Chapter 6

By treating the insolated paper with these solutions, the image is destroyed, and the paper can be used again. One operates as for sensitizing, taking care to desiccate the paper, as it has been directed.

_The proofs are brilliant during the development, but become dull in drying._

The paper not well sized. It has been dried too slowly.

Remember that it should be quite desiccated within fifteen minutes.

_The paper is more or less yellow._

1st. The paper tinted with ultramarine. 2d. The sensitizing solution or the developer are not sufficiently acid. 3d. The washing (fixing) in the solution of hydrochloric acid was not sufficient to eliminate the iron salts from the paper.

_The proofs harsh, devoid of half tones._

1st. The sensitizing solution contains too much iron chlorate. 2d. Exposure too short.

_The paper is stained._

The brush not kept clean while sensitizing.

_Black spots._

They are generally due to metallic dust in the paste of the paper, or from particles of undissolved salt in the platinite solution.

NB: No good results can be expected unless the paper be kept absolutely dry before, during and after exposure, when using the former (original) process.

Impaired sensitiveness of the paper, want of vigor, tinged whites, muddiness, indicate dampness.

ARTIGUES’ PROCESS

The Artigues process, so called, is, without any doubt, the best to be employed for the reproduction of plans and drawings in lines. It is simple, expeditious, and yields black impressions on a very pure white ground which are absolutely permanent. And this is of the utmost importance when the copies are to be used for military purpose, or kept in archives, such as those of the Patent Office, for example. Should it not require the use of negative clichés, it would certainly supersede any of the processes previously described; moreover, as it will be seen, it can be employed for many other purposes than that of obtaining duplicates from original drawings. The objection is not even very great indeed, for the design can be, without great trouble, transformed into a negative by the aniline method described in the beginning of this work.

The Artigues process is an adaptation for the purposes in question of the carbon process invented by Poitevin. We shall describe it in extenso.

The paper can be prepared with any one of the following solutions:

1st. Dissolve 2½ parts of ammonium bichromate and 5 parts of best gum arabic in 15 parts of water and neutralize with a few drops of concentrated aqueous ammonia; then add 100 parts in volume of whites of egg and a certain quantity of thick India ink, and, this done, beat the whole to a thick froth. In ten or twelve hours the albumen will be deposited and ready for use.

The quantity of India ink added to the albumen should be such as the paper be black when coated, but, however, sufficiently transparent for one to see the shadow of objects placed on the back of it, and the coating should not be thick. This is important in order to allow the light acting through the whole thickness of the preparation when the paper is insolated under the cliché, for, if the film be too opaque or too thick (by addition of too much gum arabic), it would be only impressed on its surface, and the image dissolved during the development. The cause of this failure must be explained. Under the action of light the bichromate employed to sensitize the albumen is reduced into chromic oxide which render insoluble this organic substance—or any other, such as caseine, gelatine, gum arabic, etc.; therefore whenever the film is not acted on in its whole thickness, the subjacent part being still soluble, is necessary washed off and with it the superficial impressed part, that is, the image.

2d. Take 10 parts of lamp black and work it up in a mortar to the consistency of a thin paste by gradually pouring a little of a solution of from 6 to 8 parts of gum arabic and 1 part of liquid glucose in 100 parts of water, adding afterwards the remainder, into which 2½ parts of ammonium bichromate have been dissolved, and filter through flannel. With this, coat the paper by brushing so as to form a thin and uniform film, and pin it up to dry in the dark.

These solutions keep well for a certain period. We have kept the albumen, which we prefer to use, for two months in good condition; but the sensitive paper does not for more than three or four days in taking the usual care. It is more practical—and this is recommended—to leave out the bichromate from the preparations, and to coat the paper, in quantity, beforehand, and for use to sensitize it with a solution of potassium bichromate at 3½ per cent. of water applied on the verso with a Buckle brush.(25)

The bichromate solution should be allowed to imbue the paper for about one minute, and having brushed it once more, the paper is pinned up to dry in the dark room. It can also be sensitized from the back by floating, if this manner is found more convenient.

