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The origins of paint.

The history of paint from past to present day

Paint is almost as old as the hills and during its immense lifetime the essentials have not changed. The earliest paint contained a pigment and a vehicle and the pigment had to be dispersed in the vehicle by some kind of shearing process requiring work.

Some method of application to different surfaces was needed.
What then has changed? Has paint improved? The answers lie in the ingredients, in the methods, in the end results. We must go back to the cavemen and follow the progress of paint, through the dawning of civilisation in early Egypt to Greece and Rome, to the artists and craftsmen of the Middle Ages and Renaissance and on from the Industrial Revolution to the present day.

Pre history

Primitive men are credited with making the first paints about 25,000 years ago. They were hunters and cave dwellers and were probably inspired by the rock formations of their cave walls to outline and colour the shapes of the animals they hunted - possibly in the hope that it would give them power over their prey.

Chemical analysis of cave paintings discovered at Altamira (Spain) and Lascaux (France) show that the main pigments used by Palaeolithic artists were based on iron and manganese oxides. These provide the three fundamental colours found in most cave paintings, namely, black, red and yellow, together with intermediate tints. The oxides were dug out of the local soil, possibly even from the cave floors. Carbon from burnt wood, yellow iron carbonate and chalk may also have been used. Surprisingly, there is no trace of white (today's commonest coloured pigment) at Lasceaux, where the natural colour of the rock was used as a pale background. However, white pigments do occur in some prehistoric paintings found in Africa.

The earth pigments were ground to a fine powder in a pestle and mortar. Naturally hollowed stones are thought to have been used as mortars and leg bones as pestles. The powdered pigments were most probably mixed with water or bone marrow or animal fats and possibly even with egg white or vegetable sugars to form paints. These were then applied by finger dabbing with pads of lichen, animal fur or moss, or with a brush made from hair or chewed twig. It is possible that paint may have been applied by blowing it down a hollow tube, such as a bone. These crude methods of applying paint are the forerunners of our current brushing and spraying techniques.

Cave paintings have survived because of their sheltered positions deep inside caves, which were subsequently sealed off. The paints had very poor durability and the binders served merely to make the pigments stick to cave walls.

Paint 3,000 BC to 600 BC

Simple paints were made from sour milk and lime. Water aided application, casein from the milk acted as a resin and the lime reduced the water sensitivity of the final paint film. These 'cold water paints' contained a water-soluble resin, thus differing from today's emulsion paints, which contain fine particles of polymer dispersed in water.
The Egyptians prepared surfaces for painting by priming, sealing or plastering them prior to finishing. Wood was normally primed, or coated with a layer of gypsum or whitening, prior to painting with lime-based paints, unless a single colour was used.

Wall paintings relating stories were painted on clay or gypsum plaster. The plaster was originally applied very thinly on walls and then finished by a primer coat to which glue, probably from curd (casein) of milk had been added.

Portraits were painted with a binder consisting of wax or a mixture of wax and resins. Buildings and statues were painted with gum-based paints and pitches and balsams were used for protecting ships. These paints were commonly applied by spatula, finger or with crude reed brushes.

Egyptian paints

Possibly the most obvious part of a paint. Pigments are fine powders that give the film its colour and help it to hide the surface underneath. They may provide other properties too, such as altering the way paints flow or providing corrosion resistance. Not all coloured powders are suitable as pigments. They must be insoluble in water. It is helpful if the pigment is chemically inert and colourfast when exposed to light.

Similarly not all white powders are useful as white pigments. Not only do we seek insolubility and inertness, but we want them to be opaque in use. If they are not opaque however, they may still be of value in a paint for other reasons than opacity. We call these transparent white pigments "ex- tenders". They may help to prevent pigment settlement in the can, act as a matting aid, and provide a micro-toughness of the surface to assist adhesion of the next coat or act as reinforcement to strengthen the film.

Coloured pigments range from simply inorganic compounds such as red iron oxide (Fe203) to complex organic pigments, for example, Dioxazine Violet.By far the most commonly used white pigment is Titanium Dioxide (TiO2) although Zinc Oxide (ZnO) and Lithopone (ZnS+BaSO4) find small use.

Many of the extenders used are naturally occurring minerals such as whitening (CaCO3) Barytes (BaSO4) Silica (SiO2) and China Clay (Al2SiO2.2H20).

Greece and Rome 600 BC to AD 400

The Greeks almost certainly appreciated that paint could preserve and protect objects as well as decorate them. Pitch was used for tarring ships and pitch and wax for protecting ships' bottoms. Clarified beeswax was melted on a heated brass palette prior to application by brush or spatula. The Greeks and Romans used similar binders to the Egyptians. In Roman times, drying oils and varnishes were also incorporated and the process was termed 'encasutic painting'.
Roman artists used a number of lake pigments including woad (blue dye obtained from the leaves of the woad plant and used as warpaint by ancient Britons). Artist’s colours also included Tyrian Purple. Tyrian Purple was a highly prized purple dye at one time reserved for the Roman Emperor's toga. It was obtained from a mollusc found in the Mediterranean. About a quarter of a million molluscs were required to produce an ounce of the pure dyestuff.

We know that professional decorators existed at this time. An early record (Marcus Terentius Varro 116 to27BC) posed the following question: "Would a house be worth less if it had not been decorated, or if it had been decorated and the owner lived in it with his donkey?"

