Chapter 4

Good well-sized paper should be employed. Rives is too tender and absorbs too much. Steinbach is better. For small sizes, whatever be the paper selected, it is well to size it with starch and, if possible, to calender it on a hot steel plate, or, in lieu, to iron it. This is not, however, a sine qua non. The paper is sensitized by brushing or by floating. To sensitize by floating, it should be left but for a few seconds on the solution and removed by dragging it on a glass rod in order to remove the superfluous liquid. Only the surface of the paper should be impregnated, otherwise the whites would be more or less tinted and the image imbedded not as sharp.

Sensitized, the paper must be dried as rapidly as possible. It does not keep, and should be employed the day it is prepared or the day after, keeping it well wrapped in paper.

As said above, it is exposed under a positive cliché, plans, designs, etc., drawn on tracing paper or linen. The more transparent the material, the more rapid the chemical changes. During the insolation—and it is very short—the chromic compound is reduced, the parts corresponding to the ground, that is, the transparent parts of the cliché, are discolored, while those under the design remain unaltered; the image being, therefore, faintly visible, and being formed of the chromic mixture, it is developed by the fumes of aniline in a blue black tone. Therefore, if the paper be not sufficiently exposed, the ground is colored like the image, although not as deeply, since the dye formed is proportionate to the more or less quantity of unreduced compound, and if exposed too long the image is imperfectly developed or not at all by excess.

The discoloration of the ground, which turns to a greenish hue, easily indicates when the exposure is sufficient. But, to ascertain it, the beginner should use _tests_ as in the cyanofer process. Mr. Endemann regulates the time of exposure by partly covering a strip of the sensitive paper with a piece of the tracing material upon which the design is made, and exposing the whole until the covered part of the paper assumes the same shade as the part directly exposed to light.

To develop the print is placed in the bottom of a tray, which is then covered with a lid upon which is pinned blotting paper well imbued with an aniline and benzine mixture, or the reverse; that is, exposing the print fastened to the lid and placing the aniline on the bottom of the tray. The tray should be hermetically closed; that is a condition to obtain a fine and equal coloration. For this purpose the lid should be well lined with sheets of blotting paper and a weight placed over it during the operation. Large prints are necessarily developed in a fumigating box made ad hoc. The aniline solution consists of

Aniline (commercial for 8 parts red) Benzine, rectified 100 parts

In place of benzine, ether U.S.P., sp. grav. 0.837, may be used.

When the proof is not over-exposed the development commences in a few minutes. The image first takes a dirty black olive color which turns blue in water, then the tone darkens to a dark-brownish tint. The time of exposure to the aniline fumes depends on the time of insolation; if short, the ground is soon tinted, and consequently the development should then be stopped; if over-exposed, the development proceeds slowly. The darkest tone is obtained by a rather full exposure which admits a long fumigation. Sometimes the image takes a green color; it suffices then to wash the proof in water rendered alkaline by a few drops of aqueous ammonia to obtain the normal color.

To somewhat improve the tone of the image and, if objectionable, to remove the chromic oxide which tinges the ground greenish, the proof should be immersed in a dilute solution of sulphuric acid 1:100, then washed twice, and finally passed in ammoniacal water 1:100.

Mr. Hermann Endemann has published, in 1866, the following process in the _Journal of the American Chemical Society_, pp. 189 et seq.:

The paper, which must be well sized with glue, 1:50, is sensitized with the following solution and exposed when dry, but still slightly damp:

A. Potassium 1 ounce or 480 bicarbonate parts Salt 1 ounce or 480 parts Sodium vanadate 2/3 grain or 0.66 part Water 20 ounces or 9,600 parts B. Sulphuric acid 2 ounces or 960 parts Water 10 ounces or 4,800 parts

When cold mix to A.

