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Pigments
Many of those who own valuable
paintings, that need to be authenticated, often labor
under the illusion that expensive scientific techniques
can answer all the questions they may have about their
painting. This unfortunately is not the case. Although,
there is no doubt that the collaboration of art, and
science is sometimes imperative to authenticate or date
a painting, this is just part of the jigsaw puzzle. The
results of scientific techniques alone will not give you
all the answers you need in relation to your painting.
The History of Pigment in Art
The biggest element that researchers look for in pigment
analysis is the specific type of pigment. This will tell
researchers and authenticators a lot, from what type of
pigment that certain artists used, to whether or not a
certain pigment was even in existence at the time the
painting was created.
The following is a timeline of popular pigments that
were used in the creation of paint throughout the years.
Some from the prehistoric era are still used today!
Prehistoric/Ancient Pigments
Ochre: Often used for glazes, ochre can either be opaque
or transparent. Used throughout history and today. Made
from naturally tinted clay. This is perhaps one of the
most commonly found pigments families in the history of
color, and are still used today.
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Brown Ochre |
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Yellow Ochre: (limonite) |
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Red Ochre: (haemetite) |
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Madder Red: This pigment
made its artistic debut in the early 1800s, with a
synthetic version created nearly 100 years later.
However, Madder Red, also known as Alizarin has
been around since 1,500 B.C. |
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Azurite: This beautiful blue
pigment was used from 2,500 B. C. and was commonly
known as Egyptian blue. Used from the Renaissance
through the 1700s. |
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Orpiment: The sulfide of
arsenic, this yellow pigment was used 3,000 B.C.
until the early 1900s due to toxicity. |
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Ultramarine: First used in
600 A.D., ultramarine was a highly sought after
blue pigment, but also one of the most expensive.
Coveted in the Renaissance era for religious
paintings was created from the precious stone
lapis lazuli. A synthetic version was created in
the 1800s, and became more widely used in art
after that. |
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Vermilion: Another very
expensive pigment, the lovely red vermilion is
created from the ground mineral cinnabar. First
used around 500 A.D., vermilion is rarely used
today because it is considered to be toxic. |
Antique Pigments
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Carmine: Though South
Americans were the first to use Carmine, this
lovely red pigment came to European artist in the
1600s. Created from the dried bodies of the
cochineal bug, this pigment was used to make dyes,
paint and stains, but isn't widely used today in
art. |
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Charcoal Black: Used from
the 1300s to today, charcoal black is also
referred to as "carbon black." This is created
when organic materials are partially burned, or
carbonized, and then turned into charcoal. Popular
amongst painters for creating sketches on their
canvas first because it was easily covered and
hidden by the oil paint. |
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Chalk: Made from limestone
or calcium carbonate, chalk has been used in art
since before the Renaissance. Typically used, as
it is today in drawing, chalk can also be used in
pastel form. |
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Malachite: Mainly used in
art from the 1400s to the 1500s, malachite is a
lovely pigment ground from the ore of copper
carbonate. Very popular during the Renaissance but
finally replaced by a synthetic version in the
1800s due to toxicity. |
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Indian Yellow: (euxanthin)
Discovered in the 1400s and not used much after
the 1900's, Indian Yellow was a very popular
pigment for oil and watercolor paints. Ground from
magnesium euxanthate-basically, dried cow
urine-this yellow pigment can be quite
transparent. This practice was banned and
considered inhumane in the early 1900's because to
achieve the bright yellow hue, the cows were only
fed mango leaves and water. A synthetic version
shortly followed. |
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Terra Verte: This greenish
pigment was highly sought after by Renaissance
painters to create skin undertones. Derived from
iron silicate and clay, terra verte is still
around but very rare today. |
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Indigo: Discovered by none
other than Marco Polo in the 1200s, Indigo is
still widely used today. Derived from Indigo
plants and popularly used as a dye or an ink.
Replaced by a synthetic version in the 1800s. |
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Lead White: Used in art from
the 1300s to the late 1800s, and eventually
replaced due to toxicity, lead white was widely
used in the art world. Made by disintegrating lead
with acid, lead white is the leftover pigment.
Easy to spot in x-ray authentications due to its
metal based nature. |
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Verdigris: Verdigris was a
popular pigment used from the Middle Ages through
the late 1800s. Verdigris is created by placing
grape skins on copper plates, allowing them to
ferment, and thus, creating a green crust. Similar
what happens to a copper penny. Use of verdigris
was discontinued because of toxicity. |
Contemporary Pigments
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Cadmium Orange: Created from
cadmium metal, this pigment was first discovered
and used in the early 1800s. Still used today. |
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Cadmium Yellow: Created from
cadmium metal, this pigment was first discovered
and used in the early 1800s. Still used today. |
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Cerulean Blue: Used since
the 1860s, Cerulean blue was a popular pigment
that painters generally used in landscapes for
their skies. Created by heating cobalt oxide with
other metallic bases. |
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Cobalt Blue: Used in the
early 1800s, Cobalt Blue is a created pigment.
Cobalt blue is created from smalt, the isolation
of the blue pigment in cobalt glass, and is still
used today. |
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Cobalt Green: Created by
mixing cobalt with zinc oxides, then heating them
together. The sediment from this process is then
ground to create the cobalt green pigment. Used
from the early 1800s to today, it is generally not
easy for artists to use, and expensive, so it is
rare to find in paintings. |
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Cobalt Violet: Discovered in
the mid 1800s, cobalt violet is created by mixing
cobalt with disodium posphate and heated at a high
temperature. |
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Emerald Green: Created by
dissolving verdigris in vinegar, and then boiled
to create a green blue sediment. Used from the
early 1800s to the mid 1960s. |
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Viridian: Created in the
mid-1800s in Paris and is an opaque oxide of
chromium. Also mixed with zinc or cadmium yellow
to create permanent green. |
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White Zinc: Used in art
since the early 1800s through today, white zinc.
Created from a raw material, white zinc replaced
lead white and is non-toxic. |
It has been our experience here at Art
Experts that people will often pay expensive fees to
have Pigment Analysis carried out on a painting, only to
be disappointed when the results do not answer all their
questions on the painting. Often this disappointment
stems from the fact that they have been unaware of the
limitations of scientific techniques such as Pigment
Analysis. The results of this technique are normally of
no use whatsoever, unless they are used in conjunction
with the expertise of an art expert.