When dry the paper is impressed under a negative cliché of good intensity until the design, well defined in all its details, is visible on the back of the paper, which requires an insolation of about two minutes in clear sunshine, and from eight to ten times longer in the shade. In cloudy weather the exposure to light is necessarily very long.

As explained before, the luminous action, by reducing the chromic salt in presence of certain organic substances, causes the latter to become insoluble; consequently if, on its removal from the printing frame, the proof be soaked in cold water, for, say, ten minutes, and, placing it on a glass plate or a smooth board, gently rubbed with a brush or a soft rag, the parts of the albumen or gum arabic preparation not acted on will dissolve, leaving behind the black image standing out on the white ground of the paper. This done, and when the unreduced bichromate is washed out in two changes of water, the operation is at an end.

As to the theory of this and similar processes, the insolubilization of the bichromate organic substance acted on by light was formerly attributed to the oxidation of the substance by the oxygen evolved during the reduction of the chromic salt into chromic oxide; but from the fact that oxidation generally tends to destroy organic matters, or to increase their solubility, it is more probable that it results from the formation of a peculiar compound of the substance with chromic oxide (J. W. Swan); moreover, gelatine imbued with an alkaline bichromate, then immersed first in a solution of ferrous sulphate and afterwards in hot water, is insolubilized with formation of chromium trioxide, Cr2O7K2+SO4Fe = SO4K2+C2O4Fe+C2O3 (Monckhoven). A similar but inverse action occurs, as shown by Poitevin, when gelatine rendered insoluble by ferric chloride becomes soluble by the transformation, under the influence of light, of the ferric salt into one at the minimum.

The writer has improved the above process by simplifying the modus operandi as follows:

Instead of compounding the preparation with gum arabic and the coloring matter, the albumen is simply clarified by beating the whites of eggs to a froth, etc., and the paper is coated by floating for one minute, then hung up to dry in a place free from dust.

If the reader has any objection for albumenizing his own paper, he can use the albumen paper found in the market for the printing-out silver process generally employed by photographers.

The paper is sensitized from the back with the potassium bichromate bath by floating or by brushing. When dry, it is exposed as usual, but for a shorter period than when the preparation contains the India ink or other coloring matters which impede the action of light.

The progress of the impression is followed by viewing, from time to time, the albumenized side of the paper. When the design is visible, well defined and brownish, the proof, being removed from the printing frame, is rubbed with very finely powdered, or, better, levigated graphite, and, this done, immersed in cold water for from fifteen to twenty minutes, when by gently rubbing it under a jet of water with a soft rag, or with a sponge imbued with water, the albumen is washed off from the parts not acted on, leaving the design on a perfectly white ground.

If instead of graphite, or any dry color insoluble in water, lithographic ink, much thinned with turpentine oil, be applied on the print in a light coating which permits one to see the design under it, and if, then, the print be soaked in water and afterwards developed as just directed, an image in greasy ink is obtained. And, furthermore, by replacing the printing by transfer ink, one readily obtains a transfer ready for the stone or a zinc plate to be etched in the ordinary manner.

As usual there are two causes of failures in these processes, viz., under and over-exposures. In the former case the image is partly washed off; in the latter the ground cannot be cleared. The reasons are obvious.

Mr. de Saint Florent gives the following processes:(26) A sheet of albumenized or gelatinized paper is sensitized from the verso on a solution of potassium bichromate, dried in the dark and exposed under a positive cliché. After insolation, the proof is washed in water, to which are added few drops of ammonia, then inked all over with an ink consisting of 100 parts of liquid India ink, 7 parts of sulphuric acid and 3 parts of caustic potassa, and dried in a horizontal position. When quite dry, the proof is placed in water, and after an immersion of about ten minutes, rubbed with a soft brush: the image little by little appears, and if the time of exposure be right, it is soon entirely cleared, and, then, if not enough vigorous, it may be inked again. The gloss of the image is removed by means of a solution of caustic potassa at 10 per 100, and the proof finally washed with care.

