History of Ink and It's Development
Its greatest impact was to spread knowledge, in the form of the printed word, long before Johann Gutenberg invented the printing press in Germany in the mid fifteenth Century. Ink has been a dye since the dawn of man; early examples were a mixture of soot from wood smoke and animal fat, thickened with the gelatine from skins.
Ink is everywhere, its used to print the labels of the food in the supermarket, newspapers, advertising, regular and ballpoint pens.
Composition of ink
They are all comprised of two components, a vehicle and a colorant.
History of Ink.
The ancient Egyptians and the Chinese, both developed ink at approximately the same time around 2500. B.C. They used fine particles of carbon called lampblack for the colorant, and gums, saps or glues were the vehicles.
Despite the fact that ancient inks were crude efforts the ancients strove to make them enduring, so that the information they passed on remained a permanent record. The ancient Hebrew word for ink is “deyo”, which when translated means blackness.
Ink and its production has always been to a certain extent problematic, it has always had issues regarding durability, it fades when exposed to sunlight and different types of paper absorb different amounts of ink.
Between the eighth and the eleventh Century a chemical ink, iron gall ink developed from tannic acid and iron salt became a popular colorant bound by resin. To understand the chemical structure of ink it is necessary to understand the properties of the chemicals that have gone into ink production and why certain chemicals improve or debase its durability.
Water based inks have humectants added so that the resultant ink does not dry out too quickly. At the same time, the ink must have the correct consistency for its purpose and added biocides ensure the consistency. Sometimes a pH level is necessary and buffering additives stabilise the level. In today’s complex world, the ink must be compatible with the type of machinery using it. Inkjet printers have revolutionised the printing industry, but the printing heads are so sensitive several different types of ink have developed for them.
Inkjet ink does not use dyes as the colorant but pigments. despite the early problems with inkjet ink the process has now been improved so that colours do not fade and lose their brilliance outdoors in bright natural light. This development itself has revolutionised many aspects of the printing business not the least of which is in the sign industry.
Types of Ink
There are three basic types of ink.
Inks using a pigment plus a binder, Chinese ink sticks are in this group where the pigment is soot. In general, ink sticks are regarded as the best general type of all-purpose inks, though there are differences in properties especially when writing on modern paper.
Inks with a dyestuff added such as fountain pen ink.
Inks with a chemical precipitation added such as Ferro Gallic (iron gall) inks.
India Ink (Chinese Ink)
The Latin name for all these types of carbon (C) or cinnabar (HgS) based inks ink was “atramentum librarium”.
Carbon inks are made of finely powdered lampblack, a type of carbon, held together by glue. The Chinese tend to apply it with small brushes, rather than pens. India ink is in liquid form is made by mixing gum Arabic, shellac, and borax, and then the carbon is suspended in the liquid. Sometimes the Indians add camphor to the ink. Borax and shellac react chemically together to produce a soap, which is soluble in liquid form, but is insoluble once it evaporates. Indian ink is a writing ink, but its widest application is as a drawing ink. It is popular with artists and for technical drawings. It has fast drying properties and an intense concentrated black color, but it is viscous, hence its popularity as a paint. If the formula includes bichromate of ammonium or potassium and the ink is exposed to sunlight, it becomes insoluble and it cannot be removed even with modern chemicals.
One of the earliest examples we have of this type of ink is on the Dead Sea Scrolls, which date from the third Century B.C. to A.D. 68. However, this base was a red cinnabar (HgS) rather than carbon. Once the liquid in the ink dries the C or HgS leaves a permanent mark. Chemically this reaction lasted longest when the writing was on semi absorbent material such as paper or papyrus; they do not make a good writing medium for parchment.
Carbon inks should be used on paper which is just slightly absorbent because the coloring material is suspended in the liquid. Writing with this ink on a non-absorbent surface will flake off when it evaporates, but it is very permanent when used on absorbent materials. The difficulties of Indian ink was the process of flocculation, which causes particles suspended in water to aggregate into flakes large enough to sink to the bottom of the container. Some early ink recipes had plant juices added rather than water, and gum Arabic to bind the ink. Its primary use is a stabiliser, but it does control the viscosity of ink, it also binds watercolors with the addition of honey, a humectant.
Traditionally Chinese ink was not bottled, but the ink was watered down when required by grinding the ink stick in an inkstone, which doubled up as the inkwell. The soot was normally made from pine oil or lacquer, a tree sap soluble resin was used to bind the ink and hold it in colloidal suspension.
They burnt resins of tar or oil, and then honey or gum was added to bind the tablet, before the whole mixture was compressed and dried. Later water was added when it was necessary to write with it. The early ink compressed into tablet form for two reasons; there was a shortage of bottles to store ink, and it was easier to transport.
The Chinese created raised hieroglyphics by mixing smoke and oil and the gelatinous content of animal skin, then they added musk to make the finished product fragrant. They required a process to blacken these raised hieroglyphics, they perfected the manufacturing process of Indian ink roughly around 1,000 years B.C.
Many ancient civilisations had dyeing arts; some of these techniques are still employed today. The colors were, in general, magenta, purple, blue, red, yellow, green, white, and black. Different colours were used to display a characteristic pictorially. Green meant regeneration, re-growth, but it was also the colour used to denote prosperity. Purity was epitomised by white, which every society recognised as innocence as conversely blackness meant disaster, misfortunes, and suffering. Blue was the chosen celestial color, it represented revelation. In Hinduism it meant to be lucky, it was an auspicious colour. India made a cyan colored dye. Scarlet became the universal symbol of life as it most resembled blood, while purple was the colour of kings.
Many of the ancient dyes were natural. The cuttle fish secreted one of the earliest inks, a brown-black dye, it created a smoke screen to confuse the cuttlefish’s enemies. Many pigments and dyes were used to achieve the coloration, the blacks were commonly charcoal or soot, while the white was white lead. Cleaned earth dirt made all of the tan, ocher, sepia, Sienna, browns, and earth red pigments. The rusted earth iron could from make yellow or red to dark brown, when silicon was added to the brown, naturally, we got translucent Senna. Firing any brown made it a redder brown.
