INK, a black liquor used, in writing, generally made of an infusion of galls, copperas, and gum-arabic.
The properties which this liquor ought to have, are,
1. To flow freely from the pen, and sink a little into the paper, that the writing be not easily discharged. 2. A very deep black colour, which should be as deep at first as at any time afterwards. 3. Durability, so that the writing may not be subject to decay by age. 4. Ink should be destitute of any corrosive quality, that it may not destroy the paper, or go through it in such a manner as to render the writing illegible. No kind of ink, however, hath yet appeared which is possessed of all these qualities. The ink used by the ancients was possessed of the second, third, and fourth qualities above mentioned, but wanted the first. Dr Lewis hath discovered its composition from some passages in ancient authors. "Pliny and Vitruvius (says he) expressly mention the preparation of foot, or what we now call lamp-black, and the composition of writing-ink from lamp-black and gum. Dioscorides is more particular, setting down the proportions of the two ingredients, viz. three ounces of the foot to one of the gum. It seems the mixture was formed into cakes or rolls; which being dried in the sun, were occasionally tempered with water, as the cakes of Indian ink are among us for painting."
In Mr Delaval's Treatise on Colours, p. 37. he acquaints us, that with an infusion of galls and iron filings, he had not only made an exceedingly black and durable ink, but by its means, without the addition of any acid, dyed silk and woollen cloth of a good and lasting black. This kind of ink, however, though the colour is far superior to that of any other, has the inconvenience of being very easily discharged, either by the smallest quantity of any acid, or even by simple water; because it does not penetrate the paper in such a manner as is necessary to preserve it from the instantaneous action of the acid or of the water. During the action of the infusion of galls upon the iron in making this kind of ink, a very considerable effervescence takes place, and a quantity of air is discharged, the nature of which has not yet been examined.
The materials usually employed for the making of ink are, common green vitriol, or copperas and galls; but almost all of them are deficient in durability, which is a property of such importance, that Dr Lewis hath thought the subject of ink-making not unworthy of his attention. From experiments made by that author, he infers, that the decay of inks is chiefly owing to a deficiency of galls; that the galls are the most perishable ingredient, the quantity of these, which gives the greatest blackness at first (which is about equal parts with the vitriol), being insufficient to maintain the colour: that, for a durable ink, the quantity of galls cannot be much less than three times that of the vitriol; that it cannot be much greater without lessening the blackness of the ink: that by diminishing the quantity of water, the ink is rendered blacker and more durable; that distilled water, rain-water, and hard spring-water, have the same effects: that white wine produces a deeper black colour than water; that the colour produced by vinegar is deeper than that by wine; that proof-spirit extracts only a reddish brown tinge; that the last-mentioned tincture sinks into, and spreads upon, the paper; and hence the impropriety of adding spirit of wine to ink, as is frequently directed, to prevent mouldiness or freezing: that other astringents, as oak-
bark, bistort, sloe-bark, &c. are not so effectual as galls, nor give so good a black, the colour produced by most of these, excepting oak-bark, being greenish: that the juice of sloes does not produce a black colour with martial vitriol; but that, nevertheless, the writing made with it becomes black, and is found to be more durable than common ink: that inks made with saturated solutions of iron, in nitrous, marine, or acetic acids, in tartar, or in lemon juice, were much inferior to the ink made with martial vitriol: that the colour of ink is depraved by adding quicklime, which is done with an intention of destroying any superabundant acid which may be supposed to be the cause of the loss of the colour of ink: that the best method of preventing the effects of this superabundant acid is probably by adding pieces of iron to engage it; and that this conjecture is confirmed by an instance the author had heard, of the great durability of the colour of an ink in which pieces of iron had been long immersed: and lastly, that a decoction of logwood used instead of water, sensibly improves both the beauty and deepness of the black, without disposing it to fade. The same author observes, that the addition of gum-arabic is not only useful, by keeping the colouring matter suspended in the fluid, but also by preventing the ink from spreading, by which means a greater quantity of it is collected on each stroke of the pen. Sugar, which is sometimes added to ink, is found to be much less effectual than gums, and to have the inconvenience of preventing the drying of the ink. The colour of ink is found to be greatly injured by keeping the ink in vessels made of copper or of lead, and probably of any other metal, excepting iron, which the vitriolic acid can dissolve.
