow ochre clays, undoubtedly used

for body painting.

Body painting is believed to be the earliest form of

color use. Primitive men used colors for religious as well

as magical purposes; for example, primitive men believed that

red was the color of life and other colors as well had symbolic

associations with natural forces and primitive Gods. Primitive

man also believed that if he painted an animal on a cave

wall he would capture the spirit of the animal and therefore

have a better chance to capture the animal itself. Thus, the

use of colors at its very beginnings was greatly associated

with religion and art, primitive art being a vehicle for

religious expression and color being one of the principal

vehicles of primitive art. Color and art have been associated

with each other from ancient times to the present, however,

today colors are used for many purposes other than art;

textiles, industry architecture, furniture making, cinema-

tography and even psychology have taken advantage of the use

of color, whether in the form of paints and dyes or in the












form of decomposition of white light,

The following report concerns itself with the historical

development of the processes for pigment preparation, that is,

this report deals with pigments and the way they were prepared

to be used as coloring agents at different periods of human

development.



Color Theory


An introduction to basic color theory is necessary to

understand color perception as well as color technology.

Color is not a substance, but rather the result of selec-

tive or partial absorption or transmission of irregular or

scattered reflection, or of dispersion in refraction of white

light. Sunlight (white light) is made up of many rays of

varying vibrations; if the various rays that compose the sun-

light are broken up by means of a prism, we obtain an elongated

band of different colors called solar spectrum.

The solar spectrum or prismatic spectrum is made up of

a series of colors arranged in the same way as the rainbow.

The location of the colors in the prismatic spectrum depends

on the wavelength of the rays that make up the colors. For

example, colors of a shorter wavelength occur at one end of

the prismatic spectrum--these are the blues and indigo--then

as the wavelength of the rays increases the colors move to

the other end of the prismatic spectrum where red is the

final color. The colors of the spectrum blend into each other











and although we can name hundreds of different colors, we

can not distinguish such fine divisions with the eye, However,

we can distinguish up to seven regions in the prismatic spec-

trums, and they are: red, orange, yellow, green, blue, indigo

and violet.


Pigments

Pigments are powdered substances used for the represen-

tation of colors, a pigment mixed with a medium constitutes a

paint. Pigments are only visible by reflected light, each

reflective pigment obtaining its color from the ray or rays

of light that are not absorbed and which are reflected back

from the surface. Thus, a body which absorbs the blues, yellow

and green rays of the spectrum and reflects the red rays will

appear to be red in color. Therefore, if we examine a red

object under a yellow light, it will appear dull because of

the small amount of red rays emitted by the yellow light that

is falling on the object.

If we mix blue pigment with a yellow pigment the result

would be a green color. The green produced by the admixture

of these pigments are due to absorbtion taking place in the

blue and yellow pigments respectively. It is the light which

escapes absorbtion by both pigments which gives the resultant

green color.

Artists have found that by skillfully using three color

pigments, red, yellow and blue, nearly all the hues or tones

of colors can be obtained, thus, these colors have been called

primary colors.












Primary Colors are colors that can not be reproduced by

admixture of other colors,

Secondary Colors are colors produced by admixture of two

primary colors.

Tertiary Colors are colors produced by admixture of two

secondary colors.


Color Chart

PRIMARY COLORS red, yellow, blue

SECONDARY COLORS orange, green, violet

TERTIARY COLORS red-orange, yellow-orange, yellow-green,

blue-green, blue-violet, red-violet,


Origin and Classification of Pigments


PIGMENTS are obtained from the mineral, animal and vegetable

kingdoms and they are classified;

MINERAL PIGMENTS natural

artificial

ORGANIC PIGMENTS animal

vegetable

artificial


Mineral Pigments


Native pigments; this class comprises geniune Ultramarine,

the Ochres, Umbers, Siennas and other native earth. They re-

quire no preparation except for washing, grinding and in some

cases calcining; as a rule they are rather dull but they are













durable; also, they were the first employed in painting.

Artificial (Mineral pigments): These are prepared

either by the action of heat on the proper ingredients, or by

precipitation from aqueous solutions, that is, they are made

by either a wet or dry process.

I. Pigments made by the Dry Process

These are the Vermillions, Cadmiums and Mass Colours,

Artificial Ultramarine, Cobalt, Smalt, Venetian Red, etc.

These pigments obtained by the dry process as a rule are more

permanent than those obtained by the wet process.

II. Pigments made by the Wet Process

These are Aurelin, Chrome Yellows, Lemon Yellow, Pure

Scarlet, Emerald Greens, White Lead, etc.


Organic Pigments

Pigments Obtained from the Animal Kingdom: The cochineal

insects provide us with: Carmine, Crimson, Scarlet and Purple

Lakes.

Indian Yellow is obtained from the urine of a camel,

euxanthate of magnesium.

Gallstone is derived from a calculus which is formed

in the gall-bladder of oxen.

Sepia is obtained from the secretion of the Sepia

Officinalis a cuttle fish a sea mollusk,

Prussian Blue is obtained by fusing refuse animal

matter with impure potassium carbonate.












Pigments Obtained from the Vegetable Kingdom. These

are mostly Lakes.

A Lake is a pigment prepared by precipitating an

animal or vegetable colouring matter in combination with a

metallic base, usually alumina,

A Carmine when two or more lakes of different strength

are prepared from the same colouring matter, that lake which

contains the greatest proportion of colouring matter to

metallic oxide is termed a Carmine.

A Pink. Some lakes are erroniously called pinks --

Italian Pink and Brown Pink.

It has been shown that much vegetable colouring matter

exists in the plants, as glucosites; they are bodies that can

be decomposed by chemical agents or by the natural process of

fermentation into glucose and a colouring principal. Examples:

Indigo obtained from the leaves of the fera plant and

it is formed by fermentation of the glucosite Indicon.

Brown Pink is obtained from Persian and Avignon

berries glucoside rhamnin.

Yellow Lake and Italian Pink obtained from queratron

bark glucoside quercetrin

Olive Lake is made from the green ebony or laburnum.

Indian Lake and Gambage are prepared from residous

secretion.

Madder Lakes are prepared from the madder root which

contains the glucoside rubion.












Nomenclature of Colors


The naming of colors doesn't follow any systematic

classification. Manufacturers and dealers have the habit of

calling a color pigment by names which are quite arbitrary.

Sometimes many colors are offered under one name whereas in

other cases many names apply to a single pigment. Many

colors are named after their inventor and others are named

after the material used in their production and still others

are named after the locality where they are found in nature.

However, the majority of color that is obtained from reliable

sources is sold by names more or less internationally recognized.


Note

In doing a report on the historical development of the

preparation of pigments as coloring agents, one runs across

formidable problems. Most of the books and articles that are

available today on the subject of pigments deal primarily with

the chemical composition of the pigments, their physical pro-

perties and their various applications. Very little is said

about the various processes used to prepare the pigments.

This is partially due to the fact that most people today are

interested in the acutal use of pigments rather than in their

preparation. However, there are other problems that make it

difficult to write a report on the preparation of pigments,

for example, the nomenclature of colors is such that a name

used for a particular color which is prepared a certain way,

has changed with time and thus we have two different names












for a single color. The preparation processes for certain

pigments such as those pigments obtained from ochres, have

been the same since ancient times and the technology used

to produce these pigments changed only after the Industrial

Revolution; therefore, there are many processes that have

had very little change in terms of a historical perspective,

Also, there is the problem of historical and technological

gaps. For example, there were certain processes used during

the ancient times that were lost after the fall of the Roman

Empire and they reappear during the Renaissance, Finally,

many processes for the preparation of pigments were guarded

with great secrecy and even today modern paint manufacturers

do not patent their formulas so as to maintain them secrets.

