Forty Centuries of Ink Part 15

In 1871 Professor Wattenbach of Germany published a treatise ent.i.tled "Archives during the Middle Ages," which has some valuable references to the color phenomena of inks.

William Inglis Clark in 1879 submitted to the Edinburgh University a thesis ent.i.tled "An Attempt to Place the Manufacture of Ink on a Scientific Basis,"

and which very justly received the commendation of the University authorities. His researches and rational deductions are of the greatest possible value judged from a scientific standpoint. The introduction of blue-black ink is a phase of the development towards modern methods which he discusses at much length.

The object of adding a dye in moderation, he a.s.serts, is to give temporary color to the ink and where indigo-paste is used, it has been a.s.sumed that it kept the iron gallo-tannate in solution, whereas any virtue of this kind which indigo-paste possesses is more likely due to the sulphuric acid which it contains than to the indigo itself. The essential part of the paste required is the sulpho-indiG.o.date of sodium, now commonly called indigo-carmine. He further remarks that the stability of an ink precipitate depends upon the amount of iron which it contains and which on no account should be less than eight per cent; he adds rightly, if gallic acid be preferably used in subst.i.tution for tannin, "no precipitate is obtained under precisely similar conditions." This point followed up explains in a measure why a gall infusion prepared with hot water is not suitable for a blue-black, while a cold water infusion is. In the latter case a comparatively small percentage of tannin is extracted from the galls, while much is extracted with hot water and the consequence is, on adding the indigo blue the color is not brought out as it should be. Substantially the same thing occurs with ink made with the respective acids, although the blue color remains for a time unimpaired in the tannin ink, apparently due to the fact that ferrous-tannate reduces indigo blue to indigo white, a change which the low reducing power of ferrous- gallate does little to effect. The vegetable matter in common inks facilitates the destruction, or rather alteration and precipitation of the indigo, for the dye appears in the iron precipitate and may be extracted from it with boiling water.

Dr. Clark's investigations seek to demonstrate the superiority of tannin and gallic acid over infusions of the natural galls, and he undertakes to determine the correct ratio of tannin and sulphate of iron to be used as ink. His experiments in this line show that:

1. The amount of precipitate increases as the proportion of iron to tannin is increased.

2. The composition of the precipitate is so valuable as to preclude the possibility of its being a definite body. Increase of iron in the solution has not at first any effect on the composition of the precipitate, but afterwards iron is found in it in greater but not proportional amount.

3. At one point the proportions of iron in the precipitate and in solution are the same, and this is at between 6 and 10 parts of iron to 100 parts of tannin.

4. The proportion of iron in the precipitate varies greatly with the length of time the ink has been exposed.

At first the precipitate contains 10 per cent of iron, but by and by a new one having only 7.5 per cent is formed, and in from forty to seventy days we find one of 5.7 per cent. Simultaneously iron increases in the ink (proportionate to the tannin).

5. The results show, and practice confirms, that 16 parts of iron (80 ferrous sulphate) and 100 parts of tannin are best for ink manufacture.

The research now travelled in a direction which acc.u.mulating experience showed to be obligatory.

Blue-black tannin ink lost color, and the reducing nature of the tannin tended to the formation of a highly objectionable precipitate in the ink, which made writing anything but a pleasure. These two faults were doubtless linked together in some way and seemed not to exist when gallic acid was used, for ink so made was found to precipitate only after a long exposure, it required no free acid to keep the precipitate in solution, and retained the indigo blue color for a long time; alkalis did not decompose the ink, and provided blacker and more permanent writing.

Determination of the correct proportions of gallic acid and ferrous-sulphate was the subject of prolonged experiments conducted on similar lines to those already detailed. The conclusions as to precipitation were also similar. Thirty parts of iron (150 of ferrous- sulphate) and 100 parts of gallic acid were found to be the most suitable proportions for ink-making. It is advisable, however, not to discard tannin altogether, owing to the slow blackening of the gallic acid ink, and a little tannin gives initial blackening and body, while it is absolutely necessary for copying ink.

Initial blackness can also be ensured by oxidizing 21 per cent of the ferrous-sulphate without adding the extra acid necessary to the formation of a ferric salt.

The concluding portion of his research is devoted to the influence of sugar upon the permanence of ink, and the results of the experiments are summed up in the following sentences: "It would be injurious to add 3 per cent of sugar to a tan in ink, while from 4 to 10 per cent would be quite allowable. Most copying inks contain about 3.5 per cent of sugar-- not far from the critical amount. With gallic acid more than 3 per cent of sugar hardly varies the precipitate, but the importance of this point is somewhat diminished by the fact that the presence of sugar is by no means necessary in a writing ink. Dextrin is a much superior substance to use. Curiously this body rapidly precipitates a tannin ink; hence it is useless for copying ink, but for the gallic ink it is an excellent thickener."

Chen-Ki-Souen, "Lencre de China," by Maurice Jametel, appeared in Paris in 1882, but as the t.i.tle indicates, it is the old "Indian" or Chinese ink that is discussed.