The foregoing experiments point out for the best proportions of the ingredients for ink, one part of green vitriol, one part of powdered logwood, and three parts of powdered galls. The best menstruum appears to be vinegar or white wine, though for common use water is sufficient. If the ink be required to be of a full colour, a quart, or at most three pints, of liquor, may be allowed to three ounces of galls, and to one ounce of each of the other two ingredients. Half an ounce of gum may be added to each pint of the liquor. The ingredients may be all put together at once in a convenient vessel, and well shaken four or five times each day. In 10 or 12 days the ink will be fit for use, though it will improve by remaining longer on the ingredients. Or it may be made more expeditiously, by adding the gum and vitriol to a decoction of galls and logwood in the menstruum. To the ink, after it has been separated from the feculencies, some coarse powder of galls, from which the fine dust has been sifted, together with one or two pieces of iron, may be added, by which its durability will be secured.
In some attempts made by the Doctor to endow writing ink with the great durability of that of the ancients, as well as the properties which it has at present; he first thought of using animal glues, and then of oily matters. "I mixed both lamp-black (says he) and ivory-black with solutions of gum-arabic, made of such consistency as just to flow sufficiently from the pen. The liquors wrote of a fine black colour; but when
Ink. when dry, part of the colour could be rubbed off, especially in moist weather, and a pencil dipped in water washed it away entirely.
"I tried solutions of the animal-glues with the same event. Ifinglas or fish glue being the most difficultly dissoluble of these kinds of bodies, I made a decoction of it in water, of such strength that the liquor concreted into a jelly before it was quite cold: with this jelly, kept fluid by sufficient heat, I mixed some ivory-black: characters drawn with this mixture on paper bore rubbing much better than the others, but were discharged without much difficulty by a wet pencil.
"It was now suspected, that the colour could not be sufficiently fixed on paper without an oily cement. As oils themselves are made miscible with watery fluids by the intervention of gum, I mixed some of the softer painters varnish, aftermentioned, with about half its weight of a thick mucilage of gum-arabic, working them well together in a mortar till they united into a smooth uniform mass: this was beaten with lamp-black, and some water added by little and little, the rubbing being continued till the mixture was diluted to a due consistence for writing. It wrote freely, and of a full brownish black colour: the characters could not be discharged by rubbing, but water washed them out, though not near so readily as any of the foregoing. Instead of the painters varnish or boiled oil, I mixed raw linseed oil in the same manner with mucilage and lamp-black; and on diluting the mixture with water, obtained an ink not greatly different from the other.
"Though these oily mixtures answered better than those with simple gums or glues, it was apprehended that their being dischargeable by water would render them unfit for the purposes intended. The only way of obviating this imperfection appeared to be, by using a paper which should admit the black liquid to sink a little into its substance. Accordingly I took some of the more sinking kinds of paper, and common paper made damp as for printing; and had the satisfaction to find, that neither the oily nor the simple gummy mixtures spread upon them so much as might have been expected, and that the characters were as fixed as could be desired, for they could not be washed out without rubbing off part of the substance of the paper itself.
"All these inks must be now and then stirred or shaken during the time of use, to mix up the black powder, which settles by degrees to the bottom: those with oil must be well shaken also, though not used, once a-day, or at least once in three or four days, to keep the oil united with the water and gum; for, if once the oil separates, which it is apt to do by standing at rest for some days, it can no longer be mixed with the thin fluid by any agitation. But though this imperfect union of the ingredients renders these inks less fit for general use than those commonly employed, I apprehend there are many occasions in which these kinds of inconveniences will not be thought to counterbalance the advantage of having writings which we may be assured will be as lasting as the paper they are written upon. And indeed the inconvenience may be in a great measure obviated by using cotton in the ink-stand, which, imbibing the fluid, prevents the separation of the black powder diffused through it.
Ink. "All the inks, however, made on the principle we are now speaking of, can be discharged by washing, unless the paper admits them to sink into its substance. The ancients were not insensible of this imperfection; and sometimes endeavoured to obviate it, according to Pliny, by using vinegar, instead of water, for tempering the mixture of lamp-black and gum. I tried vinegar, and found it to be of some advantage, not as giving any improvement to the cement, but by promoting the sinking of the matter into the paper. As this washing out of the ink may be prevented by using a kind of paper easy enough to be procured, it is scarce to be considered as an imperfection; and indeed, on other kinds of paper, it is an imperfection only so far as it may give occasion to fraud, for none of these inks are in danger of being otherwise discharged than by design. The vitriolic inks themselves, and those of printed books and copperplates, are all dischargeable; nor can it be expected of the ink-maker to render writings secure from frauds.
