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PHOTOGRAPHY (Gr. bias, light, and ypa...

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Originally appearing in Volume V21, Page 491 of the 1911 Encyclopedia Britannica.
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PHOTOGRAPHY (Gr. bias, light, and ypa w, to write), the science and art of producing pictures by the action of light on chemically prepared (sensitized) plates or films. History. It would be somewhat difficult to fix a date when what we now know as " photographic action " was first recorded. No doubt the tanning of the skin by the sun's rays was what was first noticed, and this is as truly the effect of solar radiation as is the darkening of the sensitive paper which is now in use in photographic printing operations. We may take it that K. W. Scheele was the first to investigate the darkening action of sunlight on silver chloride. He found that when silver chloride was exposed to the action of light beneath water there was dissolved in the fluid a substance which, on the addition of lunar caustic (silver nitrate), caused the precipitation of new silver chloride, and that on applying a solution of ammonia to the blackened chloride an insoluble residue of metallic silver was left behind. He also noticed that of the rays of the spectrum the violet most readily blackened the silver chloride. In Scheele, then, we have the first who applied combined chemical and spectrum analysis to the science of photography. In 1782 J. Senebier repeated Scheele's experiments, and found that in fifteen seconds the violet rays blackened silver chloride as much as the red rays did in twenty minutes.' In 1798 Count Rumford contributed a paper to the Philosophical Transactions entitled " An inquiry concerning the chemical properties that have been attributed to light," in which he tried to demonstrate that all effects produced on metallic solution could be brought about by a temperature somewhat less than that of boiling water. Robert Harrup in 1802, however, conclusively showed in Nicholson's Journal that, at all events, salts of mercury were reduced by visible radiation and not by change of temperature. In 18or we come to the next decided step in the study of photographic action, when Johann Wilhelm Ritter (1776–1810) proved the existence of rays lying beyond the violet, and found that they had the power of blackening silver chloride. Such a discovery naturally gave a direction to the investigations of others, and Thomas Johann Seebeck (1770–1831) (between 18o2 and 18o8) and, in 1812, Jacques Etienne Berard (1789–1869) turned their attention to this particular subject, eliciting valuable information. We need only mention two or three other cases 1 It may here be remarked that had he used a pure spectrum he would have found that the red rays did not blacken the material in the slightest degree.485 where the influence of light was noticed at the beginning of the 19th century. William Hyde Wollaston observed the conversion of yellow gum guaiacum into a green tint by the violet rays, and the restoration of the colour by the red rays—both of which are the effect of absorption of light, the original yellow colour of the gum absorbing the violet rays, whilst the green colour to which it is changed absorbs the red rays. Sir Humphry Davy found that puce-coloured lead oxide, when damp, became red in the red rays, whilst it blackened in the violet rays, and that the green mercury oxide became red in the red rays—again an example of the necessity of absorption to effect a molecular or chemical change in a substance. U. R. T. Le Bouvier Desmorties in 18or observed the change effected in Prussian blue, and Carl Wilhelm Bockman noted the action of the two ends of the spectrum on phosphorus, a research which John William Draper extended farther in America at a later date. s To England belongs the honour of first producing a photo-graph by utilizing Scheele's observations on silver chloride. In June 1802 Thomas Wedgwood (1771–1805) published in the Journal of the Royal Institution the paper-" An account of a method of copying paintings upon glass and of making profiles by the agency of light upon nitrate of silver, with observations by H. Davy." He remarks that white paper or white leather moistened with a solution of silver nitrate undergoes no change when kept in a dark place, but on being exposed to the daylight it speedily changes colour, and, after passing through various shades of grey and brown, becomes at length nearly black. The alteration of colour takes place more speedily in proportion as the light is more intense. " In the direct beam of the sun two or three minutes are sufficient to produce the full effect, in the shade several hours are required, and light transmitted through different-coloured glasses acts upon it with different degrees of intensity. Thus it is found that red rays, or the common sunbeams passed through red glass, have very little action upon it; yellow and green are more efficacious, but blue and violet light produce the most decided and powerful effects." Wedgwood goes on to describe the method of using this prepared paper by throwing shadows on it, and inferentially by what we now call " contact printing. He states that he has been unable to fix his prints, no washing being sufficient to eliminate the traces of the silver salt which occupied the unexposed or shaded portions. Davy in a note states that he has found that, though the images formed by an ordinary camera obscura were too faint to print out in the solar microscope, the images of small objects could easily be copied on such paper. " In comparing the effects produced by light upon muriate of silver (silver chloride) with those upon the nitrate it seemed evident that the muriate was the more susceptible, and