Fete Champetre

Fete Champetre X-Ray
*This x-ray of "Fete Champetre" by
Jean Antoine Watteau can uncover metals and pigments
used in the painting. But can it really tell you if it
was indeed painted by Watteau?
In all honesty, Pigment Analysis by
itself can sometimes confirm a negative. All that
Pigment Analysis does is confirm that a painting is not
by a particular artist. Pigment Analysis alone will
almost never help you determine if it is by a particular
artist. Yet, when someone decides to authenticate a
painting they often do so, because they want
confirmation of a positive statement. If they have a
painting that is signed by Degas, they want to pay money
for a service that is just as capable of confirming that
it is a Degas, as it is of telling them that it is not.

Degas Danseuses Vertes et Jaunes, 1903
*Upon pigment analysis of this pastel
composition, a researcher may find that Degas used
emerald green pigment, created from a poisonous copper.
But how many other artists used this same kind of
pigment? Only research can truly determine whether a
pastel of this kind was truly created by Degas.
In order to illustrate this point,
let's take the example of someone who thinks they own a
painting by Vermeer and would like it authenticated.
Pigment Analysis may be able to tell them that it is not
a Vermeer as the results may show pigments which were
not in use in his time. However, if the result is that
the pigments found, were in use, this in itself is not
enough to confirm that the artist was Vermeer. This does
not mean to say that it was not something that was
painted in the time of Vermeer, it could very well have
been, but what the owner wants to know is whether it is
by Vermeer. This is the question he wants the answer to.
In order to find this out the owner of the painting will
need the help of an art expert; this person, who is an
expert in signatures, in the style of paintings of
various artists, as well as being well qualified to spot
forgeries, will be able to answer the question working
in conjunction with the results of Pigment Analysis. It
is therefore important for anyone reading this and
interested in having a positive identification of a
painting by a given artist to understand that Pigment
Analysis is only useful when used together with the
expertise of a qualified art expert.

The Art of Painting by Vermeer
*Vermeer would often use lead white
pigment in his paintings, as he certainly did for "The
Art of Painting." Vermeer would also use yellow ocher,
azurite and smalt. But how many other Vermeer forgers
use these same pigments at the same time? This is why
research is also pertinent.

The Adoration of the Magi, Brown and
Yellow Ochre
*There is some controversy over Da
Vinci's "Adoration of the Magi" concerning the brown and
yellow ochre used to color in this unfinished piece.
Some authenticators have argued that it was not Da Vinci
that added the brown and yellow coloring, but another
artist. However, this is not argued just because of the
coloring, but also because of the method that the artist
used to apply the paint.
We have spoken a lot about Pigment Analysis, but what
exactly is it? Well, it is a technique that is used to
identify the raw materials and pigments used in a
painting. A pigment is simply any material which results
in color. Pigment is the result of selective absorption,
therefore strictly speaking there is no such thing as
white pigment. Pigments work by selectively absorbing
some parts of the visible spectrum. In the coloring of
paint, a pigment is a dry coloring, normally an
insoluble powder. Of course different pigments have been
used throughout art history. Some of the oldest forms of
art are cave paintings, and even at this time pigments
were being used, but in a primitive form; prehistoric
man, mixed dirt and clay with saliva to make paint. In
the famous cave paintings at the Lascaux Caves in
France, charcoal black and other pigments was used.