"But a further improvement may yet be made, namely, that of uniting the ancient and modern inks together; or using the common vitriolic ink instead of water, for tempering the ancient mixture of gum and lamp-black. By this method it should seem that the writings would have all the durability of those of former times, with all the advantage that results from the vitriolic ink fixing itself in the paper. Even where the common vitriolic mixture is depended on for the ink, it may in many cases be improved by a small addition of the ancient composition, or of the common Indian ink which answers the same purpose: when the vitriolic ink is dilute, and flows so pale from the pen, that the fine strokes, on first writing, are scarcely visible, the addition of a little Indian ink is the readiest means of giving it the due blackness. By this admixture it may be presumed also that the vitriolic ink will be made more durable, the Indian ink in some measure covering it, and defending it from the action of the air. In all cases, where Indian ink or other similar compositions are employed, cotton should be used in the ink-stand, as already mentioned, to prevent the settling of the black powder."
Since the invention of printing much less attention than formerly has been paid to the making of ink, so that now the art seems to be in a great measure lost. This will appear from a comparison of some ancient manuscripts with the writings of modern times. It being of the utmost importance, however, that public records, wills, and other valuable papers, which cannot admit of being printed, should be written with ink of a durable quality, this inattention seems to have been very culpable, and a restoration of the method of making writing ink a very valuable acquisition. "The necessity (says Mr Asle3) of paying greater attention to this matter may readily be seen, by comparing the rolls Alphab. and records that have been written from the 15th Writing. century to the end of the 17th, with the writings we have remaining of various dates from the 5th to the 12th centuries. Notwithstanding the superior antiquity of the latter, they are in excellent preservation; but we frequently find the former, though of more modern date, so much defaced, that they are scarcely legible."
Our author agrees with Dr Lewis in the opinion that
that the ancient inks were composed of foot or ivory black instead of the galls, copperas, and gums, which form the composition of ours. Besides their black inks, however, the ancients used various other colours, as red, gold and silver, purple, &c. Green ink was frequently used in Latin manuscripts, especially in the latter ages; and it was frequently employed in signatures by the guardians of the Greek emperors till their wards were of age. Blue or yellow ink was seldom used except in manuscripts; but (says Mr Aſtle) "the yellow has not been much in use, as far as we can learn, these 600 years." Some kinds of characters, particularly the metallic, were burnished. Wax was used by the Latins and Greeks as a varnish, but especially by the former, and particularly in the 9th century. It continued a long time in vogue.
A treatise upon inks was published by Peter Caniparius professor of medicine at Venice; of which an edition was printed at London in 1660. It is divided into six parts. The first treats of inks made from pyrites, stones, and metals; the second of such as are made from metals and calces; the third from foats and vitriols; the fourth of the different kinds of inks used by the librarii or book-writers, by printers, and engravers; likewise of staining or writing upon marble, stucco, or scialolia, and of encaustic modes of writing; also of liquids for painting or colouring leather and linen or woollen cloth; restoring inks that had been decayed by time; together with many methods of effacing writing, restoring decayed paper, and different modes of secret writing. The fifth treats of writing inks made in different countries from gums, woods, the juices of plants, &c. as well as of different kinds of varnishes. The sixth treats of the different methods of extracting vitriol, and the chemical uses of it.
Weckerus de Secretis, a treatise printed at Basil in 1612, contains a number of curious particulars concerning ink. He gives also receipts for making gold and silver inks, composed both with these metals and without them; directions for making inks for secret writing, and for defacing them; though in this last part there are many particulars bordering too much on the marvellous.
In the Philosophical Transactions for 1787, Dr Blagden gives some account of a method of restoring decayed inks so as to render them legible. His experiments originated from a conversation with Mr Aſtle already quoted, on the question whether the inks made eight or ten centuries ago, and which are found to have preserved their colour very well, were made of the same materials now employed or not? In order to decide the question, Mr Aſtle furnished the doctor with several manuscripts on parchment and vellum from the 9th to the 15th centuries inclusively. Some of these were still very black; others of different shades, from a deep yellowish brown to a very pale yellow, in some parts so faint that it could scarcely be seen. This was tried with simple and phlogisticated alkalies, the mineral acids, and infusion of galls. From these experiments it appeared that the ink anciently employed was of the same nature as at present: the letters turned of a reddish or yellowish brown with alkalies became pale, and were at length obliterated by the dilute mineral acids. The drop of acid liquor, which
had been put upon a letter, changed to a deep blue or green on the addition of phlogisticated alkalies; with an infusion of galls, in some cases the letters acquired a deep tinge, in others a slight one. "Hence (says the doctor) it is evident, that one of the ingredients was iron, which there is no reason to doubt was joined with the vitriolic acid; and the colour of the more perfect MSS. which in some was a deep black, and in others a purplish black, together with the restitution of that colour in those which had lost it by the infusion of galls, sufficiently proved that another of the ingredients was astringent matter, which from history appears to have been that of galls. No trace of a black pigment of any sort was discovered; the drop of acid, which had completely extracted a letter, appearing of an uniform pale and ferruginous colour, without an atom of black powder, or other extraneous matter floating in it."