both were more readily acted upon when moist than when dry—a fact long ago known. Even in the twilight the colour of the moist muriate of silver, spread upon paper, slowly changed from white to faint violet; though under similar circumstances no intermediate alteration was produced upon the nitrate. . Nothing but a method of preventing the unshaded parts of the delineations from being coloured by exposure to the day is wanting to render this process as useful as it is elegant." In this method of preparing the paper lies the germ of the silver-printing processes of modern times, and it was only by the spread of chemical knowledge that the hiatus which was to render the " process as useful as it is elegant " was filled up—when sodium thiosulphate (hyposulphite of soda), discovered by Francois Chaussier in 1999, or three years before Wedgwood published his paper, was used for making the print permanent. Here we must call attention to an important observation by Seebeck of Jena in 181o. In the Farbenlehre ofGoethe he says: " When a spectrum produced by a properly constructed prism is thrown upon moist chloride of silver paper, if the printing be continued for from fifteen to twenty minutes, whilst a constant position for the spectrum is maintained by any means, I observe the following. In the violet the chloride is a reddish brown (sometimes more violet, sometimes more blue), and this coloration extends well beyond the limit of the violet; in the blue the chloride takes a clear blue tint, which fades away, becoming lighter in the green. In the yellow I usually found the chloride unaltered; sometimes, however, it had a light yellow tint ; in the red and beyond the red it took a rose or lilac tint. This image of the spectrum shows beyond the red and the violet a region more or less light and uncoloured. This is how the decomposition of the silver chloride is seen in this region. Beyond the brown band, . which was produced in the violet, the silver chloride was coloured a grey-violet for a distance-of several inches. In proportion as the distance from the violet increased, the tint became lighter. Beyond the red, on the contrary, the chloride took a feeble red tint for a considerable distance. When moist chloride of silver, having received the action of light for a time, is exposed to the spectrum, the blue and violet behave as above. In the yellow and red regions, on the other hand, it is found that the silver chloride becomes paler; . the parts acted upon by the red rays and by those beyond take a light coloration." This has been brought forward by J. M. Eder as being the first record we have of photographic action lending itself to production of natural colours. This observation of Seebeck was allowed to lie fallow for many years, until it was again taken up and published as a novelty. The first to found a process of photography which gave pictures that were subsequently unaffected by light was Nicephore de Niepce. His process, which he called provisionally " heliographic, dessins, et gravures," consists in coating the surface of a metallic plate with a solution of asphaltum in oil of lavender and exposing it to a camera image. He recommends that the asphaltum be powdered and the oil of lavender dropped upon it in a wine-glass, and that it be then gently heated. A polished plate is covered with this varnish, and, when dried, is ready for employment in the camera. After requisite exposure, which is very long indeed, a very faint image, requiring development, is seen. Development is effected by diluting oil of lavender with ten parts by volume of white petroleum. After this mixture has been allowed to stand two or three days it becomes clear and is ready to be used. The plate is placed in a dish and covered with the solvent. By degrees the parts unaffected by light dissolve away, and the picture, formed of modified asphaltum, is developed. The plate is then lifted from the dish, allowed to drain, and finally freed from the remaining solvents by washing in water. Subsequently, instead of using oil of lavender as the asphaltum solvent, Niepce employed an animal oil, which gave a deeper colour and more tenacity to the surface-film. Later, Louis Jacques Mande Daguerre (1789–1851) and Niepce used as a solvent the brittle residue obtained from evaporating the oil of lavender dissolved in ether or alcohol—a transparent solution of a lemon-yellow colour being formed. This solution was used for covering glass or silver plates, which, when dried, could be used in the camera. The time of exposure varied somewhat in length. Daguerre remarked that " the time required to procure a photographic copy of a landscape is from seven to eight hours, but single monuments, when strongly lighted by the sun, or which are themselves very bright, can be taken in about three hours." Perhaps there is no sentence that illustrates more forcibly the advance made in photography from the days when this process was described. The ratio of three hours to - -hth of a second is a fair estimate of the progress made since Niepce. The development was conducted by means of petroleum-vapour, which dissolved the parts not acted upon by light. As a rule silver plates seem to have been used, and occasionally glass; but it does not appear whether the latter material was chosen because an image would be projected through it or whether simply for the sake of effect. Viewed in the light of present knowledge, a more perfectly developable image in half-tone would be obtained by exposing the film through the back of the glass. The action of light on most organic matter is apparently one of oxidation. In the case of asphaltum or bitumen of Judaea the oxidation causes a hardening of the material and an insolubility in the usual solvents. Hence that surface of the film is generally hardened first which