Cave Paintings at the Lascaux Cave
Prehistoric man also used iron oxide
pigments to obtain the deep red colors that he often
used. Iron Oxide and other minerals continued to be used
in the Renaissance, and such painters as Michelangelo
used the natural red chalk dug from the earth to create
their masterpieces. Renaissance painters often used
terra verte (or "green earth") to create the under
painting shadow flesh tones. Of course as time went by,
man began to use pigments manufactured in laboratories,
and today there are very sophisticated chemically
manufactured pigments available.
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Charcoal |
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Natural red chalk |
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Terra verte |
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Iron oxide |
As a result of the fact that different
pigments were used throughout periods of art history,
the identification of the pigments in a painting by
Pigment Analysis can give art experts clues as to the
period when the painting was executed. The result of the
Pigment Analysis can also help the art expert to
conclude that the painting was not by a particular
artist. If the expert is brought a painting which the
owner purports to be by an artist from the sixteenth
century, and the pigment analysis shows materials which
were manufactured in laboratories only from the
nineteenth century onwards, then clearly this is not a
painting from an artist from the sixteenth century.
Likewise, if the expert is brought a painting of which
the owner does not know the date and the pigment
analysis shows terra verte then the expert will use this
as evidence of it being by a Renaissance painter.
However in both cases, not even the most sophisticated
Pigment Analysis procedure or machine can conclude who
is the artist that executed the painting, for this, the
human skills of the art expert are needed.
I hope now that readers will understand that Pigment
Analysis is essentially a technique used to identify
pigments and raw materials used in a painting. But how
exactly does it work? Pigment analysis falls into two
categories; invasive and non-invasive analysis.
The non-invasive techniques normally involve the use of
spectroscopy. When we talk about spectroscopy, we mean
the study of spectra, which is basically light. The
study of spectra is the dependence of physical
quantities on frequency. Spectroscopy therefore is the
study of light on matter and it is thus useful for
identifying substances and materials. Spectroscopy is
often used in physical and analytical chemistry. It is
also frequently used in astronomy.

Optical spectroscopy
The two non-invasive techniques of Pigment Analysis
using spectroscopy are called X-Ray Fluorescence
Spectroscopy, and Raman Spectroscopy. X-Ray Fluorescence
Spectroscopy (often known as XRFS) is based on elemental
analysis, and can be used to identify most elements with
an atomic number equal or greater to aluminum. It can
therefore not only identify pigments and materials in
paintings, but can also for example, identify the major
and minor elements in bronze works of art.
Raman Spectroscopy is based on the analysis of molecular
structural motives. There are some pigments that Raman
Spectroscopy is not able to identify due to the
fluorescence of binding materials. When this is the
case, XFRS may also be used to provide complimentary
results. Both of these techniques are applicable, and
are non-invasive as neither requires the taking of a
sample of the painting.
In contrast, Gas Chromatography is classed as an
invasive technique which requires a small sample of the
painting. This technique was used, for example, to
identify the wall paintings of the Mogoa Grottoes in
China, which is a world heritage site on the Silk Road.

Gas chromatography machine
Gas Chromatography is used to identify
organic substances, and is widely used by the
pharmaceutical industry. In the world of art it is used
to identify the artist's media, such as oils, resins and
waxes. In Gas Chromatography, a vaporized sample is
introduced, and carried along through a thin column by
an inert carrier gas where the sample components are
separated. The components are then flushed sequentially
from the column, through a detector. The end of the
column can be coupled directly to the mass spectrometer.
The mass spectrometer breaks up the constituents into
molecule ions which then pass through a magnetic field
that separates them, and allows the materials to be
identified.
This article could go on for many more pages explaining
the complicated physics and science behind the different
techniques of Pigment Analysis. At the end of the day,
the most important thing to understand is that they are
only techniques for identifying pigments, and materials.
They can not tell you who the artist of a painting is.
Paintings can often be authenticated solely using the
skills of a well qualified art expert, without recourse
to expensive scientific techniques.
Here at Art Experts it is often a case of collaboration
between art experts world wide. We aim to give the best
service possible, and if the skills of an expert in
France are needed we do not hesitate to call upon them.
We do not dismiss the role of Pigment Analysis when it
is needed, and we have enough experience to be able to
identify this need according to the piece of art
involved. When it is needed we work in collaboration
with one of the best laboratories in the field.
If you need to authenticate your painting, before you
write out a large check for Pigment Analysis, please
call us, and we can advice whether it really is
necessary. |