If in lieu of albumen paper, one employs paper prepared with a thin coating of gelatine, and dissolves the not acted on gelatine in warm water, a very fine positive image is obtained by means of acidified inks which will fix themselves on the bare paper.

Positive impressions from positive clichés can also be obtained in operating in the following manner: On its removal from the printing frame the proof is washed, sponged between sheets of blotting paper, then covered with not acidified India ink mixed with potassium bichromate, and, when dry, exposed from the verso to the action of light. This done the image is cleared with a somewhat hard brush.

THE CARBON PROCESS.

The carbon tissue is seldom prepared by photographers. However, for the sake of completeness, we shall give the formula of the mixtures most generally employed, and describe the manner of coating the paper on a small scale.

_Preparation of the Tissue.—_The gelatine generally recommended to compound the mixture is the Nelson’s autotype gelatine. Coignet’s gold label gelatine, mixed with a more soluble product, such as Cox’s gelatine, for example, gives also excellent results.

Gelatine 110 parts Sugar 25 parts Soap, dry 12 parts Water 350 parts

The coloring substances consist of:

FOR ENGRAVING BLACK. Lamp-black 20 parts Crimson lake 2 parts Indigo 1 part

FOR WARM BLACK. Lamp-black 3 parts Crimson lake 3 parts Burnt amber 2 parts Indigo 1 part

FOR SEPIA Lamp-black 2 parts Sepia of Cologne 18 parts

FOR PHOTOGRAPHIC RED BROWN. India ink 3 parts Crimson lake 4 parts Van Dyck brown 4 parts

For blue, Turnbull’s blue is employed; for yellow, light chrome yellow; for red, carmine dissolved in aqueous ammonia, evaporating, then adding water, etc. (See further on.)

To prepare the mixture, dissolve the sugar and soap in the cold water, add the gelatine, let it soak for an hour, then dissolve it in a water bath and mix by small quantity the colors finely ground together and wetted to the consistency of a paste. After filtering through flannel the mixture is ready for use.

For coating, the method devised by Mr. Alf. Harman has been found excellent in the hands of the writer, not only for the purpose in question, but also for coating paper with gelatinous or viscous (gum arabic) preparations.

“Take two tin dishes, such as used for the development of the carbon prints; arrange one on your bench tilted to an angle; the lower angle is intended to receive the warm water for keeping the gelatine mixture to a proper temperature. Into this angle of the tray arrange another tray somewhat smaller, and keep it from touching the bottom of the outer one by the insertion of any small article that will suggest itself. Into the inner tray the gelatine mixture is to be poured.”

“The actual making of the tissue can now be proceeded with, and is so simple and certain as not to be believed until put to the test. Purchase a roll of paper-hanger’s lining paper of good quality, cut it into widths of about one and a half inch less than the width of your inner tray, and in length of, say, thirty inches. For the success of the operation it is necessary that the paper be rolled up the narrow way. Now having just sufficient water at a temperature of 100 deg. Fahr. (38 deg. C.) into the outer tray, pour the gelatine mixture into the inner one, and take one of the lengths of rolled paper, and, holding it by both ends, gently lower it on the surface of the gelatine; then at once slowly raise the end of the paper, which will unroll itself and become beautifully coated in far less time than it takes to describe. Twenty sheets may be coated in a quarter of an hour, and be equal in all respects to that made by the most expensive machine.”

In the description of this method of coating, Mr. Harman does not explain how the gelatine should be allowed to set before hanging up the paper to dry, which is, however, obviously important. It is as follows: Place on the tray a smooth board a little larger than the sheet of paper, leaving a small space at the end furthest from the body, and slowly, without a stop, draw off the paper, prepared side uppermost, on the board upon which it should remain until the gelatine is set. If the paper curls up, wet the back a little with a sponge before coating.