In order to study the processes for the preparation of

pigments from a historical perspective, I have organized the

following report into a series of historical periods, from

pre-historic times to the present. I have listed the colors

used during these particular periods of history, the sources

used as pigments for the preparation of these colors and the

preparation process as well. I have tried to document those

processes of which there is reliable data available and I have

omitted in many cases those colors produced by admixtures of

various pigments since it is well known that most colors

can be obtained by admixture of the primary colors, red,

yellow and blue,

The last two sections of this report dealing with the

process for the preparation of pigments during the period






























9


of the Industrial Revolution to the present and the develop-

ment of synthetic pigments, are covered in very general terms

due to the magnitude of the topic in question,











Historical Development of Color Technology

Pre-Historic Times


Color Name/Source

Red ochers

Yellow ochers

Brown ochers


Chief Chemical Composition

iron oxide

iron hydroxide

iron hydroxide


It is believed that prehistoric men used color for body

painting, cave painting and for painting personal objects of

symbolic and utilitarian importance such as tools and weapons.

During pre-historic times, there was very little prepa-

ration of the pigments before their use with a binding medium.

Ochers were ground by rubbing them with stone and other various

tools while they were reduced to a powder form, then, the

pigments were mixed with animal fats which was the principal

binding media used during pre-historical times.


Early Time to the Fall of the Ancient Empires


Color Name/Source

Red ocher
cinnabar

Yellow ocher

Green malachite
artificial & admixture

Blue lapis lazuli
artificial

Black ivory black
bone black


Chief Chemical Composition

iron oxide
mercury sulphide

iron hydroxide

copper carbonate


sodium, sulphur


calcium carbonate
calcium phosphate












White chalk calcium carbonate
plaster Paris

Brown ochers iron oxide


Color/Preparation Process

Red. Red pigments were the most widely used pigments

since Pre-dynastic times. Natural supplies of ochers and

cinnabar (native vermillion) were plentiful near the Aswon

and the oases of the Western Desert, Red pigments from Egypt

had a tremendous reputationand they were imported to Mesopo-

tamia, Palestine and Asia Minor. Red ochers and cinnabar, like

most other natural clays, followed a standard process of

grinding, washing and storing, prior to their mixture with the

binding media. The ancients used a stone pestle and a stone

mortar to gring the ocher stones and cinnabar clays into a

fine powder. After the pigments were ground, they would be

washed with clear water, placed in the sun to dry and finally

made into small cakes which would be stored in small bags until

the time of their usage.

Yellow. Yellow pigments were obtained from ochers and

the processes and tools used to prepare them are the same as

those used for red ochers. Briefly described, the process

involved grinding with a stone pestle and mortar, washing with

clear water and making the powdered pigments into small cakes.

Green. During ancient times, the color green was obtained

through three different methods, The most common way to obtain

green was by admixture of blue and yellow pigments.












Green was also obtained by the use of powdered Malochite,

a natural form of copper carbonate which was found in stones.

These stones were crushed with a mallet prior to being ground

with a stone pestle and mortar; the resulting powdery stuff

was then washed in water and dried in the sun. The dried

powder would then be mixed with a few drops of a binding media

and made into cakes which would be stored in small bags until

their usage.

A green pigment was also made artificially by melting

sand, alkali and copper minerals. These substances were

crushed and ground into a fine powder which was placed into

clay pots and melted. The resulting compound was ground again,

made into cakes and stored in small bags until their usage.

Blue. Powdered lapis lazuli, a semi-precious stone, was

the principal source of blue pigments during the ancient times.

The preparation of this pigment involved crushing the lapis

lazuli stones and grinding the resulting product with a stone

pestle and mortar into a fine powder. These powders would

then be washed in water, dried in the sun and made into small

cakes. The ancients had a hard time consistently grinding

the lapis lazuli into a fine powder, and consequently it was

thought of as a hard pigment to prepare.

An artificial blue pigment was developed to substitute

the powdered lapis; lazuli. The preparation of this artificial

pigment involved heating a powdered form of silica malichite

(a stone) and natron (also a stone) to a temperature of

approximately 830 C. However, this artificial pigment was











not as brilliant as the pigment derived from lapis lazuli,

thus, lapis lazuli remained as the favorite blue pigment.

Black. Black pigments were available in a considerable

variety, however, most black pigments were derived from

carbonaceous substances. Ivory black and bone black were

the most popular black pigments of the time and they were

prepared by identical processes, Ivory or animal bones were

calcinated in a fire; the resulting substances, calcium

carbonate or calcium phosphate, were crushed and then ground

into a fine powder. The powder would then be washed with clear

water, placed in the sun to dry, and mixed with a few drops

of binding media. Afterwards, the resulting mixture would be

made into small cakes and stored in bags until their usage.

White. White pigments were obtained from chalk, calcium

carbonate, and gypsum, calcium sulphate. These substances were

readily available in their natural form. Their preparation

involved the usual crushing, grinding, washing and storing--

very much the same way ochers and stone pigments were prepared.

Brown. Calcinated raw sienna and calcinated raw umber

were the primary sources for brown pigments during ancient

times. Raw sienna and raw umber are natural ochers found in

many areas of the ancient world. These clays were collected

in their natural state, ground into a fine powder and placed

in a clay pot where they would be calcinated until the desired

color was obtained. Later, the resulting substance would be

ground again, washed with clear water, placed in the sun to

dry and made into small cakes which would be stored in bags

until their usage.












Middle Ages Mediterranean Civilizations


Color Name/Source

Red ochers
cinnabar
loc
red lead

Yellow ochers
organic pigments
gold

Green malachite
organic pigments
copper

Blue lapis lazuli
copper

Black lamp black
charcoal black
bone black

White white lead
chalk

Brown ochers


Chief Chemical Composition

iron oxide
mercury sulphite
carminic acid
oxide of lead

iron oxide
varies
gold

iron oxide
varies
copper carbonate

sodium, sulpher
copper carbonate

carbon
cargon
calcium phosphate

carbonate, acetate
calcium carbonate

iron oxide


Red. During the middle ages red pigments were obtained

from three sources: red ochers, red loc and red lead.

The process used for preparing red ochers was the same

process as that used during ancient times. First, the ochers

would be ground in a stone slab or stone mortar with a stone

pestle, then the fine powder would be washed with clear water

and placed in the sun to dry. Later, the powder would be

stored in small bags or clay pots (unlike their ancient counter-

part, the artists from the Middle Ages did not make small cakes

with the powdered pigments).

Red loc was obtained from a resinous secretion found on













the branches of certain plants (this secretion was produced

by an insect, Contenia lacca), This secretion was ground,

mixed with a binding media and stored until usage.

Red lead was obtained by roasting white lead and

exposing it to air. White lead was obtained by storing long

lead plates in clay pots containing vinegar for a period of

3 to 4 months. After this period of time, a white deposit

would form (a mixture of carbonate and. acetate); this deposit

woudl be scraped off, finely ground and bailed.

Yellow. Yellow pigments were obtained from ochers,

organic pigments and gold.

The process for preparing yellow pigments from ochers

is the same process as the one used during ancient times;

grinding, washing and storing being essential operations for

the preparation of this pigment.

Yellow pigments obtained from organic materials such

as Persian berries, saffron and weld, were prepared by bailing

these organic materials in clear water so as to obtain a deep

yellow dye which would later be mixed with a metallic media

and boiled, thus forming a chemical compound which behaves as

a pigment.

Finely divided gold made by grinding gold leaf with

honey and salt was very popular as well as a very expensive

pigment.

Green. Green pigments were obtained from Malachite

stones, organic substances and from copper.












The process for preparing green from Malochite stones

is the same as the process used by the ancients, grinding,

washing and storing being basic operations for this prepara-

tion.

Green pigments obtained from organic substances such

as buckhorn berries and iris flowers were prepared by crushing

these organic materials on a stone slab and collecting the

resulting juices in clay pots. These juices would later be

mixed with a metallic medium and boiled so as to obtain a

chemical compound that behaves as a pigment.

Green pigments obtained from copper were prepared by

either moistening copper plates with vinegar and exposing it

to air or by storing copper plate in clay pots with fermenting

grape skin. Both methods would produce a form of green copper

acetate on the outer surface of the copper plates which would

be scraped off, ground to a fine powder and stored in bags

until used.