The blue achieved to dye material came from wood, the ancient Egyptians used cobalt and oxide of copper. The yellow dye normally came from plants saffron, turmeric, and weld. Red's pigments were minium or red lead and vermilion. Scarlet came from an Arabian insect called Kermez, and the name crimson is derived from this as the dye cochineal is extracted from a beetle. Pliny named it granum, as it resembles a berry. Kermez from Armenia was a common dye until the Spanish brought cochineal back in the middle of the sixteenth century. The cochineal colour was richer and more vibrant and despite being far more expensive to use.
Indigo was in common use in India and Egypt long before the Christian era. The cyan strips of material used around mummies by the ancient Egyptians have been carbon dated and they originate about 2500 B.C. Transparent indigo was developed in India as the cyan ink, at the same time Egypt made the opaque scarabs that were crushed and used as a glass frit pigment paint. The Phoenicians distributed both in the Mediterranean area. Madder is a vegetable dye used for Centuries, a piece of clothe dyed with the madder root has been found in the tomb of Tutankhamen.
In 1988, the Vatican allowed three pieces of the Shroud of Turin, to be independently tested. The University of Arizona in Tucson, Oxford University in England, and the Swiss Federal Institute in Zurich, all tested it with state of the art carbon dating materials. Chemical and microscopic analysis, has revealed that a madder dye and a mordant and gum mixture, had been wiped onto the cloth at another time. This would indicate that the Shroud had undergone repair at some stage.
Cloth was once one of the most important commodities for trading, and the basis of many early industries, and the fabric dyes were worth their weight in gold. The colours found in nature the sepia browns and blacks, were relatively cheap, but the brighter colours were more expensive because they were more difficult to produce. The reds were especially difficult and purple has been associated with royalty. While sepia is the longest lasting of the natural stains because one drop of sepia renders a thousand drops of water obscure, and the ink fades when exposed to light.
“Your sail was of fine embroidered linen from Egypt So that it became your distinguishing mark. Your awning was blue and purple from the coastlands of Elishah”. Ezekiel 27:7
When Ezekiel wrote these words, he was referring to the people who lived on the coast of Aeolis, who were famed for their wool dying skills.
Pliny the younger confirms the expense of the dye.
“The Tyrian purple was the juice of the Purpurea, a shell-fish, the veins of its neck and jaws secreting this royal colour, but so little was obtained that it was very rare and cost one thousand Denarii per pound.”
Ancient writings compare the Tyrean purple to be the approximate deep colour of the blood of coagulated bullocks. The people of Tyre were not the only civilisation to utilise a purple dye the Phoenicians obtained the dye from shellfish, Buccinum found on land and Pelagia, which was from the sea. The Buccinum shell-fish itself yielded two colours, the shells found along the Atlantic coast was darker, while the Phoenician coast shellfish was a scarlet dye. Modern archaeologists believe that the Tyrian dye works operated about 600 B.C. and the dye came from a mollusc, the Janthina prolongata, which was then an abundant shell in the Mediterranean region.
Many of these natural vegetable dyes were employed as ink. As it was not set with morter, it was certainly not permanent and water will dissolve the ink. It was not until the middle ages that the story of ink was bound to the history of writing materials. Paintings remain from the time of the ancient Egyptians that have many colours and ancient hieroglyphic writings are written in more than one colour. The Egyptians had two types of paintings, fresco (painted on wet lime which absorbed the colors completely) and cara-colla (wax), there is no reason why both types could not use the same pigments. The pigments can be found in their Fayian grave paintings which are cara-colla or their frescos. Usually dirt earth pigments. The precise construction of ancient inks has been lost over the Centuries. What appears to be certain is there was a form of writing in Egypt and China long before the art of handwriting was perfected in Europe.
The ancient Greeks were too proud to consider the civilisations of other nations except perhaps the Ancient Egyptians, and they altered the language of the people they conquered, and rewrote their history books.
They were a conquering nation and even their concept of democracy was built on war and war councils. Under threat from the Persian Empire, they rewrote history to suit themselves, but then history has always been the story of the victor rather than the vanquished.
“There is the utmost uncertainty in the chronology of ancient kingdoms, arising from the vanity of each claiming the greatest antiquity, while those pretensions were favoured by their having no exact account of time.” Isaac Newton
Certainly, the tablets of ancient writings have been more important than the ink. The stone on which Moses wrote the ten commandments, the pillars in Crete on which Corybantic ceremonies were recorded. Many of the of the oldest writings were intended to be preserved, when God instructed Moses to write the ten commandments, there is an assumption that Moses understood the instruction, when Noah was instructed to build the ark he was given precise instructions, but there was no such command to Moses.
Character writing was begun on stone, then later clay or wax tablets, and a sharp pointed instrument was used. Some ancient Egyptian obelisks carved in this way survive today such as Cleopatra’s Needle, which stands in Central Park, New York, this stone dates to about 1500 B.C.
The Persians developed Clay tablets, while the Greeks used tablets of metal or ivory, the Romans used beech and fir, first coating them with wax. These forms of waxed writing tablets were in common use amongst scribes until the middle ages. Hebrew Scriptures were written on one side of skins, so that they could be rolled up and preserved.
It has been recorded that a copy of the Samaritan Pentateuch was written by the great-grandson of Aaron, Abisha, in the thirteenth year of the settlement of the land of Canaa, but that claim made in the dictionary of the bible is not substantiated by scholars.
The Romans had a word “encaustunt” for their purple ink with which they signed their edicts, a literal translation of the word means “burnt ink”. The French for ink is “encre”, or in Old French “enqwe” and the old English word is enke or ilzke; all of these words are probably a shorter version of encaustunt.
Ink was used by the Egyptians as early as 2500 B. C, when they wrote on old papyri, which is still in existence today. Papyrus was made by taking two pieces of rush and crossing them at right angles, and then sticking them together. The trimmed ends made a rectangular leaf, which was capable of withstanding pressure when pulled in any direction because the fibres at right angles made it strong. Once one leaf dried about twenty were stuck together to make a continuous scroll. The drawback with the early papyrus was it could neither be folded nor creased, as it was extremely brittle; it had to be wound around a metal or wooden roller.
To write on this new soft material rather than stone meant using reeds and then pens, as well as a semi fluid writing material. Early Christian paintings held at St Catherine’s monastery depict books, the reeds used for writing, and the inkstands.
Pliny, the Elder (A. D. 23-79), mentions that writing could he removed by means of a wet sponge. Martial (A. D. 100), a Roman Poet, always sent a sponge when he submitted new works of poetry, so that any of then could be deleted by his publisher. Although the Roman oil carbon ink, could not have been removed by water, it is likely to refer to the natural sepia ink.