Early Japanese paints AD 400

Japanese lacquer was a highly developed art in Japan and China about AD400. This lacquer was obtained as a sap from the Rhus Vernicifera (varnish tree) and dried by oxidation. Oriental resins included shellac, the resinous secretion from the lac insect, sealing wax, gum Arabic and natural tree saps. The commercial importance of tree sap was recognised in the seventh century AD when the Japanese put a tax on sap from the varnish tree.

Paint in the Middle ages and renaisance period. AD400 to 1600

During the Middle Ages much painting, especially on wood was protected by varnishing. The varnish was made by dissolving suitable resins in hot linseed, hempseed or walnut oil, all of which tended to darken with time. Honey, eggs and size were still used for distemper painting.

Pigments remained important articles of trade and in some cases were of similar value to precious metals and stones. White lead, the most important pigment was prepared by hanging lead plates in vinegar. The lead acetate so formed was converted to carbonate by carbon dioxide, in the air and the resulting mixture of acetate and carbonate, obtained as a white deposit on the lead surface, was removed, ground and boiled. Bone white (mainly calcium phosphate), cuprammonium blue compounds and verdigris (green) were commonly used pigments. The latter was made by moistening copper with vinegar and exposing it to air, or by packing copper plates in fermenting grape skins.

Artists pigments included extracts from various trees and plants, such as Logwood, Gamboge, and Mummy. Mummy was a brown bituminous pigment, which was prepared from the bones and bodily remains of Egyptian mummies, which had been embalmed with ashphalturn - a brownish black mixture of oils.

The Middle Ages saw the roles of the artist and craftsman becoming more closely defined, but whilst little progress was made in improving paint constituents and the mechanics of making paint, the period is renowned for developments, in artistic technique. Art forms had continually evolved from the caveman's primitive efforts, but with the discovery of oil painting (attributed to the Van Eyck brothers in Flanders) artistic painting received a great injection of talent and new ideas.

Arts, crafts and the Industrial revolution. 1600 to 1914

In the Middle Ages, and in the beginning of this period, the user of paint was also the paint maker. Artists sometimes achieved their special effects by secret paint formulations of their own. But though they worked to improve the effects they could obtain, their main energies were devoted to painting itself and it is not surprising that paints changed only slowly.

By the late eighteenth century, demands for paints of all types had increased to such an extent that it became worthwhile for people to go into business to make paint and varnishes for others to use. Factory production had begun. In 1833, J.W. Neil advised varnish makers always to have an assistant present (for safety). "Never do anything in a hurry or a flutter. ... A nervous or timorous person is unfit either for a maker or assistant, and the greatest number of accidents occur either through hurry, fear, or drunkenness".

In other ways, the Industrial Revolution was changing paint. The increasing use of iron and steel for construction and engineering purposes resulted in the need for anti-corrosive primers which would delay or prevent rusting and corrosion. Lead and zinc based paints were developed to fulfil these requirements.

Science was awakening and some of its discoveries became paint ingredients. Prussian Blue (K4(Fe(CN)6)3) the first artificial pigment with a known chemistry was discovered in 1704. In about l740, the use of turpentine as a paint solvent was disclosed. The role of lead and other metal compounds in speeding up the drying of oils became clear after 1840 and in 1856 Perkin synthesised the first synthetic dyestuff, mauve.

Science and mass production 1914

In 1903 Henry Ford founded the Ford Motor Company and in 1908 he launched the Model T made by mass production techniques. These techniques were to spread to Europe, but the First World War intervened.
At around this time, the petroleum industry was growing in order to supply fuel for vehicles and cars. In the process of making petrol a large number of side products were generated which resulted in a range of new liquids, hydrocarbons, alcohol’s, esters and ketones.

The war had accelerated the exploitation of the discoveries of chemistry and the growth of the chemical industry. New coloured pigments and dyestuffs, synthetically manufactured, became available and in 1918, the new whiter pigment, titanium dioxide, which was to replace white lead completely and make paints safer, brighter and better for 'hiding' or obliterating. Typical of the new organic chemistry approach to coloured pigments was the discovery of Monastral Blue (Copper Phthalocyanine). Pigments and resins could be now made from simple, pure chemicals by scientifically controlled methods.

Paint in the present day

Paint science has advanced rapidly since the world wars. The industry employs scientists in a large number of disciplines including: organic chemistry, polymer chemistry, catalysis, rheology, pigment technology, computing, colour chemistry, etc. The aim of the scientists is to understand why particular paint formulations work and how to make new coatings to meet modern day requirements.

Looking back

We have seen that the earliest paints were limited in colour, were not durable in unsheltered conditions and were crudely applied. They were suitable for decoration and not protection.
During the intervening years, changes have taken place at varying rates; sometimes progress was fast, sometimes at a standstill. The choice of pigments and resins widened. Some records of how to make paints and their ingredients were kept. Quality and durability improved. Paint making became a job and a skill in itself.

Then in the twentieth century the pace quickened markedly. The discoveries of science vastly increased the range of ingredients available. The methods of science ensured that their quality could be controlled and reproduced again and again. The demands of mass production industry and modern products set new standards for ease of application and speed of drying, for new bright colours, for durability and protection. The challenge set for the future is for all paints to be waterborne which requires dedicated scientists to understand paint chemistry and so create innovative new products.

This article was submitted by a user of this website and originally appeared on the website of ICI. We respect their trade marks and copyright, and issue this article as a resource. We do not infer that we have authored this, which we have not.