Blue. Blue pigments were obtained from powdered lapis

lazuli or artificially from a compound of ores of cobalt,

alkali and sand. The process for preparing blue pigments from

lapis lazuli is the same as the process used during ancient

times, grinding washing and storing being basic operations

for this preparation,

Blue pigments were obtained artificially by heating ores

of cobalt with alkali and sand in a clay pot, the mixture and

fusion of these substances would separate into an upper layer

of blue cobalt silicate and a lower layer of metallic silicate












The cobalt silicate would be extracted from the pot and

ground into a fine powder which would then be washed and

placed in the sun to dry. Later it would be stored in bags

until their usage.

An artificial blue pigment was also obtained by mixing

copper compounds with amonia (stale urine), This mixture

would yield a deep blue solution which would later be mixed

with a metallic media resulting in a compound that behaves

as a pigment,

Black. During the Middle Ages black pigments were

obtained from lamp black, charcoal black and bone black.

Lamp black was obtained by burning various oil waxes

and resins and collecting the soot on suitable surface (it

did not need any further preparation).

Charcoal black was obtained by heating various plant

materials in earthen pots and grinding the resultant substances

into a fine powder which would then be washed in clear water,

placed in the sun to dry and stored until usage.

Bone black was made by calcinated animal bones, the

resulting calcium carbonate would then be crushed and ground

into a fine powder which would later be washed, placed in the

sun to dry, mixed with a binding media and stored until usage.

White. White pigments were obtained from white lead,

chalk and gypsum lime.

White lead was prepared by storing lead plates in pots

containing vinegar for a period of three to four months. A

white deposit of carbonate and acetate would appear on the


























surface of the lead plates which would then be scrapped off,

ground to a fine powder and bailed (it did not need any further

preparation).

The process for making white pigments from chalk and

gypsum lime is the same process as that used during ancient

times; grinding, washing and storing being basic operations

for the preparation of these pigments,

Brown. Calcinated raw sienna and calcinated raw umber

were the primary sources for brown pigments during the Middle

Ages. The preparation of these pigments followed the same

process as that used during ancient times. Brown was not one

of the favorite colors during the Middle Ages,











Renaissance to the Industrial Revolution


Color Name/Source

Red sinoper
cinabrese
vermillion
red lead
hematted.
lac

Yellow ochers
gaillorino
opiment
saffron
arzica

Green verdignis
admixture
malachite

Blue azurite
lapis lazuli
admixture

Black lamp black
charcoal black

White white lead
lime

Brown ochers


Chief Chemical Composition


iron oxide
oxide of lead
ferric oxide


iron oxide

sulphite of arsenic






sodium, sulphur
sodium, sulphur


carbon
carbon

oxide of lead
calcium carbonate

iron oxide


Working up a color: Method of Preparing Pigments by Cennini

Take a slab or red porphyny (a very strong and solid

red stone) and get a stone to hold in your hand also made out

of porphyny which is flat on the bottom and round on top.

Take the raw material approximately the size of a nut

and place it in th-e stone slab and crush it with the stone

you have in your hand.

Take some clear river, fountain or well water and grind

the pigment for a period of one half hour minimum or for as

long as you like. The more you grind it the better it would












get. Then with a wooden spatula, scape the slab stone and

place the powder in a jar. Fill the jar with water and prevent

it from being contaminated.

Red. Red pigments were obtainedfrom sineoper, cinabrese,

vermillion, red lead, hematte and loc,

Sinoper red was prepared from a red Egyptian stone

called porphyny. This stone would be worked up according to

the method outlined by Cennini,

Cinabrese red was obtained from a mixture of sineoper

red and white lime worked up together according to the method

outlined by Cennini.

Vermillion red (a natural clay) was obtained by working

it up according to the method outlined by Cennini.

Red lead was obtained by roasting white lead and expos-

ing it to air and white lead was obtained by storing long lead

plates in clay pots containing vinegar for a period of 3 to 4

months. After this period of time, a white deposit would form

(a mixture of carbonate and acetate). This deposit would be

scraped off and worked up according to the method outlined by

Cennini.

Hemattic red obtained by a form of ferric oxide which

occurs in various forms, amorphous or crystalline, when in a

solid state, hematte is a very strong and solid stone.

Cennini recommends that when solid state, this stone should

be crushed in a bronze morter before working it up.

Red loc was obtained from a resinous secretion found

in the branches of certain plants (this secretion was produced












by an insect, Conteria locca), This secretion was ground,

mixed with a binding media and stored until its usage,

Yellow. Yellow pigments were obtained from ochers,

gaillorino, orpiment, saffron and arzica.

Yellow pigments obtained from ochers were worked up

according to the methods outlined by Cennini.

Gaillorino is a mineral found in a solid state in

areas common to volcanic activity. Cennini recommends that

this stone should be crushed first before working it up.

Yellow pigments obtained from orpiment sulphidee of

arsenic produced through alchemy) were mixed with pieces of

broken glass and worked up according to the methods outlined

by Cennini.

Yellow saffron and yellow arzica were yellow pigments

obtained from herbs and prepared by placing these herbs

(saffron and weld) on a linen cloth over hot stones or bricks

and crushing the herbs with a stone pestle to obtain deep

yellow solution that when mixed with a metallic media would

behave as a pigment.

Green. Green pigments were obtained by alchemy

(Verdignis), green malachite and by admixture.

Verdignes was produced by storing copper plates in

earthen pots containing vinegar (for an undetermined period

of time). A green substance would form on the outside of the

copper plates which would be scraped off and worked up

(using vinegar instead of water) according to the method

outlined by Cennini.













Green malachite was obtained from working up malochite

stones according to the method outlined by Cennini. In work-

ing up the malachite stones Cennini recommends not to grind

this particular stone as much as you would other stones for it

loses some of its brilliancy when ground too finely,

A popular method of obtaining green was by admixture of

yellow orpiment and indigo pigments. Cennini recommends

two parts of orpiment per 1 part of indigo worked up together,

Blue. Blue pigments were obtained from azurite, lapis

lazuli and by admixture.

Blue azurite was obtained by working up azurite stones

(volcanic rocks) according to the method outlined by Cennini.

Blue lapiz lazuli was obtained by working up lapiz

lazuli (a semi-precious stone) according to the method

outlined by Cennini.

A popular method of obtaining blue was by admixture of

Bagdad Indigo and white lead pigments. No specific proportions

are given by Cennini.

Black. Black pigments were obtained from lamp black

and charcoal black.

Lamp black was obtained by lighting a lamp filled with

linseed oil and placing a clean baking dish two or three

fingers away from the flame of the lamp so as to collect the

soot produced by the burning oil. This soot was very fine

and it did not need to be worked up.

Charcoal black was obtained by burning twigs and working

















up the resultant material according to the method outlined

by Cennini.

White. White pigments were obtained from white lead

and lime.

The process for preparing white lead is the same process

as that used during the Middle Ages, White lead was prepared

by storing lead plates into pots containing vinegar for a

period of three to four months; a white deposit of carbonate

and acetate would appear on the surface of the lead plates which

would then be scraped off and worked up according to the method

outlined by Cennini.

Lime is found in a natural state in many parts of the

world, Cennini recommends to work up the lime into a powder

form and placing it in a pail with clear water for eight days

(changing the water each day). After eight days, the lime

powder should be made into small cakes and placed in the sun

to dry; the longer they are exposed to the sun, the better

pigment they will make.

Brown, Brown pigments were obtained from ochers.

Ochers are to be worked up according to the method

outlined by Cennini.













Industrial Revolution to the Present


Red red lead
venetian red
indian red

Yellow American yellow ocher
French yellow ocher
raw sienna
chrome yellow
cadmium yellow
antimony sulphide
arsenic sulphide
yellow iron oxide

Green chrome green
chromium oxide
copper green
hydrated chrome oxide

Blue ultramarine blue
artificial cobalt blue
Prussian blue

Black lamp black
carbon black
graphite
ivory black
charcoal black
vine black
benca black
acetylene black
mineral black

White lead sulphate
white lead
sublimed white lead
ozark white
zinc oxide
zinox
tatanium white
atimony oxide

Brown American burnt sienna
Italian burnt sienna
raw and burnt umber
burnt umber
burnt ocher
Vandyke brown












Industrial Revolution to the Present


With the beginning of the Industrial Revolution, the

paint industry as well as many other industries of the time,

were greatly affected by the introduction of mechanization

processes of production.

