Forensic Research

 


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.

Brown Ochre

   

Yellow Ochre: (limonite)

   

Red Ochre: (haemetite)

   

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.

   

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.

   

Orpiment: The sulfide of arsenic, this yellow pigment was used 3,000 B.C. until the early 1900s due to  toxicity.

   

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.

   

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

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.

   

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.

   

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.

   

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.

   

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.

   

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.

   

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.

   

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.

   

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

Cadmium Orange: Created from cadmium metal, this pigment was first discovered and used in the early 1800s. Still used today.

   

Cadmium Yellow: Created from cadmium metal, this pigment was first discovered and used in the early 1800s. Still used today.

   

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.

   

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.

   

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.

   

Cobalt Violet: Discovered in the mid 1800s, cobalt violet is created by mixing cobalt with disodium posphate and heated at a high temperature.

   

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.

   

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.

   

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.

Charcoal

   

Natural red chalk

   

Terra verte

   

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.

 

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