Ink Phenomena

[This is taken from David N. Carvalho's Forty Centuries of Ink, originally published in 1904.]

CONDITION OF INK WHEN FIRST PLACED ON PAPER—ITS METAMORPHOSIS AND AFFINITIES—IGNORANCE OF THE FORGER AS TO ITS ORIGINAL ENVIRONMENT— TREATMENT OF OLD INK MARKS—HOW PAPER MAY DISCOLOR INK—THE USES OF ACID IN INK—VEHICLES TO HOLD INK PARTICLES AND PRESERVE THEM—INKS FIVE CENTURIES OLD DO PRESERVE THEIR GLOSS—SOME CAUSES OF INK DISINTEGRATION—WHEN INK BECOMES IRRESPONSIVE TO THE ELEMENTS—DEMONSTRATED TRUTHS ABOUT INK CONSTITUENTS AND COLOR PHENOMENA—NATURAL EVOLUTION OF AN INK MARK—LENGTH OF TIME REQUIRED TO BECOME BLACK—FIRST INDICATIONS OF AGE—DISAPPEARANCE OF INK QUALITIES—ARTIFICIAL AGING OF INK—TESTS FOR IT AND HOW TO CONFIRM THEM—BLEACHING AND REMOVAL OF INK FROM PAPER CRIMINALLY CONSIDERED—CHEMISTRY OF SUCH MARKS—THEIR RESTORATION—VARIATIONS IN METHODS WHICH CAN BE EMPLOYED.

 

ALL inks when first placed on paper are of course in a fluid state. Gradual evaporation of moisture causes a change not only in color but in the case of the iron and gall inks, in their chemical constitution, being immediately affected by their environment, whether due to the character of the paper on which they rest, the kind or condition of the pen used, or most important of all, the elements. Those who use the black inks and chemical writing fluids will have noticed these characteristics. The pale brown, blue or green as first written, and the gradual change after a short period to an approaching blackness, are reactions due largely to atmospheric conditions, the oxygen uniting with that for which it has affinity and instantly beginning with TIME to make its march, producing natural phenomena, which can be only superficially imitated but never exactly reproduced. When we further take into consideration that the forger cannot always know of the circumstances which surround the placing of original ink on paper and that be cannot manufacture the TIME which has already elapsed, it is not strange that attempted fraud can often be made evident and complete demonstrations given of the methods employed.

With the passage of time, the particles in some inks which are held together on the paper by gummy vehicles, commence to disintegrate and change from intense black to the brown color of iron rust, the “added” color which of itself is fugitive in character, soon departs; the vegetable astringent separating from the iron salt decays gradually and disappears and finally terminates in a mere stain or dust mark which can be blown off the paper. Sometimes, the written surface of such paper can be treated by carefully moistening it with a decoction of nut-galls or its equivalent in the presence of a weak acid, then if any iron be present, a measurable degree of restoration of color will ensue and remain for a short period.

Again, the discoloration of an iron ink may be due to the character of the paper; if of the cheaper grades and the bleaching compounds employed in their manufacture are not thoroughly washed out, then the ink not only begins to absorb oxygen from the atmosphere but the chlorine in the paper attacks it and the process of destruction is thereby hastened.

The introduction of acid into ink has two purposes, one to secure more limpidity, and the other to cause it to penetrate the paper and in this way bind together the constituent particles of both ink and paper. Most of the chemical writing fluids of this decade carry a superabundance of acid in their composition, which in time will burn through the paper and ultimately destroy it.

All tanno-gallate of iron inks require some vehicle to hold their particles in a state of suspension, otherwise there would be precipitation and such an ink could not be used. To meet this requirement a variety of gums are employed by manufacturers, gum acacia being the principal one. Its purpose is threefold—as before stated, to hold the ink particles in suspension—to prevent the ink from flowing too rapidly, and after drying WITHOUT blotting, to act as an envelope to encase the now fixed ink and prevent or interfere with its absorption of an excess of oxygen.  The longer these latter conditions obtain the longer will the ink retain its pristineness, its durability and permanence. The “time proved” ink-written specimens of five hundred years or more ago which continue to retain their original intense black color and “glossy” appearance, do not, however, yield any evidence of the use of vegetable gums in their composition.  Where such instances have been noticed the gloss is invariably missing. But, where ANY gloss is present, it was and is because of the employment of isinglass (fish-glue) as the vehicle to hold the ancient ink particles.

Hence the variations of color seen in ancient paper writings, as already stated, were due not only to possible imperfect admixtures of the component parts of the inks, but to the use of vegetable gums in their preparation. In the course of time these have been absorbed by moisture which hastened disintegration, causing a gradual disappearance of their original blackness and gloss and finally a return to the rusty color of oxidized iron.