Prior to the Industrial Revolution pigments and vehicles

were sold separately and from different sources. In order to

obtain a paint, the prospective painter had to prepare the

pigments and mix them with the binding vehicle himself. How-

ever, in 1956 Sherwin and Williams introduced to the market

the first prepared paints, This event had a profound impact

on the technology and manufacture of paints, consequently,

it greatly affected the technology and preparation of pigments

With the ability to obtain paints as a manufactured

product rather than just a series of ingredients, consumer

demand for paints increased tremendously since anyone, regard-

less of their knowledge of pigments or paint technology,

would now buy paints as a product and apply them.

Greater consumer demand resulted in an increase in the

production and manufacture of paints. The paint industry

took advantage of mechanization and new technologies developed

during the Industrial Revolution to increase production and

maximize efficiency. Naturally, the processes for the prepa-

ration of pigments were greatly affected by the uses of new

technologies. The bronze mortar and pestle once used for

grinding pigments were replaced by stone and pebble mills.












These were large cylindrical containers of a rugged construc-

tion which would turn mechanically, first by power generated

from animals and later by steam. These cylinders were half

full with stones or pebbles and the raw materials would be

placed inside these cylinders, and as the cylinders turned,

the stones or pebbles would ground the raw materials into a

paste which would later be filtered out of the cylinders and

mixed with a binding media by a mechanical process.

From the time of the Industrial Revolution to the

present, the manufacture and production of paints as well as

the preparation processes of. pigments, have advanced from a

trade to a science. New advances in chemistry, engineering

and manufacturing methods have resulted in new processes for

pigment preparation which involves extremely sophisticated

equipment. Today, raw materials used in the preparation of

pigments are tested for inequities and constancy prior to any

further processing. With better understanding of the chemical

composition of the materials used for pigment preparation and

their reaction to other elements, specific machinery has been

designed to take advantage of the physical properties of these

materials and consequently produce the finest pigments.

Temperature controlled furnaces and variable speed electric

mills are now used for the preparation of pigments. This type

of scientific approach to the preparation of pigments has

allowed the paint manufacturing companies to consistently

produce paints of a the same color and tone as well as to

improve the permanancy and brilliancy of the paint products.




















It is virtually impossible to describe in detail all

the various processes that are now in use for the preparation

of pigments. These processes have become very specialized

and some of them are guarded with great secrecy by the manu-

facturing companies.

In general, the modern preparation of pigments involves

chemically testing the raw materials used to make the pigments,

grinding these raw materials in an electrically controlled

mill and mixing the resulting paste with the binding media

by mechanical means. Some processes require that the raw

materials be ground with the binding media and other processes

require that it be calcinated in temperature controlled furnaces

before it is ground or mixed with the binding media.

The following is a list of common pigments used today.

For further information on the preparation of these individual

pigments, consult the following book; Chemistry and Technology

of Paint by Maximillian Foch on reserve at the University of

Florida library.












Note


The following passages dealing with. new synthetic pig-

ments are taken from the book Painting with Synthetic Media

by Russell 0. Woody, Jr.



The New Synthetic Pigments


Few artists perhaps realize what a range of great antiquity

and recent modernity they have in the colors with which they

paint and which they regard as a traditional palette, Of

the twenty-two pigments most generally used, about half

(Flake White, Ivory Black, Naples Yellow, and seven Earth

and Iron Oxide colors) go back to the Renaissance and before.

Zinc White, Ultramarine Blue, Alizarian Crimson, Cadmium

Yellow, Cobalt Blue, Cerulean Blue, Viridian, and Prussian

Blue date from the eighteenth and nineteenth centuries. It is

since the beginning of the twentieth century that Titanium

White, Cadmium Red, and Phthalocyanine Blue and Green were

discovered. None of the colors now used, with the exception

of the naturally occurring prototypes of Alizarin and Ultra-

marine, were at the disposal of the masters of the fifteenth,

sixteenth, or seventeenth centuries.

The great masters had to know their mediums intimately

in order to develop the maximum in chromatic power from their

limited choice of colors and also to preserve as best they

could colors deficient in stability. Conversely, some of

the reason for loss of interest in the technology of handling














various forms of oils and resin oil varnishes was that bril-

liant color could be obtained with the new bright pigments

without resort to many of the time-honored technical devices,

The colored clays--Sienna, Umber, Ochre, Green Earth,

and Red Oxides--have always been available in many places

around the globe from prehistoric times. Man learned early

to roast sienas and umbers to develop the rich Burnt Siena

and Burnt Umber. As far back as the Egyptians he also had

fairly rich colored ores: blue from Azurite and green from

Malachite (both copper ores), yellow from Orpiment (arsenic

ore), bright red from Vermilion (Cinnabar-mercury ore), and

a deep, rich red from the Madder root, from which the color

was extracted and fixed on clay to make Madder Lake. The

famed Lapis Lazuli source of natural Ultramarine Blue was not

developed until the fifteenth century into its really useful

form. It was then that this semi-precious jewel (mined in

Afghanistan and imported through Venice) began to be refined

in Europe to extract the pure colored fraction. This blue was

so expensive that it was used only on contract and specified

by rich patrons.

Until early in the eighteenth century the artist's

palette was limited to the colors of antiquity listed above,

plus Naples Yellow, a lead-antimony compound; Massicot or

Litharge, yellow lead oxide; several vegetable and animal

source colors such as Carmine; and ground blue glass, Smalt.












Modern Pigments

The first truly synthetic, man-made pigment was Prussian

Blue, discovered by Diesback in 1704, The development of Co-

balt Blue in 1802, artificially made Ultramarine Blue in 1824,

and of Viridian in 1838, changed the situation entirely in

blues and greens. The mineral colors Azurite and Malachite,

which had become scarce and costly, could be abandoned, and

the painter could rely on man's own resources. The new pig-

ments were also more suitable for oil painting, the mineral

pigments having performed best in the lean tempera film

where they were originally used. The chromatic range was also

bolstered by the appearance of Cadmium Yellow in this period.

Things became even more exciting when William Perkin

initiated the. epoch of synthetic organic pigments with the

dyestuff Mauve in 1856. Most of the chemicals used to make

this and other such colors that followed were based on products

of the destructive distillation of coal, and hence were called

"coal tar" or "aniline" colors, Unfortunately these early

organic colors were mostly lacking in lightfastness or per-

manence. However, artists took them up with enthusiasm and

disaster followed. It was in this way that the stigma of

"aniline," "coal tar," or "dye" colors arose to designate

dangerous colors deficient in the permanency requisite for

serious painting. Indeed most of those developed in the nine-

teenth century were deficient; but among those that appeared

at an early date was the exact synthetically made reproduction

of Madder--Alizarin, same as the natural material, but more












pure. We were at least doing as well as nature and a bit

better.

Although the naturally occurring mineral colors were

quite stable, similar ones made artificially occasionally were

not. Verdigrin, used over quite a period, was not only

tricky but poisonous. Ultramarine could go "sick" (turn gray)

in time in the wrong kind of oil film. Under conditions more

rigorous than those a protected painting enjoys, what is

regarded as "completely permanent" does not necessarily hold

up. Given strong enough sunlight, everything eventually

breaks down to its basic, simplest, most stable form. So-

called "mineral" or inorganic pigments with the exception of

the simplest oxides and silicates (earths) will do this in

time as well as the organic colors (defined as compounds of

carbon). Like everything else on this earth, color permanency

is a relative thing and dependent on environment.


The New Era

Two of our most used mineral type colors, Cadmium Red

and Titanium White, along with minor synthetic mineral pig-

ments like Manganese Blue and Manganese Violet, date from

1900. But the turning point in color chemistry, the important

beginning of the modern epoch, has occurred in the last gene-

ration. This was the discovery of the Phthalocyanines in

1928 and their appearance as well developed, commercially

available pigments in 1935,

Phthalocyanine Colors. Phthalocyanine blues and greens












are organic pigments, complex and of large molecular size, but

so symmetrical and tightly knit in their structure that they

rival the best in mineral pigments in light resistance and

stability under the most stringent and adverse conditions,

They set a standard of perfection that gave exciting new impetus

to color research and development, In the sum total of their

useful qualities, intensive research has not improved on the

Phthalocyanines for the blue and green range in the thirty-five

years since.