first feels the influence of light. Where half-tones exist, as in a landscape picture, the film remote from the surface first receiving the image is not acted upon at all, and remains soluble in the solvent. It is thus readily seen that, in the case of half-tone pictures, or even in copying engravings, if the action were not continued sufficiently long when the surface of the film farthest from the glass was first acted upon, the layer next the glass would in some places remain soluble, and on development would be dissolved away, carrying the top layer of hardened resinousmatter with it, and thus give rise to imperfect pictures. In carbon-printing-development from the back of the exposed film is absolutely essential, since it depends on the same principles as does heliography, and in this the same mode of procedure is advisable. It would appear that Niepce began his researches as early as 1814, but it was not till 1827 that he had any success worth recounting. At that date he communicated a paper to Dr Bauer of Kew, the secretary of the Royal Society of London, with a view to its presentation to that society. Its publication, however, was pre-vented because the process, of which examples were shown, was a secret one. In an authentic MS. copy of Niepce's " Memoire," dated " Kew, le 8 Decembre 1827," he says that "in his framed drawings made on tin the tone is too feeble, but that by the use of chemical agents the tone may be darkened." This shows that Niepce was familiar with the idea of using some darkening medium even with his photographs taken on tin plates. Daguerreotype.—We have noticed in the joint process of Daguerre and Niepce that polished silver plates were used, and we know from the latter that amongst the chemical agents tried iodine suggested itself. Iodine vapour or solution applied to a silvered plate would cause the formation of silver iodide on those parts not acted upon by light. The removal of the resinous picture would leave an image formed of metallic silver, whilst the black parts of the original would be represented by the darker silver iodide. This was probably the origin of the daguerreotype process. Such observers as Niepce and Daguerre, who had formed a partnership for prosecuting their researches, would not have thus formed silver iodide without noticing that it changed in colour when exposed to the light. What parts respectively Daguerre and Niepce played in the development of the daguerreotype will probably never be known .with absolute accuracy, but in a letter from Dr Bauer to Dr J. J. Bennett. F.R.S., dated the 7th of May 1839, the former says: "I received a very interesting letter from Mons. Isidore Niepce, dated 12th March [about a month after the publication of the daguerreotype process], and that letter fully confirms what I suspected of Daguerre's manoeuvres with poor Nicephore, but Mr Isidore observes that for the present that letter might be considered confidential." Dr Bauer evidently knew more of " poor Nicephore's " work than most people, and at that early period he clearly thought that an injustice had been done to Niepce at the hands of Daguerre. It should be remarked that Nicephore de Niepce died in 1833, and a new agreement was entered into between his son Isidore de Niepce and Daguerre to continue the prosecution of their researches. It appears further that Niepce communicated his process to Daguerre on the 5th of December 1829. At his death some letters from Daguerre and others were left by him in which iodine, sulphur, phosphorus, &c., are mentioned as having been used on the metal plates, and their sensitiveness to light, when thus treated, commented upon. We are thus led to believe that a great part of the success in producing the daguerreotype is due to the elder Niepce; and indeed.it must have been thought so at the time, since, on the publication of the process, life-pensions of 6000 francs and 4000 francs were given to Daguerre and to Isidore Niepce respectively. In point of chronology the publication of the discovery of the daguerreotype process was made subsequently to the Talbot-type process. It will, however, be convenient to continue the history of the daguerreotype, premising that it was published on the 6th of February 1839, whilst Talbot's process was given to the world on the 25th of January of the same year. Daguerreotype pictures were originally taken on silver-plated copper, and even now the silvered surface thus prepared serves better than electro-deposited silver of any thickness. An outline of the operations is as follows. A brightly-polished silver plate is cleaned by finely-powdered pumice and olive oil, and then by dilute nitric acid, and a soft buff is employed to give it a brilliant polish, the slightest trace of foreign matter or stain being fatal to the production of a perfect picture. The plate, thus prepared, is ready for the iodizing operation. Small fragments of iodine are scattered over a saucer, covered with gauze. Over this the plate is placed, face downwards, resting on supports, and the vapour from the iodine is allowed to form upon it a surface of silver iodide. It is essential to note the colour of the surface-formed iodide at its several stages, the varying colours being due to interference colours caused by the different thicknesses of the minutely thin film of iodide. The stage of maximum sensitiveness is obtained when it is of a golden orange colour. In this state the plate is withdrawn and removed to the dark slide of the camera, ready for exposure. A plan frequently adopted to give an even film of iodide was to saturate a card with iodine and hold the plate a short distance above the card. Long exposures were required, varying in Paris from three to thirty minutes. The length of the exposure was evidently a matter of judgment, more particularly as