Schluttig and Neumann in 1890 issued their Edition Dresden on the subject of "Iron and Gall inks." In this valuable work is to be found the formula which has been generally adopted as the standard where one is used for tanno-gallate of iron ink.

The investigations of other scientific men like Lepowitz, Booth, Desormeaux, Chevreuse, Irvine, Traille, Bottger, Riffault, Precht, Nicholes, Runge, Gobert, Penny, Arnold, Thomson (Lord Kelvin), Davids, Kindt, Ure, Wislar and many more who have dealt with the chemistry of inks, present to us some testimony during a considerable portion of the nineteenth century of the efforts made to secure a good ink.

CHAPTER XIV.

CLa.s.sIFICATIONS OF INK.

INK USED BY US HAS NOTHING IN COMMON WITH THAT OF THE ANCIENTS--MANUFACTURERS OF THE PRESENT TIME HAVE LARGELY UTILIZED FORMULAS EMPLOYED IN PAST CENTURIES--THE COMMON ACCEPTATION OF THE TERM INK--SEVEN DIFFERENT CLa.s.sES OF INKS AND THEIR COMPOSITION BRIEFLY TOLD--FAILURE OF EFFORTS TO SECURE A REAL SAFETY INK.

THE inks used by us have nothing in common with those of the ancients except the color and gum, and mighty little of that.

Those of the "gall" cla.s.s employed in the fourteenth, fifteenth, sixteenth, seventeenth and eighteenth centuries, some formulas of which are utilized by the manufacturers of ink in our own time, consisted generally in combination; infusions of nut-galls, sulphate of copper or iron, or both, and fish-glue or gum, slightly acidulated. The frequent introduction of the so-called "added" color into these inks, time has shown to have been a grave mistake.

The common acceptation of the term "ink" may be said to characterize an immense number of fluid compounds, the function of which in connection with a marking instrument is to delineate conventional signs, characters and letters as put together and commonly called writing, on paper or like substances.

To cla.s.sify them would be impossible; but black writing ink, chemical writing fluid, colored writing ink, copying ink, India ink, secret or sympathetic ink, and indelible ink make seven cla.s.ses; the others may be denominated under the head of miscellaneous inks, and of them all, there is no single ink answering every requirement and few answer at all times the same requirements.

Ink may be either a clear solution of any coloring matter or of coloring matter held in suspension.

It is a remarkable fact that although most inks are chemical compositions and many times made after the same formula, identical results cannot always be calculated or obtained. This is more particularly to be noted in the case of black writing inks otherwise known as the tanno-gallate of iron inks [gallic and gallotanic acid obtained from nut-galls, sulphate of iron, (green copperas) and some gummy vehicle].

The variations would appear to be largely due to the difference in quality of the gall-nuts, treatment, and temperature of the atmosphere; perhaps, however, not so much to-day as it was ten or twenty years ago, when to make ink of this character boiling processes were employed. Most of them as already stated are now "cold" made.

Inks of this cla.s.s consist of a finely divided insoluble precipitate suspended in water by the use of gum and possessing a slight acidity.

The requisites of a good black writing ink or black writing fluid require it to flow readily from the pen, to indicate in a short time a black color and to penetrate the paper to an appreciable degree, and more important than all the rest, to be of great durability. When kept in a closed vessel no sediment of any account should be precipitated, although such will be the case in open ink-wells, and this the quicker the more the air is permitted to get to it. If it is to be used for record or doc.u.mentary purposes it must not be altogether obliterated if brought into contact with water or alcohol, and should depend for permanency on its chemical and not on its pigmentary qualities.

The second cla.s.s, called for distinction "chemical writing fluids," possesses the same essential ingredients to be found in cla.s.s one, but much less in quant.i.ty and with some "added" colored substance which I shall term "loading," for its real purpose is to cheapen the cost of production and not altogether as some manufacturers state "simply to give them an agreeable color."

Previous to the discovery of the soluble anilines, logwood, indigo, madder, orchil and other dyeing materials were used for a period of some eighty years and vanadium for some twenty years (very costly at that time), for this purpose, but since 1874, and with frequent changes as the newer aniline compounds were invented, these by-products of coal-tar, as well as logwood, etc., have been and are to-day employed for "loading," or as the manufacturer expresses, it "added color." The chemical writing fluids as now prepared, yield when first written a blue or green color with a tendency to change to black afterwards. They are not as permanent as those of the first cla.s.s.

Another black ink not durable, however, is "logwood;"

its extract is combined with a little chromate of pota.s.sium and boiled together in water. It possesses its own "gum" and contains some tannin. In combination with alum and water, it forms a dark purple ink.

The colored writing inks, of which "red" is the more important, are in great number and with hardly an exception at the present time, manufactured by adding water and water-gla.s.s to a soluble aniline red color. Cochineal which was used for red ink formerly is now almost obsolete. Nigrosine, one of the best known of them, is much used as a cheap "black" ink, but as it is blue black and never becomes black, it really belongs to the family of "colored" writing inks. They possess an undeserved popularity for they flow freely from the pen which they do not corrode, nor do they thicken or spoil in the inkwell; they are however very "fugitive" in character and should not be employed for record, legal, monetary or other doc.u.mentary purposes. The indigo and prussian blue inks are well known, the former under certain conditions a very permanent ink, the latter soon disintegrating.