Vat Dye Colors. Most of the valuable results arising

from the reassessment of approach and methods in developing

brilliant, highly lightfast pigments have occurred in the last

ten years. We have possessed for some time certain textile

"vat" dyes of phenomenal permanency, some so lightfast that

they outlast the fabrics they color. But the form of a color

that dyes cloth is not usually the form useful as a pigment.

A pigment to be used in paint must be insoluble and of such

a physical nature as to form fine, brilliantly reflective

color particles. A vat dye is formed in the fiber of the

cloth. To transform such materials to usable pigments has been

difficult.

So far a few colors from the vat dye fields have come

within the artist's reach. These include the more recent

Thioindigo Violets, Indo (Perinone) Orange, and Dioxazine

Purple. The latter, chemically known as Carbozole Dioxazine,

is a deep blue violet of exceptional strength and is a valuable

and unique addition in this part of the chromatic range.












Quniacridone Colors. A new class of pigments, initially

worked on in Germany but brought to practical fruition by the

DuPont Company, is the Quinacridone group that appeared in

1958. The first of these were in the blue-red to violet range

and are in the Phthalocyanine class for lightfastness, Since

then other variations have become available, reaching down

into the middle red and one blossoming into a brilliant

Magenta hue. Manufacturers of artist colors were not slow in

including various of these Quniacridones in their lines,

appearing under such trade names as Acra, Monstral, and

Shivastra, and with the particular company name designation.

To insure that any such proprietary named color is actually

a Quinacridone, the artist should look to see that it is

subtitled "Quinacridone" under the color name and that it is

specified as "Linear Quinacridone," its full descriptive name,

in a statement of pigment composition.

Azo Colors. By far the most numerous general class of

bright organic colors in general industrial use is the Azo

group. This includes most of the bright reds and yellows used

in printing inks and ordinary paints. One dependable pigment

class in this Azo category is the Hansa group, used for some

years now by artists as a dependable color. But most Azos

were not this reliable and it is in the Azos that the greatest

number of improved pigments has come in the last ten years.

By reexamining methods of synthesis and devising whole

new ways of putting these complicated chemical molecules to-

gether, color chemists have found ways to increase the molecular












weight from the 600 region to around 1500, Many of these are

doubled molecules, connecting together two of what could

previously only be made as one molecule, Hence the name

"Diazo" colors, also called Azo Condensation products.

In many cases, the making of much larger and balanced

chemical units has made for more stable colors, both chemically

and in light resistance. To give an idea of how much effort

color manufacturers have put into such a search, over 10,000

different Azo compounds have been synthesized and tested in

the last ten years. Gaertner, in his paper mentioned below,

lists twenty-three greatly improved, or "high grade," Azo

pigments resulting.

Two very thorough and excellent surveys of these new

synthetic pigments have been published: "Exposure Studies

of Organic Pigments in Paint Systems," by Vincent C. Vesce,

Official Digest, December 1959, Vol. 31, No. 419; and "Modern

Chemistry of Organic Pigments," by H. Gaertner, Journal of the

Oil and Colour Chemists' Association, 1963, No. 1, 13-44.

Both authors are leading color research chemists, Vesce in the

United States, Gaertner in Switzerland. Most of the data on

new synthetic pigments in this chapter is from these two sources

and from the testing done in artists' media by the research

laboratory of Permanent Pigments Inc.

Physical Properties

Before discussing and examining the individual colors,

it would be well to consider some of the general physical prop-

erties of synthetic organic pigments and how they adapt to












artists' media and use. As was previously mentioned, people

have the idea that organic colors are still "coal tar" or

"aniline" colors, meaning unstable and unreliable materials.

These terms are utterly obsolete and should be complete for-

gotten. There are organic colors or pigments that are not

resistant to light but are very brilliant and used for print-

ing inks and other purposes that do not require sustained

resistance to sunlight, There are also many that are good

enough for ordinary paints when they are not diluted to tints.

As tints such colors may last only a few weeks. But there are

the new synthetic pigments which we have been discussing in

a general manner here and which. will be examined in detail

following, that are in the same category of reliability as

some of the best "traditional" colors such as Cadmiums and

Viridian. So, although it had a legitimate basis up to a

generation or so ago, the stigmatic appelation of "coal tar"

and "aniline" color is completely out of date, now just an

"old wive's tale."

Texture. Most mineral type pigments such as earth colors,

cadmiums, Cobalt Blue, and whites are rather dense, substantial

feeling materials that require relatively little medium to

make a workable paint. Pure organic pigments, on the other

hand, are light anf fluffy, require considerable binder to wet

the small particles and to provide the additional fluid to

surround them and make a flowing paint. The artist is familiar

with this characteristic in Alizarin Crimson,

Tinctorial Strength. On the other hand, these organic












toners (the pure color) are usually many times as strong

tinctorially and can be diluted much further without losing

strength than such colors as Cadmium, For example, in order

to compare Cadmium Red with organic toner reds for exposure

tests, five times as much Cadmium had to be used with the

same amount of Titanium to produce a tint strength at all

comparable with the organic reds.

Inert Additives, In oil color such a pure organic

pigment ground with oil only does not have desirable qualities

for a good paint film because of the high ratio of oil to

pigment. A soft film that can show excess yellowing and even

wrinkling may result--one that is far too "fat," It is

actually desirable to include a proportion of dense, colorless,

inert mineral pigment to make a good paint, For this purpose

a paint manufacturer would use synthetically made Barium

Sulfate, known as Blanc Fixe in the trade. Artists can use

whiting or clays but these are inferior additives in an oil

film. A grind of straight organic color in oil may be 60 to 70

per cent oil. Use of a moderate amount of Blanc Fixe will not

perceptibly reduce the strength of the color and will bring

the oil content down to a normal 25 per cent as in a Cadmium

grind. In this way excessively "fat" and "lean" paints would

not be mixed in painting with resulting poor paint film

properties.

In synthetic media, such as the acrylic emulsion, pure

synthetic organic colors need no inert pigment additions

because here there is no problem of excess binder. The only












limit is having the minimum amount of the binding vehicle

sufficient to completely "wet" the pigment particles and com-

pletely surround them to make a coherent and flexible paint

film. One can get too "lean," but not too "fat." There are

virtually no problems in formulative proportions or in proce-

dural rules during painting with synthetic mediums.

Opacity. In the matter of opacity, the ability of the

paint to completely hide or obscure the color beneath, synthetic

organic pigments do present some problems since they are in-

herently transparent. This means that when finely ground

and with great excess of medium, as in a glaze, the color will

be as clear throughout as stained glass. Even with such trans-

parent colors, as the concentration of pigment becomes greater,

the opacity or hiding power increases.

A reasonable degree of opacity with these pigments is

easier to achieve in an oil grind since here greater concen-

tration of pigment can be attained. The artist is actually

used to quite a variance in opacity in his normal oil paints.

For example, Cadmium Red hides even in a thinly brushed film,

Cadmium Yellow shows a little through from underneath, Viri-

dean requires a thickly brushed coating to cover, and Alizarin

Crimson is almost transparent, hardly covering at all.

By comparison, the synthetic organic pigments usually

are more opaque than Alizarin but not quite as much as

Cadmium Yellow, Hansa Yellow, one of these synthetic organic

pigments, has been common in oil color lines for some time and

its opacity is characteristic of the stronger pigments we are












discussing here. As the hue deepens, as with Phthalocyanine

Blue and Green, the ability to hide becomes greater. Carbazole

Dioxazine (Dioxazine Purple) is so strong that it is highly

opaque as a straight color although it is transparent when very

greatly diluted.