Somewhere between the early civilization of Egypt and the Roman Empire, the art of ink production declined and became almost a lost art. It was not until about 200 A. D. that the employment of ink began again. Part of the reason for this may have been the disputes between the priests and the writers’ about what could and could not be used as ink. As we have seen Judaic law declared that only natural products could be used and these would have been water-soluble. However for whatever reason the basis of the pre Christian inks are lost to us.
The transition from the carbon based inks to the iron gall inks, which are the basis of the blue black writing fluids of today, took place gradually from the tenth to the twelfth century. It was at the same time that the development of flax or linen began to be used as an early form of paper.
The raw materials for the iron gall inks were the gall nuts and the iron sulphate, both common materials in ancient Syria.
The monk Theophilus, makes the first known reference to iron gall ink in an encyclopaedia of Christian art, during the eleventh century. He describes a method of ink preparation from a tannin bearing bark called thorn wood. The wood was first soaked in water, and then dried out; it was then mixed to a powder with green vitriol or iron sulphate.
Albertus Magnus (A. D. 1193-1280) also refers to the preparation of an ink from green vitriol in his treatise De Rebus Metallicis. Pliny’s writings have recorded ink made from soot, charcoal and a gum, although he neglects to state the type of the gum. However, he does mention that addition of acid, normally acetic acid (vinegar) was a binding agent to adhere the ink to the papyrus.
At this time, two acerbic substances were added to black ink, a yellow additive Misy that was a yellow colored earth and a slimy mineral sediment Salsugo. Salsugo was referred to as “kalkanthum” or “chalkanthum” and it was sulphate of copper. Once it was mixed with lampblack or other black substances, it became an acceptable writing medium to the priests. This type of ink was called blue vitriolic ink for several Centuries, its disadvantage was that it was extremely corrosive, it not only eroded the delicate papyrus, but also vellum, and parchment.
By the third Century A.D. the art of ink making underwent a revival, many ancient formula’s were revived. Red ink dyed vermilion by mercury, sulphur and potash or cinnabar was still popular as was ink dyed blue by indigo, oxide of copper or cobalt. Chinese ink was available for trade, as was the Tyrian purple. It had become popular to embellish writings with metallic gold or silver and specialist writers came from the East as far as Rome to illuminate manuscripts. These authors had their own jealously guarded secret ink recipes.
Julius Capitolinus wrote about gold lettering on a purple background in his biography of Emperor Maximinus the Younger. (305-313 AD). Emperor Maximus achieved fame by trying to suppress Catholicism and ordering the execution of St Catherine, whose bones were then sent to the monastery at Sinai, and today holds many ancient manuscripts from this era.
However although manuscripts have survived from this era, most of the ink has not survived. A copy of the Four Gospels was discovered in the Tenth Century although it was written in the Fourth Century, with Indian ink. However many of the older writings were in fact destroyed. In 390 A.D. the Roman Senate ordered many of the books and manuscripts in Italy and Greece to be burnt, as Rome began to adopt Christianity many older manuscripts of a pagan nature were systematically destroyed. Those that were not destroyed in this manner were destroyed in the early fifth Century when the Goths sacked Rome.
The Saracen destroyed the world-renowned library at Pergamus, the ancient name for Alexandria in A.D. 642, and with it the reputed half a million books it contained. The popular rise of Christianity did little to further knowledge and learning and the Middle Ages was commonly known as the Dark ages because the Church restricted book production to either Ecclesiastic books or a few medical textbooks.
The invention of the quill pen in the sixth century generated resurgence in the printing world. Ink had to become thinner and greater attention was given to was paid to composition. However, the spread of knowledge was still restricted to the cloistered religious world. The priests wrote the ink making recipes down and not for posterity but as instruction manuals for the younger priest scribes. Not all of these recipes yielded a satisfactory ink, though they did include soot and vitriol, they also included metal and stones.
The following is an extract of an instruction left by the monk Theophilus.
“When you shall have re-read this often, and have committed it to your tenacious memory, you shall thus recompense me for this care of instruction, that, as often as you shall successfully have made use of my work, you pray for me for the pity of omnipotent God, who knows that I have written these things which are here arranged, neither through love of human approbation, nor through desire of temporal reward, nor have I stolen anything precious or rare through envious jealousy, nor have I kept back anything reserved for myself alone; but, in augmentation of the honour and glory of His name, I have consulted the progress and hastened to aid the necessities of many men.”
Early medieval ink
The development of black ink improved in the Eighth Century towards the later chemical inks. In one blue vitriol, yeast from the lees of wine and the rind of the pomegranate, was used during the reign of Charlemagne, the text still survives intact today, and the British museum has several examples of texts written with pomegranate ink. The Latin word “clericus” or “clerk,” in effect meant priest, literacy was taken as proof that you had taken Holy Orders. Even the verb to sign a letter evolved from this time. If a letter written by a priest had to be authenticated by a monarch they were instructed to place a sign next to the sign of the cross, which was next to the name of the scribe.
The history of writing in England was passed through Benedictine monks who established a school of writing and illuminating in Ireland during the Seventh century. Later they passed the knowledge to their brethren in Scotland. Each Benedictine monastery had a scriptorium or a place where writing and illuminating was carried out. The situation for this was chosen very carefully using the best natural light available, candles any form of artificial flame were banned lest it damage the manuscripts. The fame of the Irish Benedictine monks spread far and wide, scholars travelled from the rest of the world to study the Greek language and the Irish monks travelled to Gaul, Germany, Switzerland, and North Italy.
“The Book of Kells, named because it was preserved and kept at the Monastery of Kells, which was founded by St Columba, was written in the Seventh Century and it is an example of the style and excellence of the Irish literary schools. The four gospels in Latin are unique, it has been written and illuminated in the insular style not found anywhere else but Ireland and England. It comes from the Latin which means island style and it differs in form from the writing and style of other contemporary European works.
A popular medium was parchment or processed sheepskin, but the carbon ink on this substrate was not very successful because of the lanolin content making the surface greasy. Experiments led to tannic inks being developed, although initially the ink was transparent. The slow chemical reaction between the salts and the acid penetrated the paper and left a darker residual mark. Gum Arabic improved both the keeping qualities and the inks flow because if too much acid was added it ate through the paper.