“From the composition of the solution,” says Mr. Endemann, “it is evident that it must be strongly acid; but when this solution is exposed to light, in the presence of the organic substances of the paper, the acidity of the solution disappears, we obtain potassium and sodium sulphates, basic chromium sulphate, salt and vanadic acid. While, therefore, the unchanged parts of the paper remain acid, the changed parts acquire a neutral reaction, and while the first will readily assimilate bases, the second will not. Exposed in an atmosphere laden with water and aniline, the aniline will be absorbed in those parts where the solution remains acid and in proportion to the remaining acidity.”

To develop the image the paper is spread over the opening of a frame tightly placed on a pan, in the bottom of which is heated a solution of aniline in water, 1:50, until the image appears brown, and for further development in a box laden with steam water, which, according to Mr. Endemann, requires two hours to obtain a deep black coloration. To remove the chromium compound the picture is immersed in a solution of aqueous ammonia, 1:6, then washed and dried.

A few years ago the aniline process was improved by developing the image with the aniline-benzine mixture vaporized by steam in a box made specially for that purpose, whereby a reproduction can be obtained in less than ten minutes.

In the photographic department of Messrs Poulson & Eger’s Hecia Architectural and Ornamental Iron Works, which is directed by Charles Bilordeaux, this process is worked in the following manner:

The developing is made of sheet iron with a door sliding up and down, it being balanced by a counterpoise, and provided with a chimney. In the box is a gutter, extending the whole length of the bottom, covered with muslin and connected to a steam pipe; there is also a coil similarly connected. After the insolation, which requires about one minute in sunshine, the print is suspended in the box, the muslin brushed over with the solution of aniline, and live steam allowed to pass through the gutter for only two minutes, whereby the aniline being vaporized acts on the chromic salt and develops the image; then the steam is allowed in the coil, and, in from three to four minutes, the paper is dry and the picture finished. The image stands on a slightly greenish ground, which is not objectionable for the purpose the reproductions are made.

The sensitizing solution is similar to that published by Mr. Endemann, viz.:

Potassium bichromate 460 grams Sodium chloride 460 grams Ammonium vanadate 0.75 gram Sulphuric acid 1 liter Water 13 liters

THE PRIMULINE OR DIAZOTYPE PROCESS.

Primuline, discovered in 1887 by Mr. A. G. Green, an English chemist, is a dye of a primrose color, possessing a great affinity for cotton fibers, to which it is readily fixed by simply immersing the material for a few moments in a hot solution of the dye. If the material so dyed be placed in an acidified solution of nitrous oxide, the primuline is diazotized, forming a derivative compound of a deeper color, which fades in the light, and which in presence of amines and phenols gives rise to a variety of dyes whose color depends on the reagent employed, while, when acted on by light, the resulting compound is entirely deprived of this property. In other words, the diazotized primuline acts as a mordant only when not altered by the luminous action.

The chemical change light effects in the diazotized primuline is not well known. It is pretty certain, however, that nitrogen is set free, for if gelatine imbued with primuline be immersed in water after insulation, nitrogen is set free and can be collected as usual in a tub filled with water and inverted on the substance.

By itself diazotized primuline is slowly influenced by light, but quickly acted on in presence of organic substances. It is more sensitive when applied on cotton or paper than on wool, silk, linen, and such organic compounds as gelatine, albumen, caseine, starch, etc. Its sensitiveness is about one-tenth less with gelatine than with cotton.

The sensitiveness of diazotized primuline to light, when united to organic substances and the different colors which can be obtained with the unaltered compound, have given rise to an interesting printing method, the invention of Messrs. A. G. Green, C. F. Cross, and E. J. Bevan, which yields _positive impressions from positive clichés_. The manipulations of the process are simple:

In a certain quantity of rain water, kept at nearly the boiling temperature by an alcohol lamp placed under the vessel, dissolve per cent. 2 parts of commercial primuline, and in this immerse, by means of a glass rod, some pieces of calico—free from dressing—turning them over several times during the immersion. When the fibers are well imbued, which requires from four to five minutes, remove the calico with the glass rod and rinse it thoroughly in water. This done, wring out the superfluous liquid as much as possible, and, finally, immerse each piece separately in a solution of

Sodium nitrite, 7 parts commercial Hydrochloric acid, 16 parts commercial Water 100 parts

After turning the pieces of calico two or three times over, they are rinsed to eliminate the acid, then drained and placed between sheets of blotting paper to dry. All this, except the impregnation with primuline, should be done in the dark room.

As said above, primuline is transformed by nitrous oxide into a diazotized compound, and consequently the material is now susceptible of being acted on by light. It does not keep, and should be exposed, etc., soon after its preparation.

Paper is impregnated with primuline either by floating or brushing. The best results are obtained with paper previously sized with arrowroot or gelatine in order to keep the image entirely on the surface of the paper.

Linen, silk and wool are treated as calico.

The clichés should be positive to obtain positive expressions and somewhat more opaque than those employed in the processes before described, else vigor and intensity could not be obtained. Here we must state that the primuline process seems to be better adapted for the reproductions of drawings, such as made for the black process, and of opaque photo-clichés in lines, or white and black, than for printing in half tone.

When the material to print upon is thick and wholly impregnated with diazotized primuline, it is advisable, since the insulation could not be prolonged to effect the change through, to expose the back of the material for a certain but short period in order to _clear_ it. This is especially advantageous when the cliché is not of good intensity.

During the exposure, which varies from 30 seconds to 10 minutes and more by a dull light, the progresses of the luminous action is seen by the bleaching of the material which assumes a dingy coloration. But in order to ascertain when the decomposition is complete on the ground of the image, it is well to use _tests_ as in the cyanofer process, dipping one of them in the developer from time to time.

The developers are compounded as follows:

FOR RED. Beta-naphthol 4 parts Caustic potassa 6 parts Water 500 parts

Rub the alkali and the naphthol with a little water in a mortar and add the remainder of the water.

FOR ORANGE. Resorcin 3 parts Water 500 parts

When dissolved add

Caustic potassa 5 parts

FOR YELLOW. Carbolic acid, cryst 5 parts Water 500 parts

FOR PURPLE. Naphthylamine 6 parts Hydrochloric acid, in 6 parts volume

Mix in a mortar, then add

Water 500 parts

FOR BLACK. Eikonogen, white crystals 6 parts Water 500 parts

Pulverize the eikonogen, add the water and, at the same time, the material on its removal from the printing frame, and keep in motion until the development is effected.

FOR BROWN. Pyrogallol 5 parts Water 500 parts

After the development, which requires but a few moments, it suffices to wash the material to fix the image by eliminating the soluble compounds. However, for purple the material should be passed in a dilute solution of tartaric acid and not washed afterwards; it should remain acid.

When it is desirable to obtain an impression in several colors, the various developers are thickened with starch, then locally applied with a brush on the image, which is always visible after exposure.

For printing on wood, glass and porcelain, see further on.

PRINTING ON WOOD, CANVAS, OPAL, AND TRANSPARENCIES

_Printing on Wood._—To print on a wood block a design to be engraved on the same presents certain difficulties. In the first place, the sensitizing solution must not be absorbed by the wood, but remain wholly on its surface; then the photo film, although thick enough to produce an image sufficiently intense to be distinctly visible in all its details, should not scale or clip away under the graver, and not interfere in any way with the work of the artist; the least touch of the graver must reach the wood and make its impression. Lastly, the design should be permanent. These difficulties will be avoided by adhering to the instructions given in the lines following.

The solution to render impervious the surface of the wood consists of

Common gelatine 5 parts Gum arabic 3 parts Castile soap 3 parts Water 100 parts

Dissolve by heat on a water bath.

To apply it, the wood is rubbed with fine sandpaper, then heated over a spirit lamp to about 86 deg. Fahr. (30 deg. C.) and upon it is poured in excess the liquefied and quite warm solution, which must be allowed to penetrate in the pores of the wood by letting it gelatinize, when it is wiped off clean. Nothing must remain on the surface of the wood. This done, and while still damp, the preparation is rendered insoluble by pouring over a solution of alum at 5 per 100 of water. The object of this preliminary operation is to render the wood impervious, and therefore to prevent the sensitizing solution to penetrate its texture. The wood is then heated again and its surface whitened with a little silver white or sulphate of barium, diffused in a small quantity of the following warm solution:

Gelatine 1 parts Alum 0.1 part Water 100 parts

While wet, this is smoothed with a jeweler’s brush, taking care to leave on the wood, a very thin layer of the mixture, only sufficient to obtain a white surface which, by contrasting with color of the wood assists the engraver in his work. The wood should now be allowed to dry thoroughly, when it is coated with a tepid solution of

Isinglass 3 parts Water 100 parts

and dried.

Now the sensitizing process differs according as whether the cliché is positive or negative. In the former case the preparation is sensitized with the solution employed in the black process, proceeding afterwards as usual; in the latter, that is, when the cliché is negative, the best process is the cuprotype.(12)

For printing, special frames are employed to permit one to examine the progress of the impression from time to time without the possibility of either the wood block or the cliché moving. These frames open in two. The upper frame is provided with screws on the four sides to hold firmly the block when it is placed into contact with the cliché by means of the screws fixed on the cross bars. As to the cliché, if it is made on a glass plate, it is secured on the thick glass plate of the lower frame by two wooden bars against it pushed by screws.

When the block is ready for printing, the prepared side is usually concave. It is straightened by slightly wetting the back and resting it on one end, prepared side against the wall.

_Printing on Canvas.—_The canvas should be first brushed with a solution of aqueous ammonia in alcohol, 1:3, to remove greasiness until the thread just commences to show, then, when rinsed and dry, rubbed with fine sand to give a tooth, dusted, washed with a sponge and then coated with the following solution, proceeding afterwards as in the cuprotype process:

Isinglass 8 parts Uranic nitrate 5 parts Copper nitrate 2 parts Water 200 parts

_Printing on Opal, Celluloid, etc._, is quite simple; it suffices to coat the material with the following gelatine solution, and, when the film is dry, to proceed in operating by any one of the processes before described.

The sensitizing compound may be incorporated to the gelatine solution, but we prefer not to do it and to sensitize the plates as they are wanted for use.

A. Gelatine 4 parts Water 70 parts in volume

Dissolve and mix little by little in order:

B. Chrome alum 0.25 parts Water, hot 20 parts C. Alcohol 10 parts

When coated place the plates on a level stand until the gelatine is set, and let them dry on a rack.

_Transparencies._—Prepare the plate as directed above with

A. Gelatine 6 parts Water 70 parts B. Chrome alum 0.3 part Water, hot 20 parts C. Alcohol 10 parts

Sensitize with the uranic-copper solution employed in the cuprotype. By this process transparencies of a rich brown, not actinic, color are obtained. Consequently they can be used to reproduce negatives by the same process. For lantern slides they may be toned black by platinic chloride.

To strip off the picture, apply, first, on the glass plate a substratum of India rubber, 2 to 100 of benzole, coat with plain collodion, immerse the plate in water as soon as the film is set, and when greasiness has disappeared pour on the gelatine solution and proceed.

For tranferring on any material, a sheet of paper is immersed in a solution of India rubber cement in 20 parts of benzole, dried, coated with the gelatine solution, sensitized, etc., by operating in the ordinary manner. After development, the proof, being dry, is brushed over with alumed gelatine moderately warm, dried, immersed in tepid water until the gelatine is softened and tacky, when it is placed on the material and squeezed into contact. This done, the transfer should be allowed to dry thoroughly. Now, by imbuing the proof with benzole to dissolve the India rubber, the paper is easily stripped off, leaving behind the picture adhering to the material.

TRACING PROCESS ON METAL.