The following coating method, due to Mr. Chardon, is excellent for sheets of paper of the ordinary photographic size, 18×22 inches.

On a glass plate placed on a leveled stand, is laid a sheet of paper previously wetted, which is then flattened into contact with an India rubber squeegee, taking care to remove the air bubbles interposed. The quantity of gelatine necessary to coat the paper is regulated by means of a glass rod held by an iron lath, which serves to handle it; at each end of the rod is inserted a piece of an India rubber tube whose thickness regulates that of the gelatine layer. The mixture is poured from a small teapot, at the opening of which has been adapted a bent glass tube about three-sixteenths of an inch in diameter, between the rod and the lath, so that by a simultaneous motion, one can equalize the gelatine as it is poured on. When the gelatine is set the paper is hung up to dry. In drying, the gelatine contracts, and, necessarily, causes a deformation of the tissue, which curls up at the edges and loses its planimetry. To prevent this, while the gelatine is almost dry, the tissue is placed under pressure until quite desiccated. Dumoulin advises to apply on the film, while still soft and tacky, a wooden frame, which, by adhering to it. keeps the tissue perfectly plane as it dries.

[Chardon’s method of coating]

_Sensitizing.—_The tissue is sensitized in a bath of potassium bichromate. The degree of concentration of the bath, which varies from 2 to 5 per cent. of water, is important. The tissue sensitized in a weak bath is less rapidly acted on by light and yields more contrasts than when imbued in a concentrated one. The former should consequently be employed for printing weak negatives, and the latter for those which are intense. A bath compounded with 30 parts of potassium bichromate, 1,000 parts of water and 2 parts of aqueous ammonia, is used for printing negatives of the ordinary intensity, the tissue being, then practically of the same sensitiveness, a silvered paper insolated to obtain a print not over-exposed. For intense negatives the ammonia should be discarded and replaced by the same quantity of chromic acid.

The time of immersion has also a certain influence on the results. The less the tissue is allowed to absorb the solution the less sensitive it is, but also the more the tendency of the half tints to be washed off during the development. Generally the tissue should remain immersed until it lies flat and the edges just commence to curl up, unless white and black impressions are desired, but even then it is preferable to operate as said above, using a bath at 2 per cent.

For use the bichromate bath should be cooled down to 15 deg. C. (59 deg. Fahr.), and much lower in summer, say 10 deg. C. (50 deg. Fahr.), and kept at about this temperature by placing pieces of ice around the tray. At 20 deg. C. (68 deg. Fahr.) the prints are more or less granulated; above this the gelatine is softened and the reticulation greater; at 25 deg. C. (75 deg. Fahr.) it may dissolve.

The addition of alcohol to the bichromate bath—sometimes recommended to harden the film and allow it to stand a higher temperature, and to hasten the desiccation of the tissue—is objectionable, for the spirits tend to reduce the bichromate, which is transformed into the green salt, and, therefore, a partial or complete insolubilization of the gelatine is the result.

Aqueous ammonia added to the sensitizing solution has for its object to permit one to keep the sensitive tissue for a somewhat longer period, but it renders it less sensitive. If enough be added to turn the solution yellow weak prints are obtained.

The bichromate bath should be renewed often. It does not keep owing to the presence of gelatine and other organic matters which it dissolves and which cause the reduction of the chromic salt even in the dark. The tissue prepared in such a bath is not very sensitive and the image develops with difficulty, and even cannot be developed at all.

As said above, the tissue is well sensitized when its edges commence to curl up. It is then removed from the bath by drawing it on a glass rod fixed at the end of the tray, and placed, prepared side down, on a slightly waxed glass plate, rubbing it with an India rubber squeegee to remove the superflous liquid, when it is hung up to dry.

While wet the bichromated tissue is insensitive; the sensitizing can therefore be made by daylight, but the drying should of course be done in the dark room, that is in a room lighted by a candle or the sunlight filtered through a deep orange window glass.