Gall ink and linen paper both came from Asia, but despite the fact that little was known about chemical reactions the use of this type of ink spread. The secret of this type of ink came from the Arabs, through Spain, then France, until the knowledge reached the Vatican, and the Church spread its use. The Moors at the same time spread the manufacturing process of paper. The art of making papyrus began to decline in the Seventh Century and it had ceased to be made at all by the early middle ages. However as little new information was being written there was not much call for something to write on.
Parchment was so scarce and expensive that it had to be re-used. The lamp black carbon ink was not caustic, as it did not sink into the parchment, so the ink was easy to remove using a weak alkaline solution and a pumice stone. This does not entirely obliterate the ink but it became relatively indistinct and it could be rewritten on. Manuscripts rewritten this way are palimpsests and there are many examples of these writings in all the major European libraries. In some cases, original copies of the gospels can be seen underneath medieval sermons, in other cases the writings have been erased so that they cannot be read.
Early paper was known as cotton paper and it was of a very inferior quality, it was coarse with many knots. In 1221 the German monarch Frederick II, decreed that no public document was to be written on cotton paper, and the scribes had two years to transfer all government documents onto parchment. Better quality paper was available it was linen paper, which was durable, strong, but flexible, but it was not popular as it was very thick. The art of polishing paper was standard practise for the Persians, the paper was rubbed down and refined, but this practice was not normal in Europe. While paper was available it was considered an inferior medium to vellum. Vellum was made from fine parchment leather and by the fourteenth Century all the books that were considered valuable manuscripts were written on Vellum. Even by the Fifteenth Century less than a fifth of all books were written on paper.
It has been estimated that Florence produced more manuscripts in the Fourteenth and Fifteenth centuries than the rest of Europe put together.
It was not just writings in ink, but the richness of the illustrations, they illustrated their sacred books and their daily missals. Pope Nicholas V, (1397-1455) was nicknamed “Tommaso the Copyist” before he became the Pope. He is reputed to have donated five thousand books to the Vatican all of which were his creations. As Pope, he created the Vatican library. He wrote to the Enoch of Ascoli in 1451 just before his death to discuss the plan. He created the Bibliotheca secreta, Bibliotheca latina, and Bibliotheca Greaca. The bibliotheca Greaca was a vast establishment for translating the Greek classics; he preserved the works of the work of Herodotus and the work of Thucydides. After becoming pope he was nicknamed the Humanist Pope because the knowledge was intended for all not just the clergy.
Clerical and Abbey libraries were under the care of an “Armarian,” who had the sole charge of preserving the manuscripts from damage from insects, light or dampness. He had a record of every book borrowed and by whom and had a complete catalogue of all the books in his care. Some of these catalogues have survived to the present day and it serves an in interesting testament to the names of authors lost forever. Part of his duties was also to write the contracts for the books to be copied, and also assign the materials and supervise the quality of the work. The Armarian was also responsible for the work carried out in the scriptoria, which were adjuncts technically of a library, but at the time adjuncts of a Christian library; a room devoted for writing.
Some of the monks had skills in all branches, writing, book binding and illustrating; however it appears to be more normal that the work was specialised. When a work was being written color was important and the term “rubric” describes a printed title, heading or a beginning word of a paragraph, distinguishable from the other text because it was colored. In general pigments were not used for writing except the embellishments of capitals.
In the Middle Ages both the carbon inks and the iron gall and iron tannin inks appear to have been in common use, although it is presumed they superseded the carbon inks as the secret of making a satisfactory carbon ink was lost. The iron gall inks from the Eleventh Century until the middle of the Nineteenth Century were known as oxidised inks, as opposed to the unoxidised blue or black inks.
They were referred to as oxidised inks because the process of making them mixed the gall or tannin extract with iron sulphate and gum, which was then oxidised or exposed to the air until the insoluble iron tannates remained in suspension in the liquid. However, gall ink was not a successful writing ink as most of the ink remained on the surface of the paper, rather than sinking into the paper and this was because iron tannates were precipitated before the ink was used. If the ink does not penetrate into the writing fibre it cannot be permanent, to achieve this permanence the ink should oxidise after it comes into contact with the paper.
Writing inks are fluid substances containing a solution of coloring material or the coloring material is suspended in the liquid. The colouring material can be any type of pigment that can be suspended or dissolve. Inks are classified into;
Aniline inks are used when printing plastic materials, which contain shellac, or synthetic resins, or methyl alcohol. Aniline inks are made by dissolving aniline or coal tar dyes, in distilled water and adding a preservative. Common preservatives are phenol, or carbolic acid or thymol, and they are added to prevent the formation of mould.
About a fifth of an ounce of the dye is added to 1000 c.c’s of distilled water. They are fugitive or washable inks and they do not corrode metal pens. Washable when used in the context of ink means it is capable of being washed out of fabric without damage to the fabric or the fabrics color. By washing the ink, you do remove its color, but by writing with this ink the dye is deposited as the ink evaporates, there is no chemical reaction on paper. The new aniline inks were less corrosive than the tannic gall inks, and the range of colours available was larger than that of any other ink, but they smear when wet and also fade with exposure to light. In certain parts of the world aniline inks are used as a dye, the Fijians have long used blue ink to dye their straw hats a rather distinctive shade of blue.
Logwood inks are manufactured from extracts of the Haematoxylon campecheartzim tree mixed with crystallized sodium carbonate and potassium chromate. The pieces of wood are purchased as small chips and they are steeped in boiled water to extract the dye. The ink dries easily into a purplish black which becomes a concentrated black on the surface and in the paper. It can be washed, but when exposed to air it decomposes into small flakes.
Nutgall or iron tannin inks are made from gallic acids and ferrous sulphate, or green vitriol. When mixed together these chemicals form a substance which is virtually colorless, but which darkens when it is exposed to air. Once the ink comes into contact with paper it reacts with the paper fibres, forming a black iron compound in the fibres, which will last as long as the paper survives. Unfortunately, an almost colorless liquid is not much use as a writing material so an indigo or water-soluble blue aniline dye is added. As the ink writes the colour is blue, but with time the blue fades leaving a predominant black, which results from the oxidation of the ferrous tannate and gallate. Blue black ink describes the inks which write blue but become black. Because of the permanent nature of nutgall ink they are used for recording official documents.