over-exposure introduced an evil which was called " solarization," but which was in reality due to the oxidation of the iodide by prolonged exposure to light. As a matter of history it may be remarked that the development of the image by mercury vapour is said to be due to a chance discovery of Daguerre. It appears that for some time previous to the publication of the daguerreotype method he had been experimenting with iodized silver plates, producing images by what would now be called the "printing out " process. This operation involved so long an exposure that he sought some means of reducing it by the application of different reagents. Having on one occasion exposed such a plate to a camera-image, he accidentally placed it in the dark in a cupboard containing various chemicals, and found after the lapse of a night that he had a perfect image developed. By the process of exhaustion he arrived at the fact that it was the mercury vapour, which even at ordinary temperatures volatilizes, that had caused this intensification of the almost invisible camera-image. It was this discovery that enabled the exposures to be very consider-ably shortened from those which it was found necessary to give in mere camera-printing. The development of the image was effected by placing the exposed plate over a slightly heated (about 75° C.) cup of mercury. The vapour of mercury condensed on those places where the light had acted in an almost exact ratio to the intensity of its action. This produced a picture in an amalgam, the vapour of which attached itself to the altered silver iodide. Proof that such was the case was subsequently afforded by the fact that the mercurial image could be removed by heat. The developing box was so constructed that it was possible to examine the picture through a yellow glass window whilst the image was being brought out. The next operation was to fix the picture by dipping it in a solution of hyposulphite of soda. The image produced by this method is so delicate that it will not bear the slightest handling, and has to be protected from accidental touching. The first great improvement in the daguerreotype process was the resensitizing of the iodized film by bromine vapour. John Frederick Goddard published his account of the use of bromine in conjunction with iodine in 184o, and A. F. J. Claudet (1797-1867) employed a combination of iodine and chlorine vapour in 1841. In 1844 Daguerre published his improved method of preparing the plates, which is in reality based on the use of bromine with iodine. That this addition points to additional sensitiveness will be readily understood when we remark that so-called instantaneous pictures of yachts in full sail, and of large size, have been taken on plates so prepared—a feat which is utterly impossible with the original process as described by Daguerre. The next improvement in the process was toning or gilding the image by a solution of gold, a practice introduced by H. L. Fizeau. Gold chloride is mixed with hyposulphite of soda, and the levelled plate, bearing a sufficient quantity of the fluid, is warmed by a spirit-lamp until the required vigour is given to the image, as a consequence of which it is better seen in most lights. Nearly all the daguerreotypes extant have been treated in this manner, and no doubt their permanence is in a great measure due to this operation. Images of this class can be copied by taking electrotypes from them, as shown by Sir W. R. Grove and others. These reproductions are admirable in every way, and furnish a proof that the daguerrean image is a relief. Fox-Talbot Process.—In January 1839 Fox Talbot described the first of his processes, photogenic drawing, in a paper to the Royal Society. He states that he began experimenting in 1834, and that in the solar microscope he obtained an outline of the object to be depicted in full sunshine in half a second. He published in the Philosophical Magazine full details of his method, which consisted essentially in soaking paper in common salt, brushing one side only of it with about a 12% solution of silver nitrate in water, and drying at the fire. Fox Talbot stated that by repeating the alternate washes of the silver and salt—always ending, however, with the former—greater sensitiveness was attained. This is the same in every respect as the method practised by Wedgwood in 1802; but, when we come Albumen Process on Glass.—It was a decided advance when Niepce de St Victor, a nephew of Nicephore de Niepce, employed a glass plate and coated it with iodized albumen. The originator of this method did not meet with much success. In the hands of Blanquart Evrard it became more practicable; but it was carried out in its greatest perfection by G. Le Gray. The outline of the operations is as follows: The whites of five fresh eggs are mixed with about one hundred grains of potassium iodide, about twenty grains of potassium bromide and ten grains of common salt. The mixture is beaten up into a froth and allowed to settle for twenty-four hours, when the clear liquid is decanted off. A circular pool of albumen is poured on a glass plate, and a straight ruler (its ends being wrapped with waxed paper to prevent its edge from touching the plate anywhere except at the margins) is drawn over the plate, sweeping off the excess of albumen. and so leaving an even film. The plate is first allowed to dry spontaneously, a final heating being given to it in an oven or before the fire. The heat hardens the albumen, and it becomes insoluble and ready for the silver nitrate bath. One of the difficulties. is to prevent crystallization of the salts held in solution, and this can only be effected by keeping them in defect rather than in excess. The plate is sensitized for five minutes in a bath of silver nitrate, acidified with acetic acid, and exposed