The chronological history of such of these artificial colors which appertain to ink or its manufacture is important as locating the dates of their invention and commercial use.

The first discovery of "aniline" is credited to Helot in 1750. In 1825 Faraday in rectifying naphtha discovered benzole, which by the action of strong nitric acid be converted into nitro-benzole; and this latter, when agitated with water, acetic acid and iron filings produced aniline. Unverdorben in 1826 discovered an a.n.a.logous material in products obtained by the destructive distillation of indigo. Runge in 1834 claims to have detected it in coal tar and called it kyanol, which after oxidation became an insoluble black pigment and known as aniline black. It could not, however, be used as an ink. Zinan in 1840, experimenting along the same lines, produced another compound terming it benzidam. Fritsche in the same year by the distillation of indigo with caustic potash developed a product which he also called aniline, the name being derived from the Portuguese word anil, meaning indigo. Shortly afterwards A. W. Hoffman established the ident.i.ty of these substances.

Aniline when pure is a colorless liquid, possessing a rather ammoniacal odor. It soon becomes yellow and yellow-brown under the influence of light and air.

It does not affect litmus paper.

In 1856 Perkins accidentally discovered the violet dye called mauve, which acquired considerable commercial importance besides its utility for ink purposes.

Nicholson in 1862 succeeded in producing the first of the soluble blue anilines.

The discovery of induline, one of the modifications of aniline black, was made known in 1864.

Nigrosine, produced by the action of concentrated sulphuric acid on the insoluble indulines, was discovered in 1868.

The soluble indulines and nigrosines differentiate in appearance, the first a bronzy powder and the latter a black l.u.s.trous powder. When made into ink they possess about equal color values.

In 1870 the German chemists, Graebe and Liebermann, announced that they had succeeded in producing artificial alizarin,--the coloring matter of the madder root. Commercial value was not given to this discovery until it was put on the market in 1873, although it did not meet all the requirements.

Springmuhl in 1873 obtained an accessory product in the artificial manufacture of alizarin out of anthracene, from which a beautiful blue was made, superior in many respect to the aniline blues. It differed from aniline in having the same color in solution. Alkalis destroyed the color but acids restored it. The process was kept a secret for a long time. This product was originally sold as high as $1,500 for a single pound.

Caro, a German chemist, invented in 1874 the red color known as eosine, which was brought to this country in the following year and sold for $125 per pound. Its color is destroyed by acids.

Orchil or archil (the red color) was discovered in 1879. The commercial use of the so-called "orchil subst.i.tutes" (purples) began, however, in the years 1885 and 1887.

Artificial indigo, as the result of many years of experimenting, came into commercial use under the name of "indigo pure" only in 1897. It had previously been produced synthetically in a variety of ways, but the cost of the production was far above that of the natural product. Baeyer and Emmerling in 1870, Suida in 1878, Baeyer in 1878, Baeyer and Drewsen in 1882, and Heumann in 1890, can be said to have been the pioneers in the production of artificial indigo.

The intensity of some of the aniline colors may be indicated by the fact that a single grain of eosine in ten millions of water exhibits a definite rose-pink color.

It is a.s.serted that in the last three years many improvements have been made in the permanent qualities of some of the soluble anilines, but no material which is soluble in plain water should ever be employed as an ink for record purposes.

Preceding the discovery of the "anilines," as already related, other substances had been employed for "added" color in the admixture of ink, princ.i.p.ally madder, Brazil wood, indigo, and logwood.

Only a casual reference has heretofore been made to Brazil wood and logwood.

Brazil wood, also called peach wood, is imported from Brazil. Its employment as a dyestuff is known to be of great antiquity, antedating considerably the discovery of South America. Bancroft states, "The name 'Brazil' was given to the country on account of the extensive forests of the already well-known 'Brazil wood,' which was found by its Portuguese discoverers. The dyestuff thus gave its name to the country from which it was afterwards princ.i.p.ally obtained. The word 'Brazil' appears to have been originally used to designate a bright red or flame color. Thus in a contract between the cities of Bologna and Ferrara, in 1194, the dyestuff kermez is referred to as grana de Brazile and Brazil wood, both dyestuffs at that time being obtained from India."

For "added" color to ink and alone it was much used in the seventeenth and eighteenth centuries.

Logwood, employed more extensively for "added"

color than any other color compound, was introduced into Europe by the Spaniards, A. D. 1502. In England it does not appear to have been much used until about 1575. In 1581 the Parliament prohibited its use "because the colours produced from it were of a fugacious character." Its use was legalized in 1673 by an act, the preamble of which reads, "The ingenious industry of modern times hath taught the dyers of England the art of fixing, the colours made of logwood, alias blackwood, so as that, by experience, they are found as lasting as the colours made with any sort of dyeing wood whatever." It is obtained princ.i.p.ally from the Campeachy tree, which grows in the West Indies and South America.