The chemical iron tannim ink can form quite naturally, in Algeria there is a River of naturally occurring ink. Two tributaries join and one of the streams runs through iron enriched soil, and the water has absorbed the iron content. The other stream comes from a peat swamp and has tannin in it. When the two streams joined, there is a chemical reaction between the tannic acid, the iron and the oxygen in the water, which causes black ferric tannate, or ink to form.
The nutgalls are abnormal growths of the oak tree, the Quercus infectoria, which is abundant in the Middle East. They yield Aleppo galls which make the most suitable tannic acid for the manufacture of inks. Tannic and gallic acids in solution gradually turn a light brown when exposed to air, before they react with the ferrous sulphate to develop black. It takes time for the black precipitate to form and to prevent this occurring while the ink is still in the ink well sulphuric or hydrochloric acid is added to the ferrous sulphate which prevents this. The acid makes it more soluble which means that it penetrates the fibres of the paper and prevents the ink from clogging the pen.
The city of Baltimore suffered a fire in 1904 and one of the city jewellers J. McDonald burnt, and their commercial records lay in water for week, once they were recovered and dried out, they were still legible.
This type of ink is the ink of espionage and subterfuge, referred to as sympathetic, or secret ink. It can be made from common foodstuffs, for instance the British used rice starch to manufacture Invisible ink during the Indian mutiny in 1857. The most common of the sympathetic ink is one made from cobalt chloride, when diluted before writing the ink dries to a very pale shade of pink, but once the ink is warmed, it becomes a clear and distinct blue. When phenolphthalein is added to the ink it remains invisible until it is exposed to ammonia vapours. Some of the earliest invisible inks were lemon, orange or onion juice it had to be scorched to make it visible, because it is an undigested juice, once heated they return to their natural colour.
Typewriter ribbon inks
The base of typewriter ink is usually castor oil, because it is slow drying and it is then mixed with oleic acid to which ground coloring agents have been added. To get the ink onto the ribbons is an art in itself. The ribbon is passed through rollers, which have been set at a specific distance apart. Most typewriter ribbons have two colours, but each section is inked at the same time from two separate reservoirs of colour. There has to be a partition at the rollers to prevent the two inks from merging. Even so, the viscosity of both inks has to be equal if it is not the colours will blend. The finished ribbon has a line in the centre, which is the width of the partition.
If one uses a typewriter continuously the ink begins to fade, because the later words are not as clearly pressed onto the paper. This is because the ink has been used, if the user leaves the ribbon for an hour the ink will flow back into the ribbon.
The first printing inks in use until 1864 were made from burnt rosin, turpentine, pitch, and petroleum oils. By 1864 the carbon black was made by burning natural gas rather than rosin, although lampblack made from the resin can still be added to printing ink.
Historically printing was a technique to apply under pressure a quantity of coloring agent onto a specified surface to form text or an illustration, it involved a press, lead and ink. When printing colours the combination of colors is achieved by submitting each sheet to successive impressions by type form each of which his designed to carry only a single color. There is sufficient wavelength in the three primary colours of magenta, cyan and yellow to make every colour when they are combined. We see colour from an inked impression because the ink reflects some colors so we are aware of them, other colors it absorbs which in effect means that they are masked from our sight.
Magenta, cyan and yellow have sufficient colours in their wavelength to reconstitute all the colours in the spectrum when they are combined appropriately. Yellow absorbs all the wavelengths of colour in the blue band, but it reflects any colour of red and green. Magenta totally absorbs green and it reflects red and blue. Cyan being close to turquoise absorbs red and reflects all blue and green. When any two of these ink colors combine, both annul the capability to reflect any of the two primary colors that it cannot itself reflect. The eye then perceives only the one primary colour that inks are capable of reflecting. When yellow and magenta are mixed, the only color they can reflect is red. Once the three inks are combined, they are incapable of reflecting any colour and they appear as black.
Nowadays illustrations and text can be reproduced without a press and a coloring agent. The print monopoly has been broken, printing has allowed the explosion of knowledge in many forms, and it is precisely the number of these applications that has challenged the role of the printing press. By its definition, it has produced newspapers, books, periodicals, textiles, plates, ceramics, microfilm, radio and television.
The age of print banished forever the dark ages, it heralded a new age of discovery, which would herald a modern world. When the printing press was discovered there was a rise of a new economic class, the feudal aristocracy was in decline and a new mercantile class based on trade was burgeoning. The trade generated by the Flemish cities, and the Italian republics fulfilled economic ambitions, but ideas were to change rapidly the religious crisis would deepen and create the Reformation. This new breed of commercial merchants also had political ambitions.
The first role of the printed book spread literacy, once literacy was established then the concept of general knowledge became possible.
The first books published often had a scientific based as well as contemporary literature. Later it was used to publicise Catholic and then Protestant tracts.
William Caxton was the first British printer and despite the fact that less than forty of his books are still in existence today, he revolutionised life in England. He was born in Tenterden, Kent in approximately 1422 and he died in 1491. His translation and print of “The Recuyell of the Historyes of Troye”, was the first book printed in English in 1474, it was a translation of a contemporary French romance. During the course of his life, he printed nearly one hundred publications and about a fifth of these were translations from the original Dutch, Latin or French manuscripts.
The more famous books from his press include The Canterbury Tales, and also Troilus, and Criseyde both written by the renowned English poet Geoffrey Chaucer. He also published “Confessio Amantis” by another English poet John Gower. “The Game and Play of Chess Moralised” was a translation of the first major European work on chess, it was the first printed book in English to make extensive use of woodcuts.
His printing press shop was in the borough of Westminster at the sign of the Red Pale. Here, he published such major works as Troilus and Creseide, Morte d’Arthur, The History of Reynart the Foxe, and The Canterbury Tales. The early typefaces used by Caxton were all varieties of “black letter” or “gothic” type. By 1490, he had acquired a more round and open typeface, a textura originally used by the Parisian printer Antoine Verard and later used more extensively by Caxton’s successor, Wynkyn de Worde.
The printing press was developed in Europe rather than in China or the orient, and there was a practical reason for this. Occidental writing characters, is based on an alphabet with a small number of letters. Chinese calligraphy has over 80,000 distinct symbols, and this vast number meant that it was technically more difficult for the moveable type to be manufactured in a series.