As this account differs very materially from the former extracted from Mr Aſtle's writings, so the reason given for the continuance of the colour differs no less. This, according to Dr Blagden, "seems to depend very much on a better preparation of the material upon which the writing was made, namely the parchment or vellum; the blackest letters being generally those which had sunk into it the deepest. Some degree of effervescence was commonly to be perceived when acids were in contact with the surface of these old vellums. I was led, however, to suspect, that the ancient inks contained rather a less proportion of iron than the more modern; for, in general, the tinge of colour produced by the phlogisticated alkali in the acid laid upon them, seemed less deep; which, however, might depend in part upon the length of time they have been kept: and perhaps more gum was used in them, or they were washed over with some kind of varnish, though not such as gave any gloss."
Among the specimens with which our author was favoured by Mr Aſtle, there was one which differed very materially from the rest. It was said to be a manuscript of the 15th century: the letters were of a full engrossing hand, angular without any fine strokes, broad, and very black. None of the chemical solvents above mentioned seemed to produce any effect. Most of them seemed rather to make the letters blacker, probably by cleaning the surface; and the acids, after having been rubbed strongly upon the letters, did not strike any deeper tinge with the phlogisticated alkali. Nothing could obliterate these but what took off part of the vellum; when small rolls of a dirty matter were to be perceived. "It is therefore unquestionable (says the doctor) that no iron was used in this ink; and, from its resistance to the chemical solvents, as well as a certain clotted appearance in the letters when examined closely, and in some places a slight degree of gloss, I have little doubt that they were formed of a foaty or carbonaceous powder and oil, probably something like our present printers ink; and am not without suspicion that they were actually printed."
On examining this MS. more fully, our author was convinced that it was really a part of a very ancient printed book. In considering the methods of restoring the legibility of decayed writings, our author observes, that perhaps one of the best may be to join phlogisticated alkali with the calx of iron which remains; because
Ink. cause the precipitate formed by these two substances greatly exceeds that of the iron alone. On this subject Dr Blagden disagrees with Mr Bergmann; but to bring the matter to a test, the following experiments were made.
1. The phlogisticated alkali was rubbed in different quantities upon the bare writing. This, in general, produced little effect; though, in a few instances, it gave a bluish tinge to the letters, and increased their intensity; "probably (says the doctor) where something of an acid nature had contributed to the diminution of their colour." 2. By adding, besides the alkali, a dilute mineral acid to the writing, our author found his expectations fully answered; the letters then changing quickly to a very deep and beautiful blue. It is but of little consequence whether the acid or phlogisticated alkali be first added; though upon farther consideration the doctor inclined to begin with the alkali. The reason is, that when the alkali is first put on, the colour seems to spread less, and thus not to hurt the legibility of the writing so much as would otherwise be done. His method is to spread the alkali thin over the writing with a feather, then to touch it as gently as possible upon or nearly over the letters with the diluted acid by means of a feather or bit of stick cut to a blunt point. The moment that the acid liquor is applied, the letters turn to a fine blue, beyond comparison stronger than the original trace of the letter; and by applying a bit of blotting-paper to suck up the superfluous liquid, we may in a great measure avoid the staining of the parchment: for it is this superfluous liquor which, absorbing part of the colouring matter from the letters, becomes a dye to whatever it touches. Care ought, however, to be taken not to allow the blotting paper to come in contact with the letters, because the colouring matter may easily be rubbed off while soft and wet. Any one of the three mineral acids will answer the purpose effectually. Dr Blagden commonly uses the marine. But whichever of the three is used, it ought to be diluted so far as not to be in danger of corroding the parchment; after which the degree of strength seems not to be a matter of great nicety.
Another method of restoring the legibility of old writings is by wetting them with an infusion of galls in white wine: but this is subject to the same inconvenience with the former, and is besides less efficacious. The doctor is of opinion that the acid of the galls by itself would be better for the purpose than the infusion of the whole substance of them; and he thinks also that a preferable kind of phlogisticated alkali might be prepared either by purifying the common kind from iron as much as possible, or by making use of the volatile alkali instead of the fixed. Mr Asle mentions a method of restoring the legibility of decayed writings; but says that it ought not to be hazarded lest a suspicion of deceit should arise.
A method has been proposed of preventing ink from decaying by washing over the paper to be written upon with the colouring matter of Prussian blue, which will
not deprave it in colour, or any other respect. By writing upon it with common ink afterwards, a ground of Prussian blue is formed under every stroke; and this remains strong after the black has been decayed by the weather or destroyed by the acids. Thus the ink will bear a larger proportion of vitriol at first, and will have the advantage of looking blacker when first written.