The practical utility of logwood as the base for an ink was a discovery of Runge in 1848, who found that a dilute solution of its coloring matter, to which had been added a small quant.i.ty of neutral chromate of pota.s.sium, produced a deep black liquid which apparently remained clear and did not deposit any sediment.

This composition became very popular on account of its cheapness and dark purple color. It is of a fugitive character, though, and has pa.s.sed almost entirely out of commercial use.

CHAPTER XXI.

ANCIENT AND MODERN INK RECEIPTS.

"INDIAN" INK--SPANISH LICORICE--BITUMEN--CARBON FROM PETROLEUM--PROCESS TO OBTAIN GALLIC ACID--EFFECT OF SUGAR IN INK--DARK COLORED GALLS BEST FOR INK MAKING--SUBSt.i.tUTES FOR GALLS--RELATIVE PROPORTIONS OF IRON AND GALLS--ANECDOTE OF PROFESSOR TRIALL-- ESTIMATION OF SULPHATE OF COPPER--QUAINT INK RECIPE--RIBAUCOURT'S INK--HORSELEY'S INK-- ELSNER'S INDELIBLE MARKING INK--BLACK INK FOR COMMON AND COPYING USES--COMMON BLACK INK--SHINING BLACK INK--PROCESS FOR "BEST"

INK--INDELIBLE BLACK INK WITHOUT GALLS OR IRON--INK POWDER--STEEL PEN INK--SOME EARLY LITERATURE OF THE COAL TAR PRODUCTS--INK PLANT OF NEW GRANADA--"IMPERISHABLE" INK--FIRE- PROOF INK--"INERADICABLE" INK--EXCHEQUER INK--"PERMANENT" RED INK--SUBSt.i.tUTE FOR "INDIAN"

INK--TO PREVENT INK FREEZING--BACTERIA IN INK--GOLD AND OTHER INKS USED FOR ILLUMlNATING.

INNUMERABLE receipts and directions for making inks of every kind, color and quality are to be found distributed in books more or less devoted to such subjects, in the encyclopaedias, chemistries, and other scientific publications. If a.s.sembled together they would occupy hundreds of pages. Those cited are exemplars indicating the trend of ideas belonging to different nations, epochs, and the diversity of materials. They can also be considered as object lessons which conclusively demonstrate the dissatisfaction always existing in respect to the const.i.tution and modes of ink admixture.

Many of them are curious and are reproduced without any amendments.

"Indian ink is a black pigment brought hither from China, which on being rubbed with water, dissolves; and forms a substance resembling ink; but of a consistence extremely well adapted to the working with a pencil-brush, on which account it is not only much used as a black colour in miniature painting; but is the black now generally made use of for all smaller drawings in chiaro obscuro (or where the effect is to be produced from light and shade only).

"The preparation of Indian ink, as well as of the other compositions used by the Chinese as paints, is not hitherto revealed on any good authority; but it appears clearly from experiments to be the coal of fish bones, or some other vegetable substance, mixed with isingla.s.s size, or other size; and most probably, honey or sugar candy to prevent its cracking. A substance, therefore, much of the same nature, and applicable to the same purposes, may be formed in the following manner.

"Take of isingla.s.s six ounces, reduce it to a size, by dissolving it over the fire in double its weight of water. Take then of Spanish liquorice one ounce; and dissolve it also in double its weight of water; and grind up with it an ounce of ivory black. Add this mixture to the size while hot; and stir the whole together till all the ingredients be thoroughly incorporated. Then evaporate away the water in baleno mariae, and cast the remaining composition into leaden molds greased; or make it up in any other form."

"The colour of this composition will be equally good with that of the Indian ink: the isingla.s.s size, mixt with the colours, works with the pencil equally well with the Indian ink; and the Spanish liquorice will both render it easily dissolvable on the rubbing with water, to which the isingla.s.s alone is somewhat reluctant; and also prevent its cracking and peeling off from the ground on which it is laid."

There is found in small currents near the Baltick Sea, in the Dutchy of Prussia a certain coagulated bitumen, which, because it seems to be a juice of the earth is called succinum; and carabe, because it will attract straws; it is likewise called electrum, glessum, anthra citrina, vulgarly yellow amber.

"This bitumen being soft and viscous, several little animals, such as flies, and ants, do stick to it, and are buried in it.

"Amber is of different colours, such as white, yellow and black.

"The white is held in greatest esteem in physick, tho' it be opacous; when it is rubbed against anything, it is odoriferous, and it yields more volatile salt than the rest. The yellow, is transparent and pleasant to the eye, wherefore beads, necklaces, and other little conceits are made of it. It is also esteemed medicinal, and it yieldeth much oil.

"The black is of least use of all. (Sometimes used by the ancients in making ink.)

"Some do think that petroleum, or Oil of Peter, is a liquor drawn from amber, by the means of subterrenean fires, which make a distillation of it, and that jet, and coals are the remainders of this distillation.