It therefore follows, my observations and deductions being correct, the older a writing made with tanno-gallate of iron ink, where isinglass is the binder, and which has not been “blotted,” the harder and more impervious and irresponsive it becomes to the action of the natural elements or of chemical reagents.

The truths demonstrated in this proposition cannot be denied. They fortify as certain that a properly proportioned mixture in water of an infusion of nut-galls or gallo-tannic acid and sulphate of iron, with isinglass as the vehicle to bold the particles in a state of suspension, if written with on good paper and allowed to dry without blotting, in a short time becomes encased or enveloped in such vehicle, which is thereby rendered substantially insoluble and absolutely prevents any extensive oxidation. Also, as a further consequent result, there is chemically created an unchangeable and continuing black color more permanent and durable than the substance on which it appears.

With a sample of standard commercial chemical writing fluid, write on “linen” paper without blotting it; in thirty hours, if exposed to the air and from three to five days if kept from it, the writing should have assumed a color bordering on black; it becomes black at the end of a month under any conditions, and so continues for a period of about five or six years, when if examined under a lens of the magnification of ten diameters, there will be a noticeable discoloration of the sides or pen tracks which slowly spreads during a continuing period of from ten to fifteen years, until the entire pen marks are of a rusty brown tint. A species of disintegration and decay is now progressing and when approximately forty years of age, has destroyed all ink qualities.

If, however, “chemical writing fluid” is first treated by exposure to the fumes of an ammoniacal gas, a “browning” of the ink occurs, not only of the pen tracks but of the entire ink mark. If examined now with a lens, the ink is found to be thin enough to permit the fibre of the paper to be seen through it, thus indicating artificial age. Furthermore, if a 20 per cent strength of hydrochloric acid be applied, the “added” color (usually a blue one) is restored to ITS original hue; alike experiment on “time” aged ink gives only the yellow brown tint of pure gall and iron combinations, the “added” color having departed caused by its fugitive characteristics. Again, if a solution of chlorinate of lime or soda be applied, the ink mark is instantly bleached, where in the case of honest old ink marks, it takes considerable time to even approximate a like result.

To confirm the chemical tests which may be employed in the determination of the artificial aging of ink marks, photographs made by permitting light to transmit through the paper and to interfere with its rays by filtering them through a “color” screen containing orange and some green, will indicate the presence of a fugitive substance in the ink, usually the “added” color employed in its manufacture.

The process of bleaching or “removal” of ink marks from paper is frequently employed in the attempted eradication of words or figures and the substitution of others on monetary instruments, commonly called “raising.” Its purpose is usually a criminal one and some observations as to the modus operandi and its chemistry are not out of place here.

Ink marks made with a compound consisting of the combination of iron and an infusion of galls or its equivalent (a tanno-gallate of iron ink), as treated with certain chemicals, change from a compound with color to a chemical compound, with no color. Nothing has in fact been absolutely removed or eradicated, but it is a mere change of form, a sort of re-arrangement of the particles, the ingredients which formed the original color being still present, but in such a condition that they are invisible to the eye. A restoration of the invisible ink marks so that they can be observed, becomes possible by the use of chemical reagents and is the reverse of the one of erasure or bleaching, and changes the constituents again into a compound which has color from the one which had none. It does, not, however, reproduce the exact composition originally existing. Such a reagent simply goes to the basis of the material as first used, takes up what was left and reforms the particles sufficiently to make them abundantly recognizable. An apt illustration of these chemical changes of color is found in what is known as the phenolphtalein test solution, which is colored deep purplish-red by alkali hydrates or carbonates, and then by the addition of an acid rendered colorless, to be again reddened by an over-plus of the alkali and so on ad infinitum.

A popular material for the purpose of making chemical erasures is chlorinated lime or soda, which becomes more active by first touching the ink mark to be removed with a one half strength solution of acetic acid; this hastens the liberation of chlorine gas, THE active agent which causes the “bleaching” to take place. Hydrogen peroxide, also a bleaching compound, is less rapid in its action than chlorinate of soda; the same may be said of combinations of oxalic and sulphurous acids.

The most effective re-agent for the restoration of a chemically “bleached” iron ink mark is the sulphide or sulphuret of ammonia (it has several names). This penetrating chemical blackens metals or their salts, whether visible or not, if brought together. It must not be used by direct contact, the best and safest plan being to place a quantity in a small saucer, to be set on the floor of a closed box; to fasten to the box lid the specimen to be operated on; in this way the restoration is due to the fumes of the chemical and a possible danger of destruction of the specimen much lessened, especially if the marks are very light or delicate ones. The restoration of color under particular conditions may also be obtained by treatment with tannic acid, potassium ferro-cyanide (acidulated) or a weak solution of an infusion of galls.