To prevent any new discovery from being lost there must be publicity, and the advent of publicity was suppressed in the dark ages. For new paradigms to grow and develop, the error of one hypothesis must be proved, and a new concept better fitted to contemporary facts must prevail. The problem with new paradigms is that they must fit their age and the civilizations of ancient Greece and Rome did not require printing.
Typography would not have bestowed any advantages on society. Writing was carried out by educated slaves, booksellers flourished, and wealthy publishers had few expenses other than feeding and clothing the slaves.
Books were present everywhere in Rome, even in the public baths, in part because they were so cheap and easy to produce.
Ancient Roman printing was not confined to books, a daily newspaper “Acta Diurna”, recorded the official business of the Senate, as well as city gossip. It was dispatched to the far flung parts of the empire to bring a taste of life on Rome, for the Roman soldiers many of whom spent years abroad, and often settled in the conquered lands.
Once the Roman Empire declined so did the need for knowledge and printing declined. By 500 A.D. Emperor Justin was illiterate, he was forced to leave his mark on state papers rather than sign them. By the end of the Seventh Century, books were so scarce in Rome that the bishops of Germany were asked to send some of theirs.
The printed word created its own impetus for questioning and change, once knowledge became general more people could participate in the debate. This in itself precipitated more debate and discussion and this in its turn led to ideas being generated. Europe, witnessed a revival of the scholastic learning, new ideas from poets, orators, novelists, writers, philosophers, chemists, alchemists, mathematicians and astronomers, breathed new life into a dawning age. Thus the middle Ages, which had accomplished their work of social renovation, made way for the Renaissance, which scattered knowledge in the fields of Science, Literature and art. The Industrial Revolution and later the enormous technological advances of the Twentieth Century accelerated this change. It could be said that there were more ideas and inventions in the last hundred years than in the accumulation of all the ideas of history combined.
It has been predicted that with the dawn of a new age of information that the printed word will die out. However, this seems to be a rather dire prediction as the printed word does have its own advantages, but only time will tell. I cannot be alone in reading newspapers online rather than buying the printed hard copy. However, one of the advantages of the printed word is that it takes longer to produce than television pictures or audio, and it has a greater visual impact that tends to be memorised.
Many people find that watching news on the television gives such a fleeting glimpse that it tends to be forgotten very quickly. Another advantage of print is that it offers time to reflect on an idea, its permanence means that one can go back to it to study. Psychologically humans learn facts easier when they read tracts quickly several times rather than watching the same information on the television.
By the Sixteenth Century despite several styles of writing, the ink color in Europe was a uniform blue-grey color, whatever the medium written on.
As the color was the same on all mediums it appears that it was either a part of the process of manufacture or a dye. The following quote from William Shakespeare attest to the use of gall ink.
“Go write it in a martial hand; be curst and brief; it is no matter how witty, so it be eloquent, and full of invention; taunt him with the license of ink; if thou thou’st him thrice, it shall nor be amiss; and as many lies as will lie on a sheet of paper, although the sheet were big enough for the bed of Ware in England, set ‘em down; go, about it. Let there be gall enough in thy ink, though thou write with a goose pen, no matter: about it.” Twelfth Night William Shakespeare Act three scene 2.
By the Seventeenth Century there is a still a long way to go before there is a standard ink, but the fact that so much black ink remains that is as colorfast now as when it was new indicates that more care must have been taken in the ink recipes and the mixing of the ingredients. Pietro Caneparius, a Venetian physician and writer of “De Atrametis”, gives an extensive treatise about inks in particular the gold, silver and sympathetic ink.
“De Atrametis”, was published in London in 1660, and it is a reference book for its time as it contains many recipes and formula for ink as well as the notes on its composition. A Dutch Chemist Jacques Lemort wrote an article called “Ink Formulas and Colors,” and while he did not have new information that had not previously been recorded he did attest to the fact that gall inks were of a superior quality if care had been taken to make sure that they were properly compounded. Curiously, about this time a whole series of books were published in Europe about calligraphy and handwriting, but not the formula of ink.
Ink manufacturer must have been an industry for many people but we have little knowledge of it. A Frenchman, Monsieur Guyot, a chemist, manufactured and sold ink in Paris in 1609, and while there must have been many manufacturers’ before him, he holds the distinction of being the first recorded ink manufacturer of which a note remains. In 1626, the French government concluded an arrangement for the manufacture of a “gall” ink without any added colour. This was the start of the process of standardising the manufacture of ink.
The quality of ink was so inferior at this time that the Royal Society became involved. The Royal Society established in the middle of the 1640’s to meet once a week to discuss the ideas of Francis Bacon. They met to discuss scientific topics and it would not be much of an exaggeration to state that the History of the Royal Society in the U.K. was synonymous with the history of science.
Dr. Charles Blagden read his paper entitled “Philosophical Transactions” in 1787. He did conclude that the quality of contemporary ink was inferior to ink manufactured centuries before. Many gall inks, looked good when new but as they aged the durability and permanence of the ink deteriorated. However, while there were documents written in the twelfth Century that still had perfect ink it would have to have been taken into consideration that these were written with Indian ink.
Although William Lewis, an English Physician, began making experiments on ink in 1748, to determine the chemical components, necessary to make ink permanent. As chemical reactions were still not understood at this time much of Lewis’s work has been subsequently disproved. However, he did discover that an excess of iron salt affects the permanence of the colour of ink and it becomes brown as it ages. His experiments did not greatly contribute to the knowledge of ink, but he was the first to record that logwood as an excellent coloring agent in the gall inks.
Dr. James Stark, a chemist, undertook one of the most comprehensive studies of contemporary ink in 1832; he did not complete his experiments until 1855, when he submitted his results to the Scottish Society of Arts.
Dr William Inglis Clark in 1879 wrote his thesis, which was entitled “An Attempt to Place the Manufacture of Ink on a Scientific Basis,” He concentrated much of his work on the modern methods of manufacturing blue black inks. He departed from modern thought because he refuted the idea indigo paste kept the gallo tannate in solution, he decided that it was the action of the sulphuric acid, which was the vital ingredient. He also concluded that a hot water gall infusion was not suitable for blue-black inks, it had to be done in cold water. The excess tannin released with a hot infusion inhibited the action of the indigo as a colouring agent.