In the synthetic mediums the organic pigments can be

concentrated to the point of semi-opacity, There is no

necessity of adding inerts because a tough film is formed at

all pigment concentrations. Since one can overpaint in almost

a matter of minutes with synthetic mediums and thick coatings

present no hazard for lasting properties, inadequate opacity

can be corrected by additional coats,

One of the greatest advantages of the beautiful and

brilliant chromatic values of the synthetic organic colors

is that in synthetic mediums the transparency can yield

unequalled glazes. When color is thinned with medium to a

completely transparent state, light penetrates down into the

layers of glazes and is reflected back with exceptional bril-

liance. By varying both the concentration of the color and

the thickness of the glazes, the artist has complete control

of his color effects.

Grinding Organic Toners

In trying to grind his own colors with synthetic organic

pigments the artist has a real problem. The fine particles

of pigment are very difficult to "wet," the agglomerates (lumps

of stuck-together particles) almost impossible to break up












by hand. Paint mixing and grinding machinery, plus the proper

additives (which can be specific for each pigment) for wetting

and for emulsion stability, are virtually mandatory for making

a good paint. Besides, the artist will find it difficult, if

not impossible, at the present time to obtain these colors in

the dry form. By the pound many are extremely expensive and

are literally so messy to handle, being extremely strong and

tending to fly into the air, that artists' material suppliers

will not want to pack them in small containers, Being new,

many are covered by patents and made only by one or a few

licensed pigment manufacturers and are available only to the

industrial paint maker.


Why New Colors are Important

Why should the artist be concerned with more colors

when he has a fairly adequate palette now? (After all, there

are fifty to one hundred colors listed in oil color lines.)

There are several reasons:

First, the colors we have been using are simply the

best we have had up to now, Many are used mostly because of

habit, not because there are not better ones both in chromatic

value and reliability. Manufacturers know this, but they are

stuck with the past list their artist users continue to demand

Second, many of the new synthetic pigments will broaden

and enhance the chromatic range, particularly where glazes and

transparent use are required in new techniques made possible

by the synthetic mediums.











Third, it may shortly become urgent to replace tradi-

tional colors. Synthetic organic pigments can be made in

limitless quantities because the organic chemicals from which

they derive can be synthesized from a wide variety of raw

materials abundant everywhere. Pigments that depend on a

limited supply of metal ore can go the same way as the natural

ore colors Azurite and Malachite which eventually became scarce

and expensive. Such a situation is developing now with the

Cadmium Yellows and Reds. Cadmium metal is only found as a

minor fraction in certain lead and zinc ores. Hence our

supply of Cadmium is entirely dependent on how much lead and

zinc are being mined and from which mines. When a new use

for Cadmium develops, such as the recent Nickel-Cadmium

rechargeable batteries, the demand becomes greater than the

supply. In 1963 ten million pounds of Cadmium were produced

and twelve millions used, the extra coming from a Government

stockpile. The result was a 66 per cent increase in metal

cost and four increases in pigment cost during the year plus

constantly threatened material shortage. So it is well to

investigate other bright yellows and reds and have them

established as replacements.

Economy is a fourth compelling reason. Although very

few of the reliable synthetic organic pigments are really

cheap and many are very expensive, most are quite strong and

need be used in much lower concentration in the grind than

mineral type pigments. In the most concentrated grind, the

net volume of organic pigment that can be included is one-












fourth of that possible with Cadmium pigment (closer to one-

eighth by weight) and the organic pigment grind will be

stronger. As a result the most expensive synthetic organic

pigments, costing five to ten times as much per pound as

Cadmium Reds can be offered as a finished paint in the same

current price range. By diluting the grind to "normal" strength

for practical use, even economy price colors of high quality

and permanence can be offered,


Permanency

Permanency, the ability of a color to last for centuries

without change, is a primary requirement to the fine artist.

A discussion of testing for permanency, for resistance to

fading, is given at the end of this chapter. The drastic

methods used for accelerated testing make permanency or

lightfastness a relative matter in all but the simplest end

product materials. What is meant by "end product" are the

metal oxides and silicates (whites, earth colors, Cobalt and

Cerulean blues, Chromium Oxide green, Venetian Red, Mars

colors, etc.) that are at the end of the line for chemical

reaction, are down to the simplest result of decomposition.

Cadmium sulfides (yellow) can oxidize to colorless cadmium

sulfate. Viridian, which holds combined water, can lose that

water under conditions of accelerated testing and its color

as well,

Let us first look at the results of actual sunlight

exposure tests. On these test panels the color pigment is












reduced with fifty times as much Titanium White pigment by

volume in the case of the "63-" series. Total exposure was

600 hours summer sunlight under single thickness glass at a

forty-five degree angle to the vertical, facing south. The

upper two-thirds of the color was covered by two separate

pieces, the bottom third being left exposed. After 300 hours

the lower (middle) cover was removed and exposure continued

for another 300 hours in sunlight, Thus the lower third was

exposed 600 hours, the middle 300 hours, while the upper

third had no sun exposure. In this way direct comparison can

be made.

The 57-C and 57-W panels are from a 1957 exposure series

and show 600 hours exposure on the lower half of the color

stripe, 300 hours on the upper half, The 57-V-20 was a 1957

test formulation but exposed with the 1963 panels to correlate

the degree of fading. In the 63-L-25 and 57-V-20 panels we

have controls to relate the exposure to other tests at other

times by comparison of the fading of Alizarin Crimson each

time and to the other panels.

Fading results on pigments in accelerated tests will

vary with the medium for several reasons, If the pigment

is one susceptible to oxidation in oil paint the effect of

the oxidation of the disintegrating oil film will cause

greater fading to show than when the pigment is in an acrylic

film under the same exaggerated conditions. The kind of

white, whether Zinc or Titanium, the rigors of widely chang-

ing temperatures and humidity, are also major factors. It












is these extraordinary envirnomental conditions, rather than

any protective value the binder has, that will cause color

fading of different rates between one medium and another and

one test and another.

In making an exposure test, it is necessary always to

have a "control" panel, a standard duplicate used in all the

tests in order to compare these variations. The amount of

fading will fall within a limited range and we can judge,

consequently, what the general category is to which a pigment

belongs--whether it is in the same range as Cadmium or

Viridian or whether it justifies rejection as being no better

than Alizarin (Madder Lake).

Minor fading in an accelerated test, as will be dis-

cussed later, does not mean that a pigment will show fading

under the normal conditions to which a painting is exposed.

There is no actual relation other than if it will stand as

much abuse as well known permanent colors, it can reasonably

be expected to perform as well under normal conditions.


Terminology Used in Listing Pigments

So the reader will know what the degree of permanency

is that these new pigments exhibit in accelerated testing,

we will relate them to the change showed by familiar colors.

These are ranges, rather than the precise values actually

measured, since fading varies with the conditions and the test.


Permanency Group (A) -- in a class with Cadmiums, Viridian,

and Phthalocyanine Blue and Green.












Permanency Group (B) -- more change than (A) and in the Hansa

Yellow range. About three times as good as Alizarin,

Permanency Group (C) -- range between (B) and Alizarin.


Where results vary between one group and the next in

different tests the classification is given as A/B or B/C.

These classifications are factual, taken from actual tests,

not a matter of "opinion" as has often been the case with past

listings of permanency.

The source of information on the permanency data is

indicated as follows:

P Permanent Pigments exposure test studies,

V Exposure test data given by Vesce.

G Listed by Gaertner.

M Pigment manufacturer's data,


The paint binder or vehicle used in the tests are

abbreviated as follows:

a acrylic polymer emulsion binder.

o oil color.

w watercolor.


Naming

Next in importance to the reliability of the pigment

itself is the ability of the artist to identify it on the

manufacturer's label. Obviously with these complex organic

pigments the proper names are too long, too unpronouncable,

to be used for label names. Without a guaranteed statement














statement of composition somewhere on the label, however,

the artist cannot be certain what the pigment is. We suggest

that the simplest way to identify the pigment is the case of

these synthetic organic pigments is to use what is known as

the Color Index Name, at least in the statement of composition.

This suggestion is made here for the first time and it will,

if followed, take years to accomplish as common practice in

labeling.

The Color Index Name is given a new color by The Textile

Institute after the identity is disclosed and the reliable

commercial use has been established. The Color Index Name

is individual and specific for each particular kind of pigment.