whilst still wet, or it may be slightly washed and again dried and exposed whilst in its desiccated state. The image is developed by gallic acid in the usual way. After the application of albumen many modifications were introduced in the shape of starch, serum of milk, gelatin, all of which were intended to hold iodide in situ on the plate; and the development in every case seems to have been by gallic acid. At one time the waxed-paper process subsequently introduced by Le Gray was a great favourite. Paper that had been made translucent by white wax was immersed in a solution of potassium iodide until impregnated with it, after which it was sensitized in the usual way, development being by gallic acid. In images obtained by this process the high lights are represented by metallic silver, whilst the shadows are translucent. Such a print is called a " negative." When silver chloride paper is darkened by the passage of light through a negative, we get the highest lights represented by white paper and the shadows by darkened chloride. A print of this kind is called a " positive." Collodion Process.—A great impetus was given to photography to the next process, which he called "calotype " or " beautiful picture," we have a distinct advance. This process Talbot protected by a patent in 1841. It may be briefly described as the application of silver iodide to a paper support. Carefully selected paper was brushed over with a solution of silver nitrate (ioo grains to the ounce of distilled water), and dried by the fire. It was then dipped into a solution of potassium iodide (50o grains being dissolved in a pint of water), where it was allowed to stay two or three minutes until silver iodide waa formed. In this state the iodide is scarcely sensitive to light, but is sensitized by brushing " gallo-nitrate of silver " over the surface to which the silver nitrate had been first applied. This "gallonitrate " is merely a mixture, consisting of 10o grains of silver nitrate dissolved in 2 oz. of water, to which is added one-sixth of its volume of acetic acid, and immediately before applying to the paper an equal bulk of a saturated solution of gallic acid in water. The prepared surface is then ready for exposure in the camera, and, after a short insolation, develops itself in the dark, or the development may be hastened by a fresh application of the " gallo-nitrate of silver." The picture is then fixed by washing it in clean water and drying slightly in blotting paper, after which it is treated with a solution of potassium bromide, and again washed and dried. Here there is no mention made of hyposulphite of soda as a fixing agent, that having been first used by Sir J. Herschel in February 1840. In a strictly historical notice it ought to be mentioned that development by means of gallic acid and silver nitrate was first known to Rev. J. B. Reade. When impressing images in the solar microscope he employed gallic acid and silver in order to render more sensitive the silver chloride paper that he was using, and he accidentally found that the image could be developed without the aid of light. The priority of the discovery was claimed by Fox Talbot; and his claim was sustained after a lawsuit, apparently on the ground that Reade's method had never been legally published. Talbot afterwards made many slight improvements in the process. In one of his patents he recognizes the value of the proper fixing of his photogenic drawings by hyposulphite of soda, and also the production of positive prints from the calotype negatives. We pass over his application of albumen to porcelain and its subsequent treatment with iodine vapour, as also his application of albumen in which silver iodide was held in suspension to a glass plate, since in this he was preceded by Niepce de St Victor in 1848. in 185o, on the introduction of collodion (q.v.), a very convenient vehicle on account of the facility with which the plates are prepared, and also because it is a substance as a rule totally unaffected by silver nitrate, which is not the case with other organic substances. Thus albumen forms a definite silver compound, as do gelatin, starch and gum. The employment of collodion was first suggested by Le Gray, but it remained for Frederick Scott Archer of London, closely followed by P. W. Fry, to make a really practical use of the discovery. When collodion is poured on a glass plate it leaves on drying a hard transparent film which under the microscope is slightly reticulated. Before drying, the film is gelatinous and perfectly adapted for holding in situ salts soluble in ether and alcohol. Where such salts are present they crystallize out when the film is dried, hence such a film is only suitable where the plates are ready to be immersed in the silver bath. As a rule, about five grains of the soluble gun-cotton are dissolved in an ounce of a mixture of equal parts of ether and alcohol, both of which must be of low specific gravity, •725 and •8o5 respectively. If the alcohol or ether be much diluted with water the gun-cotton (pyroxylin) precipitates, but, even if less diluted, it forms a film which is " Grapey " and uneven. Such was the material which Le Gray proposed and which Archer brought into practical use. The opaque silver plate with its one impression was abandoned; and the paper support of Talbot,. with its inequalities of grain and thickness, followed suit, though not immediately. When once a negative had been obtained with collodion on a glass plate—the image showing high lights by almost complete opacity and the shadows by transparency (as was the case, too, in the calotype process)—any number of impressions could be obtained by means of the silver-printing process introduced by Fox Talbot, and they were found to possess a delicacy and refinement of detail that certainly eclipsed