It has only been in the last hundred years that a standard has been adopted for ink. In 1890 Schluttig and Neumann, investigations, published a formula for what they believed to be the best iron gallo tannate ink. This formula was adopted by the State of Massachusetts as the standard ink for all its official documents. In 1912, the Prussian Government issued regulations requiring that documentary or record inks should meet certain standard specifications. The United States Government incorporated in its specification for “Treasury Standard” writing fluid the requirement that ink should conform to the standard ink of the State of Massachusetts.
The British government decreed that all ink used in the public departments are obtained by public tender, controlled by conditions set by H. M. stationery office. They are assisted in this task by the chief chemist of the Inland Revenue who test random samples of ink. In this way the British government hoped to ensure that the correct inks are used for each purpose.
Although most ink has a chemical composition, and it is possible to duplicate the formula exactly the resulting ink is not always the same. These differences are more noticeable in the inks made from nut galls, sulphate of iron and a gum and especially when the ink is black. However, the differences in the twenty first Century are not as marked because most are now manufactured by steeping the galls in a cold press, rather than the earlier method of warm water
Red is the most important colored ink in demand today, and its manufacturing process has changed. The colour used to be the natural cochineal dye made from beetle, but today soluble aniline red is added to water. Copying ink has two types, dependant on the amount of glycerine, or how soluble the pigment is in water, but copying ink is not recommended for record keeping. Apart from aniline colorings, added color for ink can either a color yielding compound or a color and a tannin. Some coloring agents can be added with tannin while others react and are best used alone. Many of the dyes used through the ages have not stood the test of time, light, humidity and heat. These affect all aniline dyes, if they are obliterated, they cannot again be rendered legible again. That is the principal reason why records, which need to be permanent, have used black ink.
Anilines, is an organic chemical compound now more commonly used in the manufacture of polyurethane, although its historical use has been a dye. The name itself derives from anil, the Sanskrit word from dark blue and later the Arab word for indigo.
So then, this is the first time, dark blue (made from cyan and magenta) and cyan (original indigo) (not today's blue-jean color), have been confused.
Early in the nineteenth century the development of synthetic chemical substances occurred. In 1825, Faraday’s experiments isolated benzole, which react with nitric acid to become nitro-benzole; when agitated acetic acid or vinegar and water and iron filings becomes aniline. At the same time mauve as a synthetic dye was discovered, by William Henry Perkins, when he was searching for a cure for malaria. Because this dye could be added to ink, it became commercially important. For the next fifty years, the number of discoveries of synthetic dyes was to increase and the Germans dominated the work as the Americans lacked industrial chemists to carry out the research.
Graebe and Liebermann synthetically produced alizarin, which was the coloring ingredient of the madder root. This was perfected in 1873 by Springmuhl who made a superior blue dye from anthracene, these new discoveries were kept very secret and the cost of the new synthetic dyes astronomical. Springmuhl’s original blue cost $1,500 for a pound. Later the reds were discovered, but the commercial cost of making these dyes still far outweighed the cost of extracting them from natural plant materials. However, these synthetic dyes were extremely intense compared to the natural product and a single grain eosine in ten million parts of water could be seen as a clear rose pink. It was not until 1897 that the commercial use of manufactured indigo was viable.
The advent of the personal computer has meant the need for home printers, and this has revolutionised the history of ink and its development. Early models of home computer printers used a process called impact printing, it worked by an electromagnetic print head, driving a number of pins into a pattern. As the pins were propelled forward, it struck the inked ribbon and transferred the pinhead dot to the paper. The pattern of the multiple dots formed either the letters or the characters.
However once this matrix of dots has been formed there are several ways of transferring the image to paper.
During the seventies Rank Xerox was one of the most powerful companies in the world. In 1959 they had developed the Xerox 914 the first plain paper office copier, and by they had formed the Palo Alto Research Centre opens in Palo Alto, California commonly shortened to Parc. Parc invented some of the world’s firsts, yet they failed to market, patent or capitalise on any of them. PARC invented the prototype of the world’s first personal computer, known as the Alto, though unless you are a geek you could be forgiven for not knowing that!
In 1981, Xerox unveiled the Star 8010, including the bitmapped screen, What you see it what you get editor, (WYSIWYG), mouse, laser printer, Smalltalk language, Ethernet, as well as software which enabled the user to combine text and graphics in the same document. Less than a hundred thousand units were produced and its launch was a total commercial flop.
Despite having the first GUI interface, the first commercial use of the mouse, as well as the first what you see is what you get editor. All of these were inventions were utilised by other companies such as Apple because Xerox having invented the technology was so arrogant and confident of its commercial position that it did nothing with it. In 1984, the Hewlett Packard company introduced the LaserJet laser printer, for sale US$3,600, they did not introduce a laser printer which retailed at less than a thousand dollars until 1990.
The story of the laser printer, yet another technology developed by Xerox PARC, epitomizes the lack of communication between the research laboratory and management that resulted in Xerox’s inability to capitalize on PARC innovations. Laser printers focus a beam of light, which etches patterns of positively charged ions, onto the surface of a cylindrical drum composing organic photosensitive material, which is negatively charged. The drum rotates and the negative toner particles adhere to the patterns etched by the laser and are transferred to the paper.
The inkjet printer is another example of a non-impact printer; they spray minute particles of ionised ink, which form a dot matrix, on the print surface. Magnetised plates that project the ink in a specific path determine the inks shape. They are capable of producing a print quality at home approaching that of the laser printers. There advantage is that they use smaller moving part and are cheaper to produce and buy. If they have a drawback it is that, they require a special type of ink and it does tend to smudge on inferior quality paper.
One of the characteristics of an inkjet printer is that the dots are minuscule, and are positioned precisely. The diameter of an average human hair is seventy microns, but the dots of an inkjet printer are between fifty and sixty microns.
The quality of print depends on the type of paper, standard photocopying paper will produce a printout, but the image will be crisper sharper and more bright if inkjet paper is used. The print quality is altered by both brightness and absorption. Paper brightness is defined by the roughness of the paper. The smoother the paper surface the brighter the resultant image will appear to be. When the light from the paper is reflected back in the same direction the image appears brighter, but this illusion is not achieved on coarse paper because it scatter lights everywhere in more than one direction. This can be illustrated by the fact that a glossy magazine illustrates a clear concise image and a newspaper does not. Dye has an opposite charge to the paper so the solvent soaks into the paper and the coating retains it.