There is also a Color Index Number but this usually has five

digits and would be more confusing and difficult to identify.

An example of a Color Index Name is Pigment Red 83 for Alizarin

Crimson.

Names used by pigment manufactures are frequently wholly

proprietary and provide no indication as to the identity of

the pigment. In the following listing we use the specific

chemical name where possible, otherwise the most used trade

designation. Even here the Color Index Name is necessary for

positive identification, although in some cases, as with those

Linear Quinacridones pioneered by DuPont, there is not yet a

Color Index Name available.










Historical Development of Pigments


Chief
Chemical
Composition


Approximate
Date and
Place of
Origin


F F B FLAKE WHITE Basic carbonate Greece A A Sensitive to sulphur fumes
LEAD WHITE of lead Rome when unvarnished. Slight
CREMNITZ WHITE Ancient yellowing in oil. Poisonous



A A ZINC WHITE Zinc oxide France C B Stays cold white. Excellent
CHINESE WHITE 1934 in water techniques.



A A A TITANIUM WHITE Titanium dioxide U.S.A. C B Soft film in oils. Good in
1920 water techniques. Much im-
proved since early manufac-
ture.



B B LITHOPONE Barium sulphate England C B Sometimes turns gray in
ORR'S WHITE and zinc sulphide 1974 strong sunlight when mois-
ture is present.



A F WHITING Calcium carbon- Ancient B B Yellows in oil.
CHALK ate



A A AUREOLIN Cobalt-potassium France A B Transparent. Replaces
COBALT YELLOW nitrite 1861 gamboge, a fugitive color


F B B BARIUM YELLOW


Barium chromate Early 19th
Century


B B Very pale color. May turn
slightly green.


Name(s)


0
1-'.



H-
, (l-
ui (D


,H
S

3 C
ip. p.
OF-
I-'rt


Remarks











A A CADMIUM-BARIUM Cadmium-barium U.S.A. C B
YELLOWS sulphate 1927
(CADMIUM LITHO-
PONES)


A A CADMIUM YELLOW Cadmium sulphide England C B
CADMIUM ORANGE 1846
AURORA YELLOW


F F F CHROME YELLOWS: Lead chromate 1800 A A Substitute cadmiums.
LIGHT, MEDIUM, Darkens. Poisonous.
DEEP


B B B HANSA YELLOW Coal-tar lake 1934 C B
MONOLITE YELLOW
TALENS YELLOW etc.


F B B INDIAN YELLOW Magnesium-calcium India B B No longer made. Coal-tar
PURREE salts of euxanthic lakes substituted.
acid


A A A MARS YELLOW Iron hydroxide Mid-19th B A
Century


F B B NAPLES YELLOW Lead antimoniate Near East 8th A A Sensitive to sulphur. Cumu-
Century B.C., lative poison. Often imita-
Italy, 19th ted by mixtures of cadmium,
Century ocher, and white.


B A Great variety of shades.


A A A YELLOW OCHERS


Iron hydroxide Prehistoric













A A A RAW SIENNA Iron hydroxide Prehistoric B A


F B A STRONTIUM YELLOW Strontium chrome Early 19th B B
LEMON YELLOW Century


A A A TRANSPARENT GOLD Iron hydroxide B B Avoid cheap grades which
OCHER aluminum sometimes contain chrome
hydrate yellow.


F F C ZINC YELLOW Zinc chromate Scotland B B Permanent only in very
LEMON YELLOW 1847 carefully made grades.


F B B ALIZARIN CRIMSON 1,2 Dihydroxyan- Germany C C Replaces fugitive natural
ALIZARIN RED thraquinone on 1868 madder lakes, which are
ALIZARIN LAKE aluminum hydrate obtained from roots.


A A CADMIUM RED: Cadmium sulphide Germany C A
LIGHT-MEDIUM- plus cadmium 1907
DEEP selenide


F A A CADMIUM-BARIUM
RED:LIGHT,MEDIUM
and DEEP


Cadmium sulphide
plus cadmium
selenide and barium


U.S.A.
1926


C A Less tinting strength than
cadmium sulphide-selenide,
but permanent.


CADMIUM LITHOPONE sulphate


F B B HARRISON RED Paratoluidine Germany
TOLUIDE RED toner 1905













F F F MADDER LAKE


A A A MARS REDS


Natural alizarin
from madder root


Iron oxide


Ancient


19th Century


C C Replaced by more permanent
artificial alizarin which
is obtained from anthracene.


B A Artificially made red ochers.


A A A RED OCHER-Eng- Iron oxide Ancient A B Shades vary, depending on
lish,Venetian Red, source.
Indian Red, Span-
ish Red,Light Red


F RHODAMINE TONER Synthetic organic 1892 C C Bleeds in oil.
dye


F F ? VERMILION


Mercuric sulphide


Ancient


C B Erratic.Some samples turn
black in spots.Others survive
in fine condition.Replaced by
cadmium reds in most cases.


A A A CERULEAN BLUE Oxides of tin and England B B Imitated in cheap paints by
cobalt 1860 mixtures of ultramarine,
viridian and white


A A A COBALT BLUE Oxides of cobalt France A A Imitated by ultramarine
THENARD'S BLUE and aluminum 1802 mixtures.


A A A MANGANESE BLUE Barium manganate 1935 A B













A A PHTHALOCYANINE
BLUE
MONASTRAL BLUE


Copper phthalocy-
anine


England
1935


A B Replaces Prussian blue,
Marketed as "Winsor blue,"
"Bocour blue,""Talens
Rembrandt blue," etc.


F B B PRUSSIAN BLUE Ferric ferrocyanide Germany A B Sensitive to alkali.
AMERICAN BLUE, 1704 Fairly permanent only in
MILORI BLUE, best grades.
PARIS BLUE, BER-
LIN BLUE


F A A ARTIFICIAL ULTRA-Sodium silicate, France C B Sensitive to weak acids.
MARINE, FRENCH aluminum and 1826
BLUE sulphur


F A A NATURAL ULTRA-
MARINE, LAPIS
LAZULI BLUE


Sodium,sulphur
and aluminum


13th-14th
Century


C B Should not come in contact
with weak acids such as
vinegar.


A A CADMIUM GREEN Viridian plus C B
cadmium yellow
(hydrated chrome
oxide plus cadmium
sulphide)


F F F CHROME GREEN Lead chromate plus Early 19th A B Not permanent. Poisonous.
CINNABAR GREEN ferric ferrocyanide
GREEN VERMILION (chrome yellow plus
Prussian blue)











A A A CHROME OXIDE
OPAQUE


A A A COBALT GREEN


F F B EMERALD GREEN
SCHWEINFURT GREEI
PARIS GREEN, VERJ
PAUL VERONESE


A A A GREEN EARTH
TERRE VERTE
VERONESE EARTH


Chromic oxide


Cobaltous oxide
and zinc oxide.


France
1862


Sweden
1780


Copper acetoarsenite Germany
N 1814


Iron silicate


Ancient


B B Do not confuse with mix-
tures of chrome yellow plus
Prussian blue, which may be
labeled chrome green.


A B Little strength in tinting.


C B Very poisonous. Must be
isolated from air, organic
lakes, cadmiums, ultra-
marines, and vermilions by
varnish.


C B Takes up much oil in grind-
ing. Heated, it yields burnt
green earth, which is per-
manent in all techniques.


F F F HOOKER'S GREEN Mixtures of Prus- Not permanent.
PRUSSIAN GREEN sian blue and
gamboge


A A PHTHALOCYANINE
GREEN
MONASTRAL GREEN


A A A VIRIDIAN
GUIGNET GREEN
VERT EMERAUDE
OXIDE OF CHROME,
TRANSPARENT


Chlorinated copper
phthalocyanine


Hydrated chromium
oxide


England
1938


France
1838


B B Very intense. Sold as Winsor
green, Talens green, etc.


B B Do not confuse with the fol-
lowing impermanent colors:
chrome green(lead chromate
and Prussian glue),emerald
green(copper aceto-arsenite).