the finest print obtained from a calotype negative. To any one who had practised the somewhat tedious calotype process, or the waxed-paper process of Le Gray with its still longer preparation and development, the advent of the collodion method must have been extremely welcome, since it effected a saving in time, money and uncertainty. The rapidity of photographic action was much increased, and the production of a different character of pictures thus became possible. We give an outline of the procedure. A glass plate is carefully cleaned by a detergent such as a cream of tripoli powder and spirits of wine (to which a little ammonia is often added), then wiped with a soft rag, and finally polished with a silk handkerchief or chamois leather. A collodion containing soluble iodides and bromides is made to flow over the plate, all excess being drained off when it is covered. A good standard formula for the collodion is—55 rains of pyroxylin, 5 oz. of alcohol, 5 oz. of ether; and in this liquid are dissolved 21 grains of ammonium iodide, 2 grains of cadmium iodide and 2 grains of cadmium bromide. When the collodion is set the plate is immersed in a bath of silver nitrate—a vertical form being that mostly used in England, whilst a horizontal dish is used on the continent of Europe—a good formula for which is 35o grains of silver nitrate with to oz. of water. The plate is steadily lowered into this solution, and moved in it until all the repellent action between the aqueous solution of the silver and the solvents of the collodion is removed, when it is allowed to rest for a couple of minutes, after which period it is taken out and placed in the dark slide ready for exposure in the camera. After undergoing proper exposure the plate is withdrawn, and in a room lighted with yellow light the developing solution is applied, which originally was a solution of pyrogallic acid in water restrained in its action by the addition of acetic acid. One of the old formulae employed by P. H. Delamotte was 9 grains of pyrogallic acid, 2 drachms of glacial acetic acid and 3 oz. of water. The image gradually appears after the application of this solution, building itself up from the silver nitrate clinging to the film, which is reduced to the metallic state by degrees. Should the density be insufficient a few drops of silver nitrate are added to the pryogallic acid solution and the developing action continued. In 1844 Robert Hunt introduced another reducing agent, which is still the favourite, viz. ferrous sulphate. By its use the time of necessary exposure of the plate is reduced and the image develops with great rapidity. A sample of this developing solution is 20 grains of ferrous sulphate, 20 minims of acetic acid, with 1 oz. of water. This often leaves the image thinner than is requisite for the formation of a good print, and it is intensified with pyrogallic acid and silver. Other intensifiers are used to increase the deposit on a plate by means of mercury or uranium, followed by other solutions to still further darken the double salts formed on the film. Such intensifying agents have to be applied to the image after the plate is fixed, which is done by a concentrated solution of hypo-sulphite of soda or by potassium cyanide, the latter salt having been first introduced by Martin and Marc Antoine Augustin Gaudin in 1853 (La Lumiere, April 23, 1$53). Twenty-five grains of potassium cyanide to one ounce of water is the strength of the solution usually employed. The reaction of both these fixing agents is to form with the sensitive salts of silver double hyposulphites or cyanides, which are soluble in water and salt. The utility of bromides in the collodion process seems to have been recognized in its earliest days, Scott Archer (1852) and R. J. Bingham (185o) both mentioning it. We notice this, since as late as 1866 a patent-right in its use was sought to be enforced in America, the patent being taken. out by James Cutting in July 1854. Positive Pictures by the Collodion Process.—In the infancy of the collodion process it was shown by Horne that a negative image could be made to assume the appearance of a positive by whitening the metallic silver deposit. This he effected by using with the pyrogallic acid developer a small quantity of nitric acid. A better result was obtained by P. W. Fry with ferrous sulphate and ferrous nitrate, whilst Hugh Diamond gave effect to the matter in a practical way. F. Scott Archer used mercuric chloride to whiten the image. To Robert Hunt, however, must be rewarded the credit of noticing the action of this salt on the image (Phil. Trans., 1843). The whitened picture may be made to stand'out against black velvet, or black varnish may be poured over the film to give the necessary black back-ground, or, more recently, the positive pictures may be produced on japanned iron plates (ferrotype plates) or on japanned leather. This process is still occasionally practised by itinerant photographers. Moist Collodion Process.—It is seen that for the successful working of the collodion process it was necessary that the plate should be exposed very shortly after its preparation; this was a drawback, inasmuch as it necessitated taking a heavy equipment into the field. In 1856, Sir William Crookes and J. Spiller published in the Philosophical Magazine a process whereby they were enabled to keep a film moist (so as to prevent crystallization of the silver nitrate) several days, enabling plates to be prepared at home, exposed in the field, and then developed in the dark room. The plate was prepared in the usual way and a solution of zinc nitrate and silver nitrate in water was made to flow over it. The hygroscopic nature of the zinc salt kept sufficient moisture on the plate to attain the desired end. Various modifications in procedure have been made. Dry Plates.