acts at distances relatively great compared with the diameters the molecules themselves. If it were possible to reduce the altered particles of silver salt it was plain that development would be more rapid, and also that the number of molecules reduced by light would be smaller if the metallic silver could be derived from silver compounds within shorter distances of the centres of molecular attraction. Alkaline development accomplished this to a very remarkable extent; but the method is only really practicable when applied to films containing silver bromide and chloride, as silver iodide is only slightly amenable to the alkaline development The introduction of this developer is believed to be of American origin; and it is known that in the year 1862 Major C. Russell used it with the dry plates he introduced.
An alkaline developer consists of an alkali, a reducing agent and a restraining agent. These bodies, when combined and applied to the solid silver bromide or chloride, after being acted upon by light, were able to reduce the sub-bromide or sub-chloride, and to build up an image upon it, leaving the unaltered bromide intact, except so far as it was used in the building up. In 1877 Sir W. Abney investigated this action. A dry plate was prepared by the bath process in the usual manner (to be described below), and exposed in the camera. The exposed film was covered with another film of collodiobromide emulsion, which of course had not seen the light. An image was obtained from the double film by means of the alkaline developer, which penetrated through the upper unexposed film. The development was prolonged until an image appeared through the unexposed film, when the plate was fixed, washed and dried. A piece of gelatinous paper was cemented on the upper film, and a similar piece on the lower after both had been stripped off the glass. When quite dry the two papers were forcibly separated, a film adhering to each. The upper film, although never exposed to light, showed an image in some cases more intense than the under film. The action of the alkaline developer was here manifest: the silver bromide in close contiguity to the exposed particles was reduced to the metallic state. Hence, from this and similar experiments, Abney concluded that silver bromide could not exist in the presence of a freshly precipitated or reduced metallic silver, and that a sub-bromide was Immediately formed. From this it will be seen that the deposited silver is well within the sphere of molecular attraction, and that consequently a less exposure (i.e. the reduction of fewer molecules of the sensitive salt) would give a developable image.
The alkalis used embraced the alkalis themselves and the mono-carbonates. The sole reducing agent up till recent times as pyrogallic acid. In the year 1880 Abney found that hydroquinone was even more effective than pyrogallic acid, its reducing power being stronger. Various other experimentalists tried other kindred substances, but without adding to the list of really useful agents until recently.
The following are some of the most effective:—
| Eikonogen Developer | ||||
| | Eikonogen | 25 | parts. | |
| Sodium sul hlte | 50 | " | ||
| Sodium carbonate | 50 | " | ||
| Potassium bromide | 12 | " | ||
| Water | 1000 | " | ||
| This is a one-solution developer, and acts energetically. | ||||
| Metol Developer | ||||
| Solution A. | ||||
| | Metol | 2 | parts. | |
| Sodium sulphite | 18 | " | ||
| Water | 1000 | " | ||
| Solution B. | ||||
| Sodium carbonate | 6 | parts. | ||
| Potassium bromide | 1 | " | ||
| Water | 1000 | " | ||
| For use, take one part of A to from 1 to 3 parts of B. | ||||
| Amzdol Deteloper | ||||
| | Amidol | 3 | parts. | |
| Sodium sulphite | 100 | " | ||
| Potassium bromide | 1 to 3 | " | ||
| Water | 1000 | " | ||
| This developer requires no addition of alkali. | ||||
| Orlol Developer. | ||||
| Solution A. | ||||
| | Ortol | 15 | parts. | |
| Sodium metabisulphite | 7 | " | ||
| Water | 1000 | " | ||
| Solution B. | ||||
| Sodium carbonate | 100 | parts | ||
| Sodium sulphate | 125 | " | ||
| Potassium bromide | 3 | " | ||
| Water | 1000 | " | ||
| A and B solutions are mixed together in equal proportions. | ||||
Besides these, there are several more, such as adurol, glycin, pyrocatechin, which have been used with more or less success. They all give a black in lieu of that dark olive-green deposit of silver which is so often found with pyrogallol developers. All are alkaline developers, and the image is built up from the sensitive salt within the film. They are applicable to gelatin or collodion plates, but for the latter rather more bromide o an alkali is added, to retard fogging.
Another set of developers for dry plates dependent on the reduction of the silver bromide and the metallic state is founded on the fact that certain organic salts of iron can be utilized. In 1877 M. Carey Lea of Philadelphia and William Willis announced almost simultaneously that a solution of ferrous oxalate in neutral potassium oxalate was effective as a developer, and from that time its use has been acknowledged. In 1882 J. M. Eder demonstrated that gelatino-silver chloride plates could be developed with ferrous citrate, which could not be so readily accomplished with ferrous oxalate. The exposure for chloride plates when developed by the latter was extremely prolonged. In the same year Abney showed that if ferrous oxalate were dissolved in potassium citrate a much more powerful agent was formed, which allowed not only gelatino-chloride plates to be readily developed but also collodio-chloride plates. These plates were undevelopable except by the precipitation method until the advent of the agents last-mentioned owing to the fact that the chloride was as readily reduced as the sub-chloride.
Amongst the components of an alkaline developer we mentioned a restrainer. This factor, generally a bromide or chloride of an alkali, serves probably to form a compound with the silver salt which has not been acted upon by light, and which is less easily reduced than is the silver salt alone-the altered particles being left intact. The action of the restrainer is regarded by some as due to its combination with the alkali. But whichever theory is correct the fact remains that the restrainer does make the primitive salt less amenable to reduction. Such restrainers as the bromides of the alkalis act through chemical means; but there are others which act through physical means, an example of which we have in the preparation of a gelatin plate. In this case the gelatin wraps up the particles of the silver compound in a colloidal sheath, as it were, and the developing solution only gets at them in a very gradual manner, for the natural tendency of all such reducing agents is to attack the particles on which least work has to be expended. In the case of silver sub-bromide the developer has only to remove one atom of bromine, whereas it has to remove two in the case of silver bromide. The sub-bromide formed by light and that subsequently produced in the act of development are therefore reduced. A large proportion of gelatin compared with the silver salt in a film enables an alkaline developer to be used without any chemical restrainer; but when the gelatin bears a small proportion to the silver such a restrainer has to be used. With collodion films the particles of bromide are more or less unenveloped, and hence in this case some kind of chemical restrainer is absolutely necessary. We may say that the organic iron developers require less restraining in their action than do the alkaline developers.
In Major Russell’s process the plate was prepared by immersion in a strong solution of silver nitrate and then washed and a preservative applied. The last-named agent executes two functions, one being to absorb the halogen liberated by the action of light and the other to preserve the film from atmospheric action. Tannin, which Major Russell employed, if we mistake not, is a good absorbent of the halogens, and acts as a varnish to the film. Other collodion dry-plate processes carried out by means of the silver-nitrate bath were very numerous at one time, many different organic bodies being also employed. In most cases ordinary iodized collodion was made use of, a small percentage of soluble bromide being as a rule added to it. When (plates were developed by the alkaline method this extra bromide induced density, since it was the silver bromide alone which was amenable to it, the iodide being almost entirely unaffected by the weak developer which was at that time in general use.