_Caution.—_The soluble bichromates are very poisonous. By absorption they produce skin diseases not without danger and very difficult to cure. Hence when handling the wet tissue the fingers should be protected by India rubber tips, and any yellow, stains on the hands should be rubbed with a dilute solution of aqueous ammonia, and the hands well rinsed in water.

_Drying.—_When the tissue dries rapidly it adheres well on the support upon which it is applied for developing and yields brilliant images which are easily cleared. On the other hand, were it allowed to dry slowly the adherence would not be so complete, the image dull and developing with difficulty. They may even refuse to develop at all from the insolubilization of the gelatine.

In winter and in the cool days of spring and autumn, the gelatine dries quick enough in the air, but when the weather is warm and damp, the gelatine, drying very slowly, may be so softened as to run off, or to produce an entirely objectionable reticulation, or the defects above mentioned. This may be avoided by drying it pinned up in a box, or a closet, over quick-lime.

When dry, the tissue is generally wrinkled, brittle, breaks easily in handling and cannot be laid flat on the cliché; but by holding it over a basin of boiling water, the steam in a few moments rendering it sufficiently pliable to lay it flat between glass plates, where it should be kept under pressure until wanted for use.

The writer always dries the tissue in the following manner, which he devised about sixteen years ago.(27) And not only the least trace of reticulation is avoided, but the tissue, drying quite flat, lies in perfect contact with the negative, which is quite important to obtain proofs exactly sharp all over.

A clean glass plate is rubbed with talc, or, which the writer prefers, flowed with a solution of(28) Yellow wax, pure 1 part Benzine, pure 100 parts

then strongly heated, allowed to cool and rubbed clean (apparently) with a piece of flannel. After once more repeating this operation the plate is coated with the following plain collodion:(29)

Ether, conc. 250 parts, in volume Alcohol, 95 deg 250 parts, in volume Pyroxyline 3 parts

When the film is set, the plate is immersed in filtered water until greasiness has disappeared, when on its removal from the bichromate bath the tissue is laid, without draining, upon it and pressed into contact with the squeegee to remove the excess of liquid and, with it, the air bubbles interposited. The tissue is then allowed to dry in the air on the collodionized plate in the cold season, or, when the weather is warm and damp, in a box in the bottom of which is placed a quantity of quicklime in earthen dishes. When dry, the plates are placed one upon another, wrapped in paper and kept in a dry place. When wanted for use the tissue is stripped off and will be found quite flat with a beautiful surface to print upon.

One should avoid to keep the sensitized tissue in a moist and warm atmosphere, for in less than ten hours it becomes insoluble even in complete darkness. It should neither be kept in the air contaminated with gaseous reductive matters, such as the products of the combustion of coal gas and petroleum, sulphydric or sulphurous emanations from any source, the fumes of turpentine oil, etc., which, by reducing the chromic salt, cause the insolubilization of gelatine, prevent the print to adhere on the support or the clearing of the image, which may even refuse to develop.

The sensitive tissue keeps well for three or four weeks in cool and dry weather, and no more than eight or ten days in summer unless well desiccated and kept in a preservative box. If kept too long the image cannot be developed.

_The Photometer.—_The time of exposure is regulated by means of a photometer. Of all the photometers which have been devised for that purpose we do not know any one more practical than that suggested in 1876 by Mr. J. Loeffler, of Staten Island. It is made as follows: On a strip of a thin glass plate, 6×2 inches, make four or five negatives, 1½×1¼ inch, exposing each one exactly for the same period and developing in the usual manner, but without any intensification whatever. It is even advisable to reduce the intensity if they were opaque. Fix, etc., and apply a good hard varnish. Now cover the back of these negatives with strips of vegetable paper or transparent celluloid, or, better, of thin sheets of mica, in such a manner as there be one thickness on the second negative, two on the third, three on the fourth, etc., leaving the first one uncovered. Then place on the whole a glass plate of the same size as the first and border like a passe-partout.