—It would appear that the first experiments with collodion dry plates were due to Marc Antoine Augustin Gaudin. In La Lumiere of the 22nd of April and the 27th of May 1854 he describes his researches on the question; whilst in England G. R. Muirhead, on the 4th of August 1854, stated that light acts almost as energetically on a dry surface as on a wet after all the silver has been washed away from the former previous to desiccation. J. M. Taupenot, however, seems to have been the first to use a dry-plate process that was really workable. His original plan was to coat a plate with collodion, sensitize it in the ordinary manner, wash it, cause a solution of albumen to flow over the surface, dry it, dip it in a bath of silver nitrate acidified with acetic acid, and wash and dry it again. The plate was then in a condition to be exposed, and was to be developed with pyrogallic acid and silver. In this method we have a double manipulation, which is long in execution, though perfectly effective. A great advance was made in all dry-plate processes by the introduction of what is known as the " alkaline developer," which is, however, inapplicable to all plates on which silver nitrate is present in the free state. The developers previously described, either for collodion or paper processes, were dependent on the reduction of metallic silver by some such agent as ferrous sulphate, the reduction taking place gradually and the reduced particles aggregating on those portions of the film which had been acted upon by light. The action of light being to reduce the silver iodide, bromide or chloride, these reduced particles really acted as nuclei for the crystallized metal. It will be evident that in such a method of development the molecular attraction acts at distances relatively great compared with the diameters of the molecules themselves. If it were possible to reduce the all ered 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 was pyrogallic acid. In the year 188o 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 sulphite 5o Sodium carbonate 5o „ Potassium bromide . . Water loon This is a one-solution developer, and acts energetically. Metol Developer. Solution A. Metol 2 parts. Sodium sulphite 18 „ Water too Solution B. Sodium carbonate 6 parts. Potassium bromide Water too For use, take one part of A to from t to 3 parts of B. Arnidol Developer. Amidol . . 3 parts. Sodium sulphite . . . . too Potassium bromide I to 3 „ Water . . Iwo This developer requires no addition of alkali. Ortol Developer. Solution A. Ortol 15 parts. Sodium metabisulphite 7 „ Water I000 „Solution B. Sodium carbonate . . . loo parts. Sodium sulphite . 125 „ Potassium bromide 3 Water Iwo A and B solutions are mixed together in equal proportions. Besides these, there are several more, such as adurol, glycin, p rocatechin, 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 of 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 icdide being almost entirely unaffected by the weak developer which was at that time in general use. Dry-Plate Bath Process.—One of the most successful bath dry-plate processes was introduced by R. Manners Gordon. The plate was given an edging of albumen and then coated with ordinary iodized collodion to which one grain per ounce of cadmium bromide had been added. It was kept in the silver-nitrate bath for ten minutes, after which it was washed thoroughly. The following preservative was then applied: Gum arabic I. Sugar candy Water 6 dr. 2. Gallic acid . 3 grs. Water . . 2 dr. These ingredients were. mixed just before use and, after filtering, applied for one minute to the plate, which was allowed to drain and set up to dry naturally. Great latitude is admissible in the exposure; it should rarely be less than four times or more than twenty times that which would be required for a wet plate under ordinary circumstances. The image may be developed with ferrous sulphate restrained by a solution of gelatin and glacial acetic acid, to which a solution of silver nitrate is added just before application, or by an alkaline developer. In photographic processes not only has the chemical condition of the film to be taken into account but also the optical. When light falls on a semi-opaque or translucent film it is scattered by the particles in it and passes through the glass plate to the back. Here the rays are partly transmitted and partly reflected, a very small quantity of them being absorbed by the material of the glass. Theory points out that the strongest reflection from the back of the glass should take place at the " critical " angle. In 1875 Abney investigated the subject and proved that practice agreed with theory in every respect, and that the image of a point of light in development on a plate was surrounded by a ring of reduced silver caused by the reflection of the scattered light from the back surface of the glass, and that this ring was shaded inwards and outwards in such a manner that the shading varied with the intensity of the light reflected at different angles. To avoid " halation," as this phenomenon is called, it was usual to cover the back of dry plates with some material which should be in optical contact with it, and as nearly as possible of the same density as glass, and which at the same time should absorb all the photographically active rays. This was called " backing a plate." Collodion Emulsion Processes.—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 collodion 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 silvernitrate, 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 photo-graphic 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, jun., 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 sub-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: 21 oz. of alcohol, 5 oz. of ether, 75 grains of pyroxylin. In r oz. of alcohol are dissolved goo 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, r 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 to 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 re-dissolved 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, &c., applied. The type of a useful alkaline developer for collodion plates is as follows:- 1. Pyrogallic acid . 