"This opinion would have probability enough in it, if the places, from whence this sort of drogues does come, were not so far asunder the one from the other; f or petroleum is not commonly found but in Italy, in Sicily, and Provence. This oil distils through the clefts of rocks, and it is very likely to be the oil of some bitumen, which the subterranean fires have raised."

There are various processes for obtaining gallic acid, one of which is to moisten the bruised galls and expose them for four or five weeks to a temperature of 80 degrees Fahr.; by which a mouldy paste is formed, which is pressed dry and then digested in boiling water, which after evaporation yields the acid, and mixed with the solution of green copperas, makes the, ink. A quicker process, however, is to put the bruised galls into a cylindrical copper of a depth equal to its diameter, and boil them in nine gallons of water--taking care to replace the water lost by evaporation. The decoction to be emptied into a tub, allowed to settle, and the clear liquid being drawn off, the lees are emptied into another tub to be drained. The green copperas must be separately dissolved in water, and then mixed with the decoction of the galls. A precipitate is then formed in the state of a fine black powder, the subsidence of which is prevented by the addition of the gum, which, separately dissolved in a small quant.i.ty of hot water, combines with the clear black liquid. Besides its effect in keeping the fine insoluble particles in suspension, the gum mucilage improves the body of the ink, prevents its spreading or sinking too much into the paper in writing, and also acts beneficially by forming a sort of compact varnish in it, which tends to preserve its colour, and shield it from the action of the air. If, however, too much mucilage is used, the ink flows badly from quill pens, and still more so from steel pens, which require a very limpid ink. The addition of sugar increases the fluidity of ink, and permits the quant.i.ty of gum to be increased over what it would bear without it; but, on the other hand, it causes it to dry more slowly, and besides it frequently pa.s.ses into vinegar, when it acts injuriously on the pens. The dark- coloured galls, known as the blue Aleppo ones, are said by Ribaucourt, and others who have given much attention to the ingredients for ink-making to be the best for that purpose, and they are generally used by the best makers.

"From their high price, however, and that of galls generally, sumach, logwood, and even oak bark are too frequently subst.i.tuted in the manufacture of inks, but it need scarcely be said always injuriously. Ink made according to the receipt given above is much more rich and powerful than many of those commonly made. To reduce it to their standard one half more water may be safely added; or even twenty gallons of tolerable ink may be made from the same weight of materials.

Sumach and logwood admit of only about one-half or less of the green copperas that galls will take, to bring out the maximum amount of black colour.

The colour of black ink gradually darkens in consequence of the peroxidation of the iron in it on exposure to the air, but it affords a more durable writing when used pale; its particles being then finer, penetrate the paper more intimately, and on its oxidation is mordanted into it. It is advisable so soon as the ink has acquired a moderately deep tint, to draw it off clear into bottles and cork them well.

"According to the most accurate experiments on the preparation of black writing inks, it appears that the proportion of the green copperas ought to be, and not to exceed, a third of the decoction of galls used; but the proportions used vary according to the practical experience of ink-makers, who have all receipts of their own, which they deem best, and, of course, keep secret. In the precipitate an excess of colouring matter, which is necessary for its durability, is preserved in it. The blue galls alone ought to be employed in making the best quality of black ink. Logwood is a useful.

ingredient, because its colouring matter unites with the sulphate of iron and renders it not only of a very dark colour, but also less capable of change from the action of acids or of the atmosphere.

Many attempts have been made by amateurs to make a good permanent black ink. A good story is told of Professor Traill. He had succeeded, after a long series of experiments, in producing an ink which he deemed to be in all respects A 1, and which resisted the action of all acids and alkalies alike. The pleased savant sent samples of it for trial to several banks and schools, where it gave general satisfaction; but, alas, an experimenting scribbler, thoughtlessly or otherwise, applied a simple test undreamt of by the Professor, and with a wet sponge completely washed off his 'indelible,' and thereby finished his career as an amateur ink-maker!"

"Nicholson, in his Dictionary of Chemistry, an old but valuable work, says that Ribaucourt found vitriol of copper, in a certain proportion, to give depth and firmness to the colour of black ink; but, from whatever cause, this has not taken a place among the commonly-used ink-making ingredients-- probably because it acts injuriously on steel pens."

"A quart of rain Wate. 3 Ounces of Blue Knolly Gawalls. Bruise ym it must stand & be stirred 3 or 4 times in ym Day & then Strain out out all ye gawells all ten Days and 2 Ounces of Clear Gummary Beck & 1/2 an Ounce of Coperous 1/2 an Ounce of Rock Alum half an Ounce of Loafe sugar ye Bigness of a Hoa.r.s.el nut of Roman Vitterall Bray ym all small Before they be put in it must be stirred very well for ye s.p.a.ce of two weeks.

"A receit forink.--1727