Ideally, inkjet images print better when the ink remains in a fixed dot, which should be symmetrical, once the dot is absorbed by the paper the edges feather out and this bleeding covers a larger non symmetrical area. The effect of the feathering is to blur the edges and make them less defined, in other words fuzzy around the edges! High quality inkjet paper is formulated to prevent the feathering it prevents the ink from splurging a larger area than it should because the paper has been treated with wax which makes it impervious to ink absorption.
The waxed paper is the key to the success of the high-resolution capabilities of inkjet printer. Just twenty-five years ago, printing shops carried out highly expensive contracts to print images. Dots per inch (dpi) are a printing term, which means how many dots centimetre the printer can place on a square inch or centimetre. Typically most printers place the same number of dots both horizontally and vertically (some printers are different) that means a 720 dpi printer prints 720 vertically as well as 720 horizontally within the given area.
In general the higher the resolution of the printer, the better quality the printed product will be. With coated paper, the resolution doubles, because the printer shifts the paper, almost imperceptivity, and adds a second row of dots both horizontally and vertically; the image will not feather because there is no absorption.
With the introduction of inkjet printers, there was a new challenge, the development of a successful ink. Changing ink cartridges was certainly easier than either the dot method of changing a ribbon or inserting a toner cartridge. Inkjet printers have also had an impact on the processes used to make ink; it has become a truly specialised industry. Inkjet inks are both water and solvent based. The older types of inks that had dyes as a colorant were no longer suitable for inkjet printers.
Inkjet orifices in the printer are miniscule; the range is between ten and twenty microns, whilst a micron being one thousandth of a millimetre. The ink for the first generation of inkjet printers was problematical; the original pigments inks constantly clogged the machinery, until an effective detergent, which acted as a dispersant was added. Both dyes and pigments are dyestuffs, because although they have a different molecular structure they both come from the same root, indistinguishable organic chemical compounds. Dyes are a solution and their molecular structure is smaller than pigments, which are a heterogeneous mixture.
Dye molecules need functional polar groups, as the plates are magnetised, and it is this, which gives the ink the disintegrating quality that is necessary to dissolve in the vehicle. Because the ink disintegrates, it becomes smaller than pigment ink. Pigments stay in their particle form, which remains insoluble in the vehicle without the polar groups.
To prevent the pigments from clustering, ink makers must add a dispersing agent to the mixture, which in effect acts as a detergent. A complication in the use of pigment ink rather than the use of dye is that pigment is composed of several hundreds of thousandths or even millions of molecules, while a dye particle is composed of a single molecule. Pigments have the advantage as their tiny size means they become less damaged by exposure to the elements and ultraviolet light. In contrast, the singular composition of dye means that it can be demolished easily, quickly and utterly, the pigment structure means that it has at its disposal an infinite number of backup particles that stops deterioration. Although pigment ink is by definition more difficult to manufacture it is this type of ink that has revolutionised the sign industry, because it is more permanent on a wider variety of materials.
The dye molecules interact with the other ingredients, and they can benefit from colour enhancing agents to increase the intensity of the colour. When the electrons in the dye interact and move the colour materialises because of the light energy that falls on the dye. If the colour enhancer absorbs light energy, the spectrum of light reflected from the dye changes are various characteristics which are necessary for the functioning of inkjet printers they require
Droplets of ink identical in size
No clogging of the printer head
High optical density
Fade resistant when used outdoors.
Both solvent and water based inks fulfil these requirements; but water-soluble inks are more common, as they are used for the smaller inkjet printers designed for home use. Water based dyes are still classified as dye based and pigment based. Stable images cannot be guaranteed without ink injection being stable. Water-soluble inks consist of water, a colorant, anti-drying agent, penetrant, pH adjuster and a type of preservative or fungicide. Water-soluble inks using dyes are less likely to clog the printing head, but they run more easily. Water-soluble pigment inks have improved dramatically since the original concept and they are now considered superior.
|Water soluble dye based ink
Water soluble pigment based ink.
The colorants have been dissolved in the vehicle
High-definition colors over a wide range of colors.
High optical density with excellent colour.
The colours deteriorate and run.
They do not have good light and water fastness.
|Water soluble pigment based ink
The colorants have been dispersed in the vehicle
The colour does not change.
High light and water fastness, they do not tend to run.
They have low optical density.
They have a limited range of color
They have a greater tendency to clog the printer.
The reduced of available pigments as colorants means the range of colour is limited.
A solid inkjet printing system means that there is no drying procedure after printing, there are no solvents used with the melted solid inks. Chemically the ink is similar to the wax used in candle manufacture; it is made up of a plasticizer, stabiliser, viscosity modifier and colorant, which may be either a dye or a pigment.
Four Colour Process Printing
This is the most common method for producing a colour print for a book or magazine. Originally, the artwork had to be separated using photographic filters to produce four different printing plates, but nowadays the separation is carried out digitally. As most inks are transparent the proportions that they can be mixed in is almost infinite and they can produce a wide range of colors.
Today ink making is a specialist industry; each printing process requires its own classification of ink. Despite the dour predictions about the future of the printing industry, the ink bill in the United States is estimated to be several billion dollars per annum. The future of ink looks as secure now as at any time in its history. Between the 1920's and the 1960’s ink had its heyday before the advent of the biro pen, but home computers and printers have made the use of ink secure at least for the next few years.
Indian Ink is also called Chinese Ink, it is a black pigment in the form of sticks that are moistened before use in drawing and lettering, or the fluid ink consisting of this pigment finely suspended in a liquid medium, such as water, and a glutinous binder.
The sticks or cakes consist of specially prepared lampblack, or carbon black, mixed with a gum or glue and sometimes a perfume. India ink was used in China and Egypt Centuries before the Christian era and is still valued for its opacity and durability. In India, burning bones, tar, pitch, and other substances obtain the carbon black from which India ink is produced.
Ink is a fluid or a paste used for writing and printing it is made up of various colors, but is usually black or dark blue. It is composed of a pigment or dyes dissolved or dispersed in a liquid called the vehicle.
Intaglio inks are composed of petroleum naphtha’s, resins, and coal tar solvents. The intaglio printing process is used mainly to print rotogravure newspaper supplements and cartons, labels, and wrappers.