Copying inks are of two kinds, one dependent on the addition of glycerine, sugar, glucose or like compounds to the black writing inks or chemical writing fluids heretofore mentioned, which are thereby kept in a moist offsetting condition; the other due to the solubility of the pigmentary color with water, such as the aniline inks which are given more body than those for ordinary purposes--and the logwoods in which the pigment is developed and given copying qualities by chemicals, and hence becomes responsive to the application of a sheet of paper dampened with water. Copying ink should never be used for "record" purposes as it is affected by changes of the temperature.

India ink, sometimes called China ink, or as formerly known by the ancients and in cla.s.sical and later times "Indian ink," is now used more for drawing and engrossing than it is for commercial purposes. It belongs to the "carbon" cla.s.s and in some form was the first one used in the very earliest times. In China it is applied with a brush or pith of some reed to the "rice" paper also there manufactured. It is easily washed away unless bichromate of ammonium or pota.s.sium in minute quant.i.ties be added to it, and then if the paper on which it appears be exposed for a short time to the action of the actinic rays of sunlight, this gummy compound will be rendered insoluble and cannot be removed with any fluid, chemical or otherwise.

It possesses also great advantages in drawing, since it acts as a paint, and will give any degree of blackness according to the quant.i.ty of water mixed with it.

Secret or sympathetic inks are invisible until the writing is subjected to a subsequent operation, such as warming or exposing to sunlight. To further aid the object in view, the paper may be first steeped in a liquid and the writing only made visible by using another liquid which has some chemical affinity with the previous one. The number of this kind were but few but have multiplied as chemistry progressed.

The ancients were acquainted with several modes.

Ovid indiscreetly advises the Roman wives and maidens if they intend to make their correspondence unreadable to the wrong persons to write with new milk, which when dried may be rendered visible by rubbing ashes upon it or a hot iron. Pliny suggests milky juices of certain plants of which there are a considerable variety.

Indelible ink is not used for writing purposes on paper, but is found best adapted for marking linen and cancellation or endorsing purposes. It is chiefly composed of nitrate of silver preparations, to which heat must be applied after it has been dried; or a pigment is commingled with the same vehicles used in making common printing ink and in its use treated as such.

Diamonds, gold, silver, platinum and a host of other materials are manufactured into ink and are to be placed under the head of miscellaneous inks. They are in great number and of no interest in respect to ink writing except for engrossing or illuminating.

Still another ink once held in much esteem and now almost obsolete is the so-called "safety" ink.

Manufacturers, chemists and laymen in great number for many years wasted money, time and energy in diligent worship at a secret shrine which could not give the information they sought. A summary of the meager and barren results they secured is of little value and unimportant. Hence, there is no REAL "safety" ink.

It is true that lampblack (carbon) as made into ink, resists any chemical or chemicals, but simple water applied on a soft sponge will soon remove such ink marks. The reason for this is obvious, the ink does not penetrate the paper.

"Safety" ink which will not respond to acids may be affected by alkalis, or if resisting them separately, will yield to them in combination.

CHAPTER XV.

OFFICIAL AND LEGAL INK.

FIRST COMPLETE OFFICIAL INVESTIGATION OF INK IN THIS COUNTRY--THE HONOR DUE TO ROBERT T. SWAN OF BOSTON--RESUME OF HIS REPORTS TO THE LEGISLATURE OF THE STATE OF Ma.s.sACHUSETTS--THE SWAN LAW ADOPTED IN 1894 BY THE STATE OF Ma.s.sACHUSETTS--UNITED STATES TREASURY DEPARTMENT ADOPTS AN OFFICIAL INK IN 1901--UNSUCCESSFUL ATTEMPT TO SECURE INK LEGISLATION IN THE STATE OF NEW YORK--COMMENTS OF THE PUBLIC PRESS OF THAT PERIOD--DIFFERENT WORKS WHICH MORE OR LESS DWELL ON THE SUBJECT OF INK FROM 1890 TO 1900--CITATIONS FROM ALLEN'S COMMERCIAL ORGANIC a.n.a.lYSIS--REFERENCE TO PAPER ABOUT INK READ BEFORE THE NEW YORK STATE BAR a.s.sOCIATION.

IT was not, however, until 1891 that the subject of the const.i.tution of an enduring record ink received the consideration its importance deserved and in this the youngest of countries. To Robert T. Swan of Boston is all honor due for the very unique and comprehensive methods adopted in his investigations.

Appointed "commissioner of public records" of the state of Ma.s.sachusetts, he has set an example which may well be followed by other states, as has been done in a lesser degree by Connecticut and ten years later by the United States Treasury Department, which in this respect is so ably represented in part by Dr. Charles A. Crampton of Washington, D. C.

Mr. Swan in his reports to the legislature of his state for the last twelve years, deals with the subject of the const.i.tution of "permanent inks" so thoroughly, and with it affords information of so practical and useful a character, that the fullest references to them prove both instructive and interesting. In his report of 1891 he remarks: