In 1864 W. B. Bolton and B. J. Sayce published the germ of a process which revolutionized photographic manipulations. In the ordinary collodion process a sensitive film is procured by coating a glass plate with collodion containing the iodide and bromide of some soluble salt, and then, when set, immersing it in a solution of silver nitrate in order to form silver iodide and bromide in the film. The question that presented itself to Bolton and Sayce was whether it might not be possible to get the sensitive salts of silver formed in the collodion whilst liquid, and a sensitive film given to a plate by merely letting this collodion, containing the salts in suspension, flow over the glass plate. Gaudin had attempted to do this with silver chloride, and later G. W. Simpson had succeeded in perfecting a printing process with coilodion containing silver chloride, citric acid and silver nitrate; but the chloride until recently has been considered a slow working salt, and nearly incapable of development. Up to the time of W. B. Bolton and B. J. Sayce's experiments silver iodide had been considered the staple of a sensitive film on which to take negatives; and though bromide had been used by Major Russell and others, it had not met with so much favour as to lead to the omission of the iodide. At the date mentioned the suspension of silver iodide in collodion was not thought practicable, and the inventors of the process turned their attention to silver bromide, which they found could be secured in such a fine state of division that it remained suspended for a considerable time in collodion, and even when precipitated could be resuspended by simple agitation. The outline of the method was to dissolve a soluble bromide in plain collodion, and add to it drop by drop an alcoholic solution of silver nitrate, the latter being in excess or defect, according to the will of the operator. To prepare a sensitive surface the collodion containing the emulsified sensitive salt was poured over a glass plate, allowed to set, and washed till all the soluble salts resulting from the double decomposition of the soluble bromide and the silver nitrate, together with the unaltered soluble bromide or silver nitrate, were removed, when the film was exposed wet, or allowed to dry and then exposed. The rapidity of these plates was not in any way remarkable, but the process had the great advantage of doing away with the sensitizing nitrate of silver bath, and thus avoiding a tiresome operation. The plates were developed by the alkaline method, and gave images which, if not primarily dense enough, could be intensified by the application of pyrogallic acid and silver nitrate’ as in the wet collodion process. Such was the crude germ of a method which was destined to effect a complete change in the aspect of photographic negative taking; but for some time it lay dormant. In fact there was at first much to discourage trial of it, since the plates often became veiled on development.
M. Carey Lea of Philadelphia, and W. Cooper, jr., of Reading, may be said to have given the real impetus to the method. Carey Lea, by introducing an acid into the emulsion, established a practicable collodion emulsion process, which was rapid and at the same time gave negative pictures free from veil. To secure the rapidity Carey Lea employed a fair excess of silver nitrate, and Colonel H. Stuart Wortley gained further rapidity by a still greater increase of it; the free use of acid was the only means by which this could be effected without hopelessly spoiling the emulsion. The addition of the mineral acids such as Carey Lea employed is to prevent the formation of (or to destroy when formed) any silver sub-bromide or oxide, either of which acts as a nucleus on which development can take place. Abney first showed the theoretical effect of acids on the stib-bromide, as also the effect of oxidizing agents on both the above compounds (see below). A more valuable modification was introduced in 1874 by W. B. Bolton, one of the originators of the process, who allowed the ether and the alcohol of the collodion to evaporate, and then washed away all the soluble salts from the gelatinous mass formed of pyroxylin and sensitive salt. After washing for a considerable time, the pellicle was dried naturally or washed with alcohol, and then the pyroxylin redissolved in ether and alcohol, leaving an emulsion of silver bromide, silver chloride or silver iodide, or mixtures of all suspended in collodion. In this state the plate could be coated and dried at once for exposure. Sometimes, in fact generally, preservatives were used, as in the case of dry plates with the bath, in order to prevent the atmosphere from rendering the surface of the film spotty or insensitive on development. This modification had the great advantage of allowing a large quantity of sensitive salt to be prepared of precisely the same value as to rapidity of action and quality of film.
A great advance in the use of the collodion. bromide process was made by Colonel Stuart Wortley, who in June 1873 made known the powerful nature of a strongly alkaline developer as opposed to the weak one which up to that time had usually been employed for a collodion emulsion plate, or indeed for any dry plate.
An example of the preparation of a collodion emulsion and the developer is the following: 2 3/4 oz. of alcohol, 5 oz. of ether, 75 grains of pyroxylin. In 1 oz. of alcohol are dissolved 200 grains of zinc bromide 2; it is then acidulated with 4 or 5 drops of nitric acid, and added to half the above collodion. In 2 drachms of water are dissolved 330 grains of silver nitrate, 1 oz. of alcohol being added. The silvered alcohol is next poured into the other half of the collodion and the brominized collodion dropped in, care being taken to shake between the operations. An emulsion of silver bromide is formed in suspension; and it is in every case left for 10 to 20 hours to what is technically called "ripen," or, in other words, to become creamy when poured out upon a glass plate. When the emulsion has ripened it may be used at once or be poured out into a flat dish and the solvents allowed to evaporate till the pyroxylin becomes gelatinous. In this state it is washed in water till all the soluble salts are carried away. After this it may be either spread out on a cloth and dried or treated with two or three doses of alcohol, and then redissolved in equal parts of alcohol (specific gravity, .805) and ether (specific gravity, .720). In this condition it is a washed emulsion, and a glass plate can be coated with it and the film dried, or it may be washed and some of the many preservatives, such as albumen, beer, coffee, gum, etc., applied.
The type of a useful alkaline developer for collodion plates is as follows:—
I. Pyrogallic acid - . - ' 96 grs.
Alcohol 1 oz.
2. S Potassium bromide - . . 12 grs.
Water distilled 1 oz.
Ammonium carbonate - . 80 grs.
Water 1 oz.
To develop the plate 6 minims of No. 1, 3/4 drachm of No. 2, and 3 drachms of No. 3 are mixed together and made to flow over the plate after washing the preservative off under the tap. Sometimes the development is conducted in a flat dish, sometimes the solution is poured on the plate.i The unreduced salts are eliminated by either cyanide of potassium or sodium hyposulphite. Intensity may be given to the image, if requisite, either before or after 'the "fixing" operation. Where resort is had to ferrous oxalate development, the developer is made in one of two ways—(1) by saturating a saturated solution of neutral potassium oxalate with ferrous oxalate, and adding an equal volume of a solution (10 grains to 1 oz. of water) of potassium bromide to restrain the action, or (2) by mixing, according to Eder's plan, 3 volumes by measure of a saturated solution of the potassium oxalate with 1 volume by measure of a saturated solution of ferrous sulphate, and adding to the ferrous oxalate solution thus obtained an equal bulk of the above solution of potassium bromide. The development is conducted in precisely the same manner as indicated above, and the image is fixed by one of the same agents.
1 An account of Sayce's process is to be found in the Photographic News of October 1865, or the Photographic Journal of the same date.
2 The advantages of this salt were pointed out by Leon Warnerke in 1875.