96 grs. Alcohol r oz. 2. Potassium bromide 12 grs. Water distilled r oz. 3. 1 Ammonium carbonate . 8o grs. Water. 1 oz. To develop the plate 6 minims of No. 1, I 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 ' 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. 20 grs. 5 development is conducted in a flat dish, sometimes the solution is poured on the plate.' 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—(T) by saturating a saturated solution of neutral potassium oxalate with ferrous oxalate, and adding an equal volume of a solution (to 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 T 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. Gelatin Emulsion Process.—The facility with which silver bromide emulsion could be prepared in collodion had turned investigation into substitutes for it. As early as September 1871 Dr R. L. Maddox had tried emulsifying the silver salt in gelatin, and had produced negatives of rare excellence. In November 1873 J. King described a similar process, getting rid of the soluble salts by washing. Efforts had also been made in this direction by J. Burgess in July 1873. R. Kennett in 1874 may be said to have been the first to put forward the gelatin emulsion process in a practical and workable form, as he then published a formula which gave good and quick results. It was not till 1878, however, that the great capabilities of silver bromide when held in suspension by gelatin were fairly known; in March of that year C. Bennett showed that by keeping the gelatin solution liquid at a low temperature for as long as seven days extraordinary rapidity was conferred on the sensitive salt. The molecular condition of the silver bromide seemed to be altered, and to be amenable to a far more powerful developer than had hitherto been dreamt of. In 1874 J. S. Stas had shown that various modifications of silver bromide and chloride were possible, and it seemed that the green. molecular condition (one of those noted by Stas) of the bromide was attained by prolonged warming. It may be said that the' advent of rapid plates was 1878, and that the full credit of this discovery should be allotted to C. Bennett. Both Kennett and Bennett got rid of the soluble salts from the emulsion by washing; and in order to attain success it was requisite that the bromide should be in excess of that necessary to combine with the silver nitrate used to form the emulsion. In June 1879 Abney showed that a good emulsion might be formed by precipitating a silver bromide by dropping a solution of a soluble bromide into a dilute solution of silver nitrate. The supernatant liquid was decanted, and after two or three washings with water the precipitate was mixed with the proper amount of gelatin. D. B. van Monckhoven of Ghent, in experimenting with this process, hit upon the plan of obtaining the emulsion by acting on silver carbonate with hydrobromic acid, which left no soluble salts to be extracted. He further, in August 1879, announced that he had obtained great rapidity by adding to the bromide emulsion a certain quantity of ammonia. This addition rapidly altered the silver bromide from its ordinary state to the green molecular condition referred to above. At this point we have the branching off of the gelatin emulsion process into two great divisions, viz. that in which rapidity was gained by long-continued heating, and the other in which it was gained by the use of ammonia—a subdivision which is maintained to the present day. Opinions as to the merits of the two methods are much divided, some maintaining that the quality of the heated emulsion is better than that produced by alkalinity, and vice versa. We may mention that in 1881 Dr A. Herschel introduced a plan for making an alcoholic gelatin emulsion with the idea of inducing rapid drying of the plates, and in the same year H. W. Vogel of Berlin introduced a method of combining gelatin and pyroxylin together by means of a solvent which acted on the gelatin and allowed the addition of alcohol in order to dissolve the pyroxylin. This " collodio-gelatin emulsion " was only a shortlived process, which is not surprising, since its preparation involved the inhalation of the fumes of acetic acid. 1 For further details the reader is referred to Instruction in Photography, 11th ed., p. 362. The warming process introduced by Bennett was soon superseded. Colonel Stuart. Wortley in 1879 announced that, by raising the temperature of the vessel in which the emulsion was stewed to 150° F., instead of days being required to give the desired sensibility only a few hours were necessary. A further advance was made by boiling the emulsion, first practised, we believe, by G. Mansfield in 1879. Another improvement was effected by W. B. Bolton by emulsifying the silver salt in a small quantity of gelatin and then raising the emulsion to boiling point, boiling it for from half an hour to an hour, when extreme rapidity was attained. Many minor improvements in this process have been made from time to time. It may be useful to give an idea of the relative rapidities of the various processes we have described. Daguerreotype, originally. . . . half an hour's exposure. Calotype 2 or 3 minutes' ,., Collodion To seconds' Collodion emulsion 15 seconds' Rapid gelatin emulsion . . . . 116th second
End of Article: PHOTOGRAPHY (Gr. bias, light, and ypa w, to write)
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