? A A COBALT VIOLET
DEEP


Cobalt phosphate


France
1859


A B Though not poisonous itself,
it may contain admixtures of
cobalt arsenate which is
poisonous.


? A A COBALT VIOLET Cobalt arsenate France A B Poisonous.
LIGHT 1859


F A A MANGANESE VIOLET
NURNBERG VIOLET


Manganese
ammonium
phosphate


Germany
1868


A A Affected by acids and alkali.


A A A MARS VIOLET Iron oxide 19th Century B A


F A A ULTRAMARINE Artificial ultra- Germany B B
VIOLET OR RED marine blue treated 1870-1880
with sal ammoniac
(for the violet) or
dry hydrochloric
acid (for the red)


F F F MAUVE Aniline dye England 1856 Impermanent.


F F F ASPHALTUM
BITUMEN
MUMMY


Asphalt (tar)


17th Century


F F Never dries. Soluble in oil.


F F F BISTRE Soot from beech 15th Century F F Fugitive. Seen only in
wood. water color.











A A A BURNT SIENNA Calcined raw Ancient A A
sienna, iron oxide


A A A BURNT UMBER


Calcined raw umber,
iron oxide plus
manganese dioxide


Ancient


A A Takes much oil in grinding.


A A A MARS BROWN Iron oxide 19th Century B A


A A A RAW UMBER


F B F SEPIA


Iron hydroxide


Ink bag of the
cuttle fish.


Ancient


Late 18th


A A Takes much oil in grinding.


Fugutive in strong sunlight.
Seen only in inks and water
colors.


F F F VAN DYKE BROWN
CASSEL BROWN
COLOGNE EARTH


Native earth con-
taining humus and
asphaltum


17th Century


F F Soluble in oil, fugitive in
water colors. Varies accord-
ing to source.


A A A BURNT GREEN EARTH Calcined terre verte B B


A A A IVORY BLACK
BONE BALCK


Charred animal bones Ancient
Carbon
Calcium carbonate
Caldium phosphate


C C Very slow drier in oil. May
crack if used unmixed in
oil. Cool tone.


A A A LAMP BLACK Carbon Ancient C C Cool tone. Slow drier.


A A A MARS BLACK Iron oxide 19th Century B A Warm tone. Good film.











SYNTHETIC ORGANIC PIGMENTS OF ACCEPTABLE PERMANENCY


SOURCE
REFERENCE
AND
TEST MEDIUM


PERMANENCY
GROUP


COLOR INDEX
NAME


YELLOWS-in order from
greenish to reddish hues
GREEN GOLD
HANSA YELLOW IOG
YELLOW NCG
HANSA YELLOW G
AZO ANISIDIDE YELLOW
ANTHRAPYRIMIDINE YELLOW
FLAVANTHRONE YELLOW
HANSA YELLOW R
HANSA YELLOW RN
YELLOW HR

ORANGES-in order of
deeper hues
HANSA ORANGE
PERINONE ORANGE
ANTHRATHRONE ORANGE

REDS-in order of yellow
reds to blue reds
RED FGG
RED FRLL
QUINACRIDONE SCARLET
RED FGR
PYRANTHRONE SCARLET
PERYLENE VERMILLION
PERYLENE RED
QUINACRIDONE RED
QUINACRIDONE CRIMSON


Nickel Azo
Azo
Diazo
Azo
Azo
Anthraquinone
Anthraquinone
Azo
Azo
Diazo




Azo
Perinone
Anthraquinone




Azo
Azo
Linear Quinacridone
Azo
Anthraquinone
Perylene
Perylene
Linear Quinacridone
Linear Quinacridone


V,G
Po,V
Pa
Pa,V
Pa
V,G,M
V,G,M
Pw, M
V,M
Pa,V,G




V,M
Pa,V,G
Pa,V,G




Pa
Pa
Pa,V,G
Pa,V
Pa,V
V,G,M
V,G,M
Pa,V,G
Pa,V,G


A
A
A
B
A/B
A
A/B
A/B
A
A/B




A/B
A
A




A
A
A
A
A
B
A
A
A


Pigment Green 10
Pigment Yellow 3
Pigment Yellow 16
Pigment Yellow 1
Pigment Yellow 74
Vat Yellow 20
Vat Yellow 1
Pigment Yellow 6 and 10
Pigment Yellow 65
Pigment Yellow 83


Pigment Orange 1
Vat Orange 7
Vat Orange 3




Pigment Red 148
Pigment Red 9
DuPong patent
Pigment Red 112
Vat Orange 4
Pigment Red 123
Pigment Red 29
DuPont patent
DuPont patent


PIGMENT


TYPE












NAPHTHOL ITR CRIMSON
ALIZARIN CRIMSON
CARMINE FBB
PERYLENE MAROON
QUINACRIDONE MAGENTA
THIOINDIGO VIOLET
THIOINDIGO BORDEAU


Arylamide Azo
Madder Lake
Azo
Perylene
Linear Quinacridone
Thioindigo
Thioindigo


VIOLETS-in order from
reddish to bluish hues
QUINACRIDONE VIOLET.
ISO VIOLANTHRONE VIOLET
DIOXAZINE PURPLE
PHTHALOCYANINE BLUE
INDANTHRONE BLUE
INDANTHRONE BLUE,REDDISH

GREENS-in order from
yellow to bluer hues
GREEN GOLD-see Yellows
PIGMENT GREEN B

PHTHALOCYANINE GREEN,
YELLOWISH
PHTHALOCYANINE GREEN,BLUISH

COMPARISON MINERAL TYPE
(INORGANIC) PIGMENTS
CADMIUM RED

CADMIUM RED,C.P.
VIRIDIAN


Linear Quinacridone
Anthraquinone
Carbazole Dioxazine
Phthalocyanine
Anthraquinone
Anthraquinone





Ferric Nitroso
Betanaphthol

Phthalocyanine
Phthalocyanine


Cadmium-Barium Seleno
Sulfide
Cadmium Seleno Sulfide
Hydrated Chromium Oxide


Pa,V,G
V,G
Pa&o,V,G
Pa,o&w,V,G
V,G
V,G


Pw,V


A
A
A/B
A
A
A


B/C


Pa,V,G
Pa,o,w,V,G


Pa,o


A/B
A/B


Pigment Violet 19
Vat Violet 1
Pigment Blue 16
Pigment Blue 15
Vat Blue 4
Vat Blue 6






Pigment Green 8

Pigment Green 36
Pigment Green 7


Pigment Red 108

Pigment Red 108
Pigment Green 18


Pa,V
Pa&o,V
Pa
G,M
Pa,V,G
Pa,V,G
V,G


Pigment
Pigment
Pigment
Vat Red
Pigment
Pigment
Pigment


Red 5
Red 83
Red 146
23
Red 122
Red 87
Red 88


















Bibliography


Cennini, Cennino, II Libro Dell' Arte: The Craftsman's
Handbook. Yale University Press, 1933,

Committee on Colorimetry, Optical Society of America, The
Science of Color, Thomas Y. Crowell Co., 1953.

Foch, Maximilian. Paints, Paintings and Restoration.
D. Von Nostrand Company, 1931,

Graves, Maitland. Color Fundamental. Mc-Graw-Hill Book
Company, Inc. 1952.

Harley, R.D. Artist's Pigments c 1600-1835, American
Elsevier Publishing Company, 1970.

Kay, Reed. Painter's Companion. Webb Books, Inc. 1965.

Mayers, Ralph. The Artist's Handbook of Materials &
Techniques. Viking Press, 1950.

McDonald, Sterling B. Color Harmony. Wilcox & Follett
Company, 1949.

Renner, Paul. Color, Order and Harmony. Reinhold Publish-
.ing Corp., 1964.

Singer, Halmyard, Halls and Williams. A History of Tech-
nology. Oxford Clarentoon Press, 1957.

Taylor, J. Scott. Field's Chromatography for Artists.
Winsor and Newton, 1885.

Thompson, Daniel V. The Materials and Techniques of Medieval
Painting. Dover Publications, Inc., 1956.

Weber, F.W. The Artist's Pigments. D. Van Nostrand Company,
1923.