We call the attention of metal engravers to this process. It is well known that wood engravers have their original designs photographed on the block in order to save considerable time by not making the drawing themselves; moreover the cost is nominal, so to say, and the copy more true and perfect than it can be done by hand. Why should not the copper engraver and the aquafortist avail themselves of the same advantages? A few do it secretly, no doubt, but the generality not knowing the process, or, if so, not having tried it, think it is not possible or that it may spoil their plates. This is an error. It can be done and very easily by adhering to the following instructions:

Dissolve 2 parts of ammonium bichromate in 100 parts of water, and in this let soak for an hour or so 10 parts of Coignet’s best gelatine, then dissolve on a water bath, filter through flannel, and the solution is ready for use.

Before being coated, the plate should necessarily be cleaned free from oxidation and greasy matters. This is done by immersing the plate for a few moments in a warm solution of common potash, then rinsing and rubbing it with chalk moistened with a little water, when after rinsing again and draining the plate should be immediately prepared.

To spread the gelatine solution in an even and thin layer, a tournette is employed. The most simple consists of a round wooden stick of which the upper part is carved in the form of a cup with an edge, or rim, about one quarter of an inch broad. On this rim is melted some gutta-percha, upon which the plate is pressed into contact and adhers quite firmly when the gutta-percha is solidified. The stick is perforated at the lower end and revolves on an iron pivot fixed at the bottom of the support, being held in the opening on the platform of the same, as shown in the diagram on the following page.

The plate being fastened to the tournette, the warm gelatine solution is flowed over it and spread to the edges by means of a glass rod or a piece of cardboard, avoiding air bubbles. This done the tournette is set into motion, and when the film is equalized, which is done in a moment, the plate is detached, placed on a leveled stand and slowly dried with the spirit lamp.

[A Tournette]

By a good light the exposure on the shade does not exceed twenty minutes with a pretty intense transparency, and should be regulated with a photometer. When the insulation is sufficient, the image is slightly visible, and should be so. The plate is then bordered with banking wax and bitten-in with a solution of ferric chloride at 45 deg. Baumé, or—

Ferric chloride, crystal 20 parts Hydrochloric acid 1 part Water 100 parts

The parts of the gelatine film the most acted on are impermeable, so to say, and consequently do not allow the etching fluid to penetrate to the copper; while those the least impressed are permeated according as to their degree of insolation, Therefore, when the ferric chloride solution is poured upon the film and carefelly brushed over with a soft brush, in a few moments the image progressively appears, the deep blacks first, then the half tints, and lastly the most delicate details, the whole requiring but a few minutes. It is now that the etching action should be stopped by washing under the tap. However, should by excess of exposure, or any other cause, the details not appear within five or six minutes, the ferric chloride should nevertheless be washed off, for then it may find its way under the film and the plate would be spoiled. After washing the gelatine is dissolved in a solution of potash, etc., when the image would be found slightly engraved.

Should the image be in half-tints, it would be advisable to apply a grain of rosin on the gelatine film just before etching. To engrave on steel the operations are the same, but on its removal from the printing frame the plate should be soaked with water renewed several times until the bichromate is washed off. The film is then dried spontaneously and afterwards flowed for about two minutes with the Solution A, then, this being thrown away, with the Solution B, which is allowed to act for a similar period.

A. Nitric acid, pure 120 parts Silver nitrate 6 parts Alcohol, 95 deg 50 parts Water 75 parts B. Nitric acid, pure 5 parts Alcohol, 95 deg 40 parts Water 60 parts

GRAPHOTYPY.

This process consists in converting a cliché in half tones into one in lines, which can be directly printed on paper, or impressed, by means of an ink transfer made as explained before, on a stone, or on a zinc or copper plate for etching in relief, or in intaglio, according as the cliché is negative or positive.

A cliché on gelatine, but preferably on a collodion film, is varnished with a solution of yellow wax and bitumen in benzole and turpentine-oil: