THE PHOTOGRAPHIC PROPERTIES OF IODIDE OF SILVER UPON COLLODION. In the preceding part of this Work the physical and chemical properties of Chloride and Iodide of Silver have been described, with the changes which they experience by the action of Light. Nothing however has been said of the surface used to support the Iodide of Silver, and to expose it in a finely divided state to the influence of the actinic radiations. This omission will now be supplied, and the use of Collodion will engage our attention. The sensibility of Iodide of Silver upon Collodion is greatly superior to that of the same salt employed in conjunction with any other vehicle at present known. Hence the Collodio-Iodide film will supersede the paper and Albumen processes in all cases where objects liable to move are to be copied. The causes of this superior sensitiveness, as far as ascertained, may be referred to the state of loose coagulation of a Collodion film and other particulars presently to be noticed. It must however be allowed that there are yet some points affecting the sensitiveness of Iodide of Silver, both mechanical and chemical, of the exact nature of which we are ignorant. The present Chapter may be divided into four Sections:—the nature of Collodion; the chemistry of the Nitrate Bath; the causes affecting the formation and development SECTION I. Collodion. Collodion (so named from the Greek word ??????, to stick) is a glutinous, transparent fluid, procured, as generally said, by dissolving Gun-Cotton in Ether. It was originally used for surgical purposes only, being smeared over wounds and raw surfaces, to preserve them from contact with the air by the tough film which it leaves on evaporation. Photographers employ it to support a delicate film of Iodide of Silver upon the surface of a smooth glass plate. Two elements enter into the composition of Collodion: first, the Gun-Cotton; second, the fluids used to dissolve it. Each of these will be treated in succession. CHEMISTRY OF PYROXYLINE. Gun-Cotton or Pyroxyline is Cotton or Paper which has been altered in composition and properties by treatment with strong acids. Both Cotton and Paper are, chemically, the same. They consist of fibres which are found on analysis to have a constant composition, containing three elementary bodies, Carbon, Hydrogen, and Oxygen, united together in fixed proportions. To this combination the term Lignine or Cellulose Cellulose is a definite chemical compound, in the same sense as Starch or Sugar, and consequently, when treated with various reagents, it exhibits properties peculiar to itself. It is insoluble in most liquids, such as Water, Alcohol, Ether, etc., and also in dilute acids; but when It has been already shown (p. 12) that when a body dissolves in Nitric Acid the solution is not usually of the same nature as an aqueous solution; and so in this case—the Nitric Acid imparts Oxygen first to the Cotton, and afterwards dissolves it. Preparation of Pyroxyline.—If, instead of treating Cotton with Nitric Acid, a mixture of Nitric and Sulphuric Acids in certain proportions be used, the effect is peculiar. The fibres contract slightly, but undergo no other visible alteration. Hence we are at first disposed to think the mixed Acids ineffectual. This idea however is not correct, since on making the experiment the properties of the cotton are found to be changed. Its weight has increased by more than one-half; it has become soluble in various liquids, such as Acetic Ether, Ether and Alcohol, etc., and, what is more remarkable, it no longer burns in the air quietly, but explodes on the application of flame with greater or less violence. This change of properties clearly shows, that although the fibrous structure of the material is unaffected, it is no longer the same substance, and consequently chemists have assigned it a different name, viz. Pyroxyline. To produce the peculiar change by which Cotton is converted into Pyroxyline, both Nitric and Sulphuric Acids are, as a rule, required; but of the two the former is the most important. On analyzing Pyroxyline, Nitric Acid, or a body analogous to it, is detected in considerable quantity, but not Sulphuric Acid. The latter Acid, in fact, serves but a temporary purpose, viz. to prevent the Nitric Acid from dissolving the pyroxyline, which it would be liable to do if employed alone. The Sulphuric Acid prevents the solution by removing water from the Nitric Acid, and so producing a higher degree of concentration; Pyroxyline, although soluble in a dilute, is not so in the strong Acid, and hence it is preserved. The property possessed by Oil of Vitriol of removing water from other bodies, is one with which it is well to be acquainted. A simple experiment will serve to illustrate it. Let a small vessel of any kind be filled to about two-thirds with Oil of Vitriol, and set aside for a few days; at the end of that time, and especially if the atmosphere be damp, it will have absorbed sufficient moisture to cause it to flow over the edge. Now even the strongest reagents employed in chemistry contain, almost invariably, water in greater or lesser quantity. Pure Anhydrous Nitric Acid is a white, solid substance; Hydrochloric Acid is a gas: and the liquids sold under those names are merely solutions. The effect then of mixing strong Oil of Vitriol with aqueous Nitric Acid is to remove water in proportion to the amount used, and to produce a liquid containing Nitric Acid in a high state of concentration, and Sulphuric Acid more or less diluted. This liquid is the Nitro-Sulphuric Acid employed in the preparation of Pyroxyline. Various forms of Pyroxyline.—Very soon after the first announcement of the discovery of Pyroxyline, most animated discussions arose amongst chemists with regard to its solubility and general properties. Some spoke of a "solution of Gun-Cotton in Ether;" whilst others denied its solubility in that menstruum; a third class, by following the process described, obtained a substance which was not explosive, and therefore could scarcely be termed Gun-Cotton. On further investigations some of these anomalies were cleared up, and it was found that there were varieties of Pyroxyline, depending mainly upon the degree of strength of the Nitro-Sulphuric Acid employed in the preparation. Still the subject was obscure until the publication of researches by Mr. E. A. Hadow. These investigations, conducted in the Laboratory of King's College, London, were published in the Journal of the Chemical Society. Constant reference will be made to them in the following remarks. We notice—first, the chemical constitution of Pyroxyline; secondly, its varieties; and thirdly, the means adopted to procure a Nitro-Sulphuric Acid of the proper strength. a. Constitution of Pyroxyline.—Pyroxyline has been sometimes spoken of as a Salt of Nitric Acid, a Nitrate of Lignine. This view however is erroneous, since it can be shown that the substance present is not Nitric Acid, although analogous to it. It is the Peroxide of Nitrogen, which is intermediate in composition between Nitrous Acid (NO3) and Nitric Acid (NO5). Peroxide of Nitrogen (NO4) is a gaseous body of a dark red colour; it possesses no acid properties, and is incapable of forming a class of salts. In order to understand in what state this body is combined with cotton fibre to form Pyroxyline, it will be necessary to digress for a short time. Law of Substitution.—By the careful study of the action of Chlorine, and of Nitric Acid, upon various organic substances, a remarkable series of compounds has been discovered, containing a portion of Chlorine or of Peroxide of Nitrogen in the place of Hydrogen. The peculiarity of these substances is, that they strongly resemble the originals in their physical, and often in their chemical properties. It might have been supposed that agents of such active chemical affinities as Chlorine and Oxide of Nitrogen would, by their mere presence in a body, produce a marked effect; yet it is not so in the case before us. The primitive type or constitution of the substance modified remains the same, even the crystalline form being often unaffected. It seems as if the body by which the Hydrogen had been displaced had stepped in quietly and taken up its position in the framework of the whole without disturbance. Many compounds of this kind are known; they are termed by chemists "substitution compounds." The law invariably observed is, that the substitution takes place in equal atoms: a single atom of Chlorine, for instance, displaces one of Hydrogen; two of Chlorine displace In illustration of these remarks, take the following instances:—Acetic Acid contains Carbon, Hydrogen, and Oxygen; by the action of Chlorine the Hydrogen may be removed in the form of Hydrochloric Acid, and an equal number of atoms of Chlorine be substituted. In this way a new compound is formed, termed Chloracetic Acid, resembling in many important particulars the Acetic Acid itself. Notice particularly that the peculiar properties characteristic of Chlorine are completely masked in the substitution body, and no indication of its presence is obtained by the usual tests! A soluble Chloride gives with Nitrate of Silver a white precipitate of Chloride of Silver, unaffected by Acids, but the Chloracetic Acid does not; hence it is plain that the Chlorine exists in a peculiar and Ultimate state of combination different from what is usual. The substance we have been previously considering, viz. Pyroxyline, affords another illustration of the Law of Substitution. Omitting, for the sake of simplicity, the number of atoms concerned in the change, the action of concentrated Nitric Acid upon ligneous fibre may be thus explained:—
equals
Or in symbols:— CH11O + NO5 = C (Hn-1NO4) O + HO By a reference to the formula, it is seen that the fifth atom of Oxygen contained in the Nitric Acid takes one of b. Chemical Composition of the varieties of Pyroxyline.—Mr. Hadow has succeeded in establishing four different substitution compounds, which, as no distinctive nomenclature has been at present proposed, may be termed compounds A, B, C, and D. Compound A is the most explosive Gun-Cotton, and contains the largest amount of Peroxide of Nitrogen. It dissolves only in Acetic Ether, and is left on evaporation as a white powder. It is produced by the strongest Nitro-Sulphuric Acid which can be made. Compounds B and C, either separate or in a state of mixture, form the soluble material employed by the Photographer. They both dissolve in Acetic Ether, and also in a mixture of Ether and Alcohol. The latter, viz. C, also dissolves in glacial Acetic Acid. They are produced by a Nitro-Sulphuric Acid slightly weaker than that used for A, and contain a smaller amount of Peroxide of Nitrogen. Compound D resembles what has been termed Xyloidine, that is, the substance produced by acting with Nitric Acid upon Starch. It contains less Peroxide of Nitrogen than the others, and dissolves in Ether and Alcohol, and also in Acetic Acid. The ethereal solution leaves, on evaporation, an opaque film, which is highly combustible, but not explosive. By bearing in mind the properties of these compounds, many of the anomalies complained of in the manufacture of Gun-Cotton disappear. If the Nitro-Sulphuric Acid employed is too strong, the product will be insoluble in Ether; whilst if it is too weak, the fibres are gelatinized by the Acid and partly dissolved. c. Means adopted to procure a Nitro-Sulphuric Acid of the requisite strength for preparing Pyroxyline.—This is a point of more difficulty than would at first appear. It To avoid the trouble necessarily attendant upon these preliminary operations, many prefer to use, in place of Nitric Acid itself, one of the salts formed by the combination of Nitric Acid with an alkaline base. The composition of these salts, provided they are pure and nicely crystallized, can be depended on. Nitrate of Potash, or Saltpetre, contains a single atom of Nitric Acid united with one of Potash. It is an anhydrous salt, that is, it has no water of crystallization. When strong Sulphuric Acid is poured upon Nitrate of Potash in a state of fine powder, in virtue of its superior chemical affinities it appropriates to itself the Alkali and liberates the Nitric Acid. If care be taken to add a sufficient excess of the Sulphuric Acid, a solution is obtained containing Sulphate of Potash dissolved in Sulphuric Acid, and free Nitric Acid. The presence of the Sulphate of Potash (or, more strictly speaking, of the Bi-Sulphate) does not in any way interfere with the result, and the effect is the same as if the mixed acids themselves had been used. The reaction may be thus represented:—
CHEMISTRY OF THE SOLUTION OF PYROXYLINE IN ETHER AND ALCOHOL, OR "COLLODION." The substitution compounds B and C, already alluded to as forming the Soluble Cotton of Photographers, are both abundantly soluble in Acetic Ether. This liquid however is not adapted for the purpose required, inasmuch as on evaporation it leaves the Pyroxyline in the form of a white powder, and not as a transparent layer. The rectified Ether of commerce has been found to answer better than any other liquid as a solvent for Pyroxyline. If the sp. gravity be about ·750, it contains invariably a small proportion of Alcohol, which appears to be necessary; the solution not taking place with absolutely pure Ether. The Pyroxyline, if properly prepared, begins almost immediately to gelatinize by the action of the Ether, and is soon completely dissolved. In this state it forms a slimy solution, which, when poured out on a glass plate, dries up into a horny transparent layer. In preparing Collodion for Photographic purposes, we find that its physical properties are liable to considerable variation. Sometimes it appears very thin and fluid, flowing on the glass almost like water, whilst at others it is thick and glutinous. The causes of these differences will now engage our attention. They may be divided into two classes: first, those relating to the Pyroxyline; second, to the solvents employed. a. Variation of Properties in different Samples of soluble Pyroxyline.—The substitution compounds A, B, C, and D differ, as already shown, in the percentage amount of Peroxide of Nitrogen present, and the former are more explosive and insoluble than the latter. But it often Taking extremes in illustration, we notice two principal modifications of soluble Pyroxyline. The first, when treated with the mixture of Ether and Alcohol, sinks down to a gummy or gelatinous mass, which gradually dissolves on agitation The solution is very fluid in proportion to the number of grains used, and when poured out spreads into a beautifully smooth and glassy surface, which is quite structureless, even when highly magnified. The film adheres tightly to the glass, and when the finger is drawn across it, separates in short fragments, and broken pieces. The second variety produces a Collodion which is thick and glutinous, flowing over the glass in a slimy manner, and soon setting into numerous small waves and cellular spaces. The film lies loose upon the glass, is apt to contract on drying, and may be pushed off by the finger in the form of a connected skin. This subject is not thoroughly understood, but it is known that the temperature of the Nitro-Sulphuric Acid at the time of immersing the Cotton influences the result. The soluble variety is produced by hot acids; the second, or glutinous, by the same acids employed cold, or only slightly warm. The best temperature appears to be from 130° to 155° Fahrenheit; if it rises much beyond that point, the acids act upon and dissolve the Cotton. b. The physical properties of Collodion affected by the proportions and purity of the Solvents.—Pyroxyline of the varieties termed B and C dissolves freely in a mixture of Ether and Alcohol; but the characters of the resulting solution vary with the relative proportions of the two solvents. When the Ether is in large excess, the film is inclined to be strong and tough, so that it can often be raised by These properties, produced by Ether in large proportion, disappear entirely on the addition of more Alcohol. The transparent layer is now soft and easily torn, possessing but little coherency. It adheres to the surface of the glass more firmly, and exhibits no tendency to contract and separate from the sides. From these remarks it will be gathered that an excess of Ether, and a low temperature in preparing the Pyroxyline, both favour the production of a contractile Collodion; whilst on the other hand an abundance of Alcohol, and a hot Nitro-Sulphuric Acid, tend to produce a short and non-contractile Collodion. The physical properties of Collodion are affected by another cause, viz. by the strength and purity of the solvents, or, in other words, their freedom from dilution with water. If a few drops of water be purposely added to a sample of Collodion, the effect is seen to be to precipitate the Pyroxyline in flakes to the bottom of the bottle. There are many substances known in chemistry which are soluble in spirituous liquids, but behave in the same manner as Pyroxyline in this respect. The manner in which water gains entrance into the Photographic Collodion is usually by the employment of Alcohol or Spirit of Wine which has not been highly rectified. In that case the Collodion is thicker, and flows less readily than if the Alcohol were stronger. Sometimes the texture of the film left upon evaporation is injured; it is no longer homogeneous and transparent, but semi-opaque, reticulated, or honeycombed, and so rotten that a stream of water projected upon the plate washes it away. These effects are to be attributed not to the Alcohol, but THE COLORATION OF IODIZED COLLODION EXPLAINED. Collodion iodized with the Iodides of Potassium, Ammonium, or Zinc, soon assumes a yellow tint, which in the course of a few days or weeks, according to the temperature of the atmosphere, deepens to a full brown. This gradual coloration, due to a development of Iodine, is caused partly by the Ether and partly by the Pyroxyline. Ether may, with proper precautions, be preserved for a long time in a pure state, but on exposure to the joint action of air and light it undergoes a slow process of oxidation, attended with formation of Acetic Acid and a peculiar principle resembling in properties ozone, or Oxygen in an allotropic and active condition. Iodide of Potassium or Ammonium is decomposed by Ether in this state. Acetate of the Alkali, and Hydriodic Acid (HI), being first produced. The ozonized substance then removes Hydrogen from the latter compound, and liberates Iodine, which dissolves and tinges the liquid yellow. A simple solution of an Alkaline Iodide in Alcohol and Ether does not, however, become so quickly coloured as Iodized Collodion; and hence it is evident that the presence of the Pyroxyline produces an effect. It may be shown that Alkaline Iodides slowly decompose Pyroxyline, and that a portion of Peroxide of Nitrogen is set free: this body, containing loosely combined oxygen, tends powerfully to eliminate Iodine, as may be seen by adding The stability of the particular Iodide used in Iodizing Collodion, influences mainly the rate of coloration, though elevation of temperature and exposure to light are not without effect. Iodide of Ammonium is the least stable, and Iodide of Cadmium the most so; Iodide of Potassium being intermediate. Collodion iodized with pure Iodide of Cadmium usually remains nearly colourless to the last drop, if kept in a cool and dark place. As the presence of free Iodine in Collodion affects its photographic properties, it may sometimes be necessary to remove it. This is done by inserting a strip of Silver-foil; which decolorizes the liquid, by forming Iodide of Silver, soluble in the excess of Alkaline Iodide (p. 42). Metallic Cadmium, and metallic Zinc, have the same effect. When Methylated Spirits are employed in the manufacture of Collodion, the Iodine first liberated is afterwards either partially or entirely reabsorbed, the liquid acquiring at the same time an acid reaction to test-paper. SECTION II. The Chemistry of the Nitrate Bath. The solution of Nitrate of Silver in which the plate coated with iodized Collodion is dipped, to form the layer of Iodide of Silver, is known technically as the Nitrate Bath. The chemistry of Nitrate of Silver has been explained at page 13, but there are some points relating to the properties of its aqueous solution which require a further notice. Solubility of Iodide of Silver in the Nitrate Bath.—Aqueous solution of Nitrate of Silver may be mentioned in the list of solvents of Iodide of Silver. The proportion dissolved is in all cases small, but it increases with the strength of the solution. If no attention were paid to this This solvent power of Nitrate of Silver on the Iodide is well shown by taking the excited Collodion plate out of the Bath, and allowing it to dry spontaneously. The layer of Nitrate on the surface, becoming concentrated by evaporation, eats away the film, so as to produce a transparent, spotted appearance. In the solution of Iodide of Silver by Nitrate of Silver a double salt is formed, which corresponds in properties to the double Iodide of Potassium and Silver in being decomposed by the addition of water. Consequently, in order to saturate a Bath with Iodide of Silver it is only necessary to dissolve the total weight of Nitrate of Silver in a small bulk of water, and to add to it a few grains of an Iodide; perfect solution takes place, and on subsequent dilution with the full amount of water, the excess of Iodide of Silver is precipitated in the form of a milky deposit. Acid condition of Nitrate of Silver.—A solution of pure Nitrate of Silver is neutral to blue litmus-paper, but that prepared from the commercial Nitrate has usually an acid reaction; the crystals having been imperfectly drained from the acid mother-liquor in which they were formed. Hence, in making a new Bath it is often advisable not only to saturate it with Iodide of Silver, but to neutralize the free Nitric acid it contains. There is also a peculiar condition of Nitrate of Silver crystallized from a solution of the metal in Nitric Acid, which renders it quite unfit for photographic purposes (see p. 101). It is thought to depend upon the presence of an oxide of Nitrogen, possibly of Nitrous Acid, and the remedy is to dry the crystals very strongly, or, better still, to fuse them at a moderate heat: mere neutralization with Carbonate of Soda does not suffice. In melting Nitrate of Silver great care should be taken not to raise the heat so high as to decompose the salt, The Nitrate Bath, although perfectly neutral when first prepared, may become acid by continued use, if Collodion containing much free Iodine be constantly employed. In that case a portion of Nitric Acid is liberated, thus:—
When Collodion is iodized entirely with alkaline Iodides, it liberates Iodine by keeping; and hence the occasional use of Ammonia may be required to remove acidity from the Bath. But since the introduction of the Iodide of Cadmium, which preserves the Collodion nearly or quite colourless, the necessity for neutralizing Nitric Acid in the Bath has ceased. Alkaline condition of the Bath.—By "alkalinity" of the Bath is meant a condition in which the blue tint is rapidly restored to reddened litmus-paper. This indicates that an Oxide of some kind is present in solution, which, by combining with the acid in the reddened paper, neutralizes it and removes the red colour. If a small portion of caustic Potash or Ammonia be added to a strong solution of Nitrate of Silver, it produces a brown precipitate, which is Oxide of Silver.
The solution however, from which the precipitate has separated, is not left in a neutral state, but possesses a faint alkaline reaction. Oxide of Silver and Carbonate of Silver are also abundantly soluble in water containing Nitrate of Ammonia; which salt is continually accumulating An alkaline Bath is perhaps of all conditions the one most fatal to success in photography. It leads to that universal darkening of the film on applying the developer to which the name of "fogging" has been given. Hence care must be used in adding to the Bath substances which tend to make it alkaline. Collodion containing free Ammonia, often sold in the shops, gradually does so. The use of Potash, Carbonate of Soda, Chalk, or Marble, to remove free Nitric Acid from the Bath, has the same effect; and hence, when they are employed, a trace of Acetic acid must afterwards be added. The mode of testing a bath for alkalinity is as follows:— a strip of porous blue litmus-paper is taken and held to the mouth of a bottle of glacial Acetic acid until it becomes reddened; it is then placed in the liquid to be examined and left for ten minutes or a quarter of an hour. If Oxide of Silver be present in solution, the original blue colour of the paper will slowly but gradually be restored. Occasional formation of Acetate of Silver in the Nitrate Bath.—In preparing a new Bath, if the crystals of Nitrate of Silver are acid, it is usual to add an alkali in small quantity. This removes the Nitric Acid, but leaves the solution faintly alkaline. Acetic Acid is then dropped in, which, by combining with the Oxide of Silver, forms Acetate of Silver. Acetate of Silver is not formed by the simple addition of Acetic Acid to the Bath, because its production under such circumstances would imply the liberation of Nitric Acid; but if an alkali be present to neutralize the Nitric Acid, then the double decomposition takes place, thus—
Acetate of Silver is a white flaky salt, sparingly soluble in water. It dissolves in the Bath only in small proportion, but yet sufficiently to affect the Photographic Substances which decompose the Nitrate Bath.—Most of the common metals, having superior affinity for Oxygen, separate the Silver from a solution of the Nitrate; hence the Bath must be kept in glass, porcelain, or gutta-percha, and contact with Iron, Copper, Mercury, etc., must be avoided, or the liquid will be discoloured, and a black deposit of metallic Silver precipitated. All developing agents, such as Gallic and Pyrogallic Acids, the Protosalts of Iron, etc., blacken the Nitrate Bath, and render it useless by reducing metallic Silver. Chlorides, Iodides, and Bromides produce a deposit in the Bath; but the solution, although weakened, may again be used after passing through a filter. Hyposulphites, Cyanides, and all fixing agents decompose Nitrate of Silver. Organic matters, generally, reduce Nitrate of Silver, either with or without the aid of light. Grape Sugar, Albumen, Serum of Milk containing caseine, etc., blacken the Bath, even in the dark. Alcohol and Ether act more slowly, and produce no injurious effect unless the liquid is constantly exposed to light. These facts indicate that the Nitrate Bath containing Changes in the Nitrate Bath by use.—The solution of Nitrate of Silver employed in exciting the Collodion film gradually decreases in strength, but not so quickly as the Bath used in sensitizing papers for printing. If the amount of Nitrate be allowed to fall as low as twenty grains to the ounce of water, the decomposition will be imperfect, and the film will be pale and blue, even with a highly iodized Collodion. A gradual accumulation of Ether and Alcohol also takes place in the Bath after long use, in consequence of which the developing solutions flow less readily upon the Collodionized plates, and oily stains are apt to be produced. Diminished sensitiveness of the Iodide film is sometimes traced to impurities in the Bath, when it is very old, and has been much used. These are probably of an organic nature and may often be partially removed by agitation with kaolin, or animal charcoal. The latter however is objectionable, being usually contaminated with Carbonate of Lime, which makes the Bath alkaline; or (in the case of purified animal charcoal) with traces of Hydrochloric Acid, which liberate Nitric Acid in the Bath. Even the kaolin may as a preliminary precaution be washed with dilute Acetic Acid to remove Carbonate of Lime if any should be present. SECTION III. The Conditions which affect the Formation and Development of the Latent Image in the Collodion process. It will be necessary to preface the observations contained in this Section by defining two terms which are frequently confounded with each other, but are in reality of distinct meaning. These terms are "Sensitiveness" and "Intensity." By Sensitiveness is meant a facility of receiving impression from very feeble rays of light, or of receiving it quickly from brighter rays. Intensity, on the other hand, relates to the appearance of the finished Photograph, independently of the time taken to produce it,—to the degree of opacity of the image, and the extent to which it obstructs transmitted light. It will be seen as we proceed that the conditions necessary to obtain extreme sensitiveness of the Iodide film are different from, and often opposed to, those which give the maximum intensity of image. CAUSES WHICH INFLUENCE THE SENSITIVENESS OF IODIDE OF SILVER ON COLLODION. Some of the most important are as follows:— a. The presence of free Nitrate of Silver.—When the sensitive film is removed from the Nitrate Bath, the Iodide of Silver is left in contact with excess of Nitrate of Silver. The presence of this compound is not essential to the action of the light, since, if it be removed by washing in distilled water, the image may still be impressed. In such a case however the effect is produced slowly, and a longer exposure in the Camera is required. The sensitiveness of the Iodide film does not increase uniformly with the amount of the excess of Nitrate of Silver, as measured by the strength of the Bath. It is found that no advantage in this respect can be gained by using a proportion of Nitrate of Silver greater than 30 or 35 grains to the ounce of water, although solutions of three times this strength have been sometimes employed. It has been asserted that a chemically pure Iodide of Silver, which is unaffected in colour by the direct action of light, is also incapable of receiving the invisible image in the Camera; and that the sensitiveness of a washed Collodion film is due to a minute quantity of Nitrate of Silver still remaining. Iodide of Silver in the state in which it is thrown down on diluting with water a strong b. Free acids in the Nitrate Bath.—Strong oxidizing agents, such as Nitric Acid, greatly diminish the sensibility of the film, and hence the importance of removing the free acid often met with in commercial samples of the Nitrate of Silver. The effect of even a single drop of strong Nitric Acid in an eight-ounce Nitrate Bath will be appreciable; and when the proportion is increased to one drop per ounce, it will be difficult to obtain a rapid impression. Acetic Acid has far less effect upon the sensitiveness than Nitric Acid, and being found useful during the development of the image is commonly employed; but when great rapidity is desired, it should be added cautiously, and in a proportion very much less than that in the solution known as the Aceto-Nitrate of Silver, which contains about one drop of the glacial acid to each grain of Nitrate of Silver. c. Addition of certain organic matters.—It has long been remarked that the use of bodies like Albumen, Gelatine, Caseine, etc., which combine with Oxides of Silver, retard the action of light upon Iodide of Silver; and the recent observations of the Author enable him to confirm this statement. It is probable that one cause, amongst others, of the great sensibility of the Collodion film is due to the fact that Pyroxyline is a substance peculiarly indifferent to the Salts of Silver, exhibiting no tendency to reduce them to the metallic state; and it is proved by experiment that the addition of Grape Sugar, or of the resinous body, Glycyrrhizine, which resembles Albumen in d. Impurities in the soluble Iodides.—Commercial Iodide of Potassium often contains Iodate of Potash, which is found to have a retarding effect upon the action of light; also Carbonate of Potash, which, in Collodion, produces Iodoform, Commercial Iodide of Cadmium is a purer salt than the Iodide of Potassium, and may be advantageously substituted for it; but it possesses the property of coagulating Albumen, and hence cannot be employed in conjunction with that substance. e. Presence of free Iodine.—Both in the waxed paper and the Collodion processes, the solutions often contain a small quantity of free Iodine. This Iodine, in contact with the Nitrate of Silver of the Bath, produces a mixed Iodide and Iodate of Silver, and liberates Nitric Acid. It thus retards the sensitiveness of the film in proportion to the quantity of Iodine present. Collodion of a full yellow colour is perceptibly less sensitive than the same rendered colourless; and when enough Iodine has been liberated to give a red or brown tint, double the original exposure will probably be required. If brown Collodion be much used, the Nitrate Bath may by degrees become sufficiently contaminated with free Nitric Acid to interfere with the sensitiveness of the film; Certain substances may be added to coloured Collodion which possess the property of counteracting the retarding influence of the free Iodine, such, for instance, as the Oils of Cloves, Cinnamon, etc.; they probably act in virtue of their affinity for Oxygen, by preventing the formation of Iodate of Silver. In colourless Collodion they produce little or no effect, neither do they remove the insensitiveness of the film when dependent upon a too acid condition of the Nitrate Bath. f. Addition of Bromide or Chloride to Collodion.—In the Daguerreotype a very exalted state of sensibility is obtained by exposing the silvered plate first to the vapour of Iodine, and afterwards to that of Bromine or Chlorine; but this rule does not apply to the Collodion process, which differs essentially in principle. Soluble Bromides added to Collodion lessen its sensibility to an appreciable extent, as also do Chlorides. This rule however may perhaps be liable to an exception when artificial light is used, which contains a greater proportion of the rays of small refrangibility, known to act more powerfully upon the Bromide than upon the Iodide of Silver (p. 66). g. Density of the sensitive film.—When the proportion of soluble Iodide in the iodizing solution is too great, the film is very dense, and the Iodide of Silver is apt to burst out upon the surface, and fall away in loose flakes into the Bath. This condition, which is highly unfavourable to sensitiveness, is very common in Collodion, and constitutes what is termed "over-iodizing." The Iodide, in fact, is formed in such a case too much upon the surface, and consequently, when the fixing agent is applied, the image not being retained by the film, is washed off and lost. On the other hand, the sensibility of the film is not lessened by reducing the amount of Iodide in Collodion to a minimum, if all the solutions are neutral; but the pale blue films formed by a dilute Collodion, and which almost h. Impurities in Ether and Alcohol.—Pure Ether should be neutral to test-paper, but the commercial samples of this article have usually either an acid or an alkaline reaction. The frequent occurrence of a peculiar oxidizing principle in Ether has also been pointed out (p. 85). Each of these three conditions is injurious to sensitiveness; the first and last by liberating Iodine when alkaline Iodides are used; and the second, by producing Iodoform under the same circumstances. In this case the Collodion remains colourless, but gives inferior results. The Author has also observed that Ether which has been redistilled from the residues of Collodion may contain a volatile principle (probably a compound Ether?) which produces a retarding effect upon the action of light. Commercial Spirit of Wine is not always uniform in composition, as sufficiently evidenced by the test of smell. It may contain "fusel oil" or other volatile substances, which become milky on dilution with water, and are believed to injure the quality of the spirit for Photographic use. i. Relative proportions of Ether and Alcohol in Collodion.—It was shown at p. 84 that the addition of Alcohol to Collodion lessens the contractility of the film, and renders it soft and gelatinous. This condition is favourable to the formation of the invisible image in the Camera, the play of affinities being promoted by the loose manner in which the particles of Iodide are held together. It is therefore usual to add to Collodion as much Alcohol as it will bear without becoming glutinous, or leaving the glass; the exact quantity required varying with the strength of the spirit or its freedom from dilution with water. k. Decomposition in the Collodion.—Collodion iodized with the metallic Iodides generally, excepting the Iodide of Cadmium, becomes brown and loses sensitiveness in the course of a few days or weeks. If the free Iodine, the cause of the brown colour, be removed, the greater part, but not the whole, of the sensitiveness is regained. The experiments of the Author, and of others, have proved that a solution of Pyroxyline in contact with an unstable iodide, slowly undergoes decomposition, the result of which is that Iodine is set free, and an equivalent quantity of the base remains in union with certain organic elements of the Collodion. Decomposition also gradually ensues when iodized Collodion is placed in contact with reducing agents, such as Proto-iodide of Iron, Gallic Acid, Grape Sugar, Glycyrrhizine, etc., so that these combinations do not retain a constant sensibility for any length of time. Even plain Collodion uniodized cannot be preserved many months without a small but perceptible amount of change. l. Decomposition in the Nitrate Bath.—A Collodion Nitrate Bath which has been much used, often gives a less sensitive film than when newly made. It is known also that many organic substances which reduce Nitrate of Silver, if added to the Bath, produce a state which is favourable to sensitiveness whilst the decomposition is taking place, but is eventually unfavourable; hence the solution will be injured by adding either Gallic or Pyrogallic Acid, and by organic matters generally if exposed to light. Recapitulation.—The conditions most favourable to extreme sensitiveness of the Iodide of Silver on Collodion may be condensed as follows:—perfect neutrality of the solutions employed; a soft, gelatinous state of the film; absence of Chlorides and other salts which precipitate Nitrate of Silver; an undecomposed Collodion, containing no organic matter of that kind which is precipitated by basic Acetate of Lead, and combines with oxides of Silver. THE CONDITIONS WHICH AFFECT THE DEVELOPMENT OF THE LATENT IMAGE. The general theory of the development of a latent image by means of a reducing agent, having been simply explained in the third Chapter, may now be more fully examined in its application to the Iodide of Silver on Collodion. a. The presence of free Nitrate of Silver essential to the development.—This subject has already been mentioned (p. 36). A sensitive Collodion plate, carefully washed in distilled water, is still capable of receiving the radiant impression in the Camera, but it does not admit of development until it has been redipped in the Bath, or treated with a reducing agent to which Nitrate of Silver has been added: and if the proportion of free Nitrate of Silver on a Collodion film be too small, the image will be feeble or altogether imperfect in parts, with patches of green or blue, due to deficient reduction. b. Comparative strength of deducing Agents.—No increase of power in a developer will suffice to bring out a perfect image on an under-exposed plate, or upon a film containing too little Nitrate of Silver. But there is considerable difference in the length of time which the various developers require to act. Gallic Acid is the most feeble, and Pyrogallic Acid the strongest, producing at least four times more effect than an equal weight of the crystallized Protosulphate of Iron, and twenty times more than the Protonitrate of Iron. c. The effect of free Acid upon the development.—Acids tend to retard the reduction of the image as well as to diminish the sensibility of the film to light. Nitric Acid especially does so, from its powerful oxidizing and solvent properties. The effect of Nitric Acid is particularly seen when the film of Iodide of Silver is very blue and transparent, and the quantity of Nitrate of Silver retained upon its surface small. Under such circumstances the Acetic Acid also moderates the rapidity of development, but it has not that tendency altogether to suspend it possessed by Nitric Acid. It is therefore usefully employed, to enable the operator to cover the plate evenly with liquid before the development commences, and to preserve the white parts of the impression from any accidental deposit of metallic Silver due to irregular action of the reducing agent. On comparing the retarding effects of free acid upon the light's action, and upon the development, we see that the former is the most marked,—that a small quantity of Nitric Acid produces a more decided influence upon the impression of the image in the Camera than upon the bringing out of that image by means of a developer. d. Accelerating effect of certain organic matters.—Organic bodies, like Albumen, Gelatine, Glycyrrhizine, etc., which combine chemically with oxides of Silver, and were shown in the last Section to lessen the sensitiveness of the Iodide film,—facilitate the development of the image, producing often a dense deposit of a brown or black colour by transmitted light. In the same way, viz. by a retention of organic matter, may partly be explained the fact, that the image developed by Pyrogallic Acid, although proved by the application of tests to contain no more than an equal quantity of Silver, possesses greater opacity by transmitted light, than that resulting from the use of protosalts of Iron: and in the case of the Collodion itself the same rule applied—if it be pure, it is liable to give a less vigorous impression than when by long keeping a partial decomposition has taken place, and products have been formed which combine e. Molecular conditions affecting Intensity.—The physical structure of the Collodion film is thought to exert an influence upon the mode in which the reduced Silver is thrown down during the development. A short and almost powdery state, such as Collodion iodized with the alkaline iodides acquires by keeping, is considered favourable, and a glutinous, coherent structure unfavourable, to density. This is certainly the case when the film is allowed to dry before development, as in the process with desiccated Collodion and, to some extent, in the Oxymel preservative process. The mode of conducting the development also affects the density; a rapid action tending to produce an image of which the particles are finely divided and offer a considerable resistance to the passage of light, whilst a slow and prolonged development often leaves a metallic and almost crystalline deposit, comparatively translucent and feeble. The writer has observed, that with certain samples of Collodion the image is much enfeebled by keeping the plate for a considerable time,—a quarter of an hour or longer,—after sensitizing, but before development. This effect is not the result of the Nitrate of Silver having partially drained away, since a second dip in the Nitrate Bath immediately before applying the Pyrogallic Acid, does not remedy it. An alteration of molecular structure may therefore be the correct explanation, and if so, a contractile Collodion would suffer more than one possessing less coherency. The actinic power of the light at the time of taking the picture, influences the appearance of the developed image; the most vigorous impressions being produced by a strong light acting for a short time. On a dull dark day, or in copying badly lighted interiors, the photograph will often lack bloom and richness, and be blue and inky by transmitted light. f. Development of images upon Bromide and Chloride of Silver.—Of the three principal Salts of Silver, the Iodide is the most sensitive to light, but the Bromide and Chloride, under some conditions, are more easily developed and give a darker image. In the Collodion process the difference is principally seen when organic bodies, like Grape Sugar, Glycyrrhizine, etc., are introduced in order to increase the intensity; a far more decided effect being produced by adding both Glycyrrhizine and a portion of Bromide or Chloride, than by using the Glycyrrhizine alone. g. The intensity of the image affected by the length of exposure.—This point has been briefly alluded to in the third Chapter. If the exposure in the Camera be prolonged beyond the proper time the development takes place rapidly but without any intensity, the picture being pale and translucent. The effects produced by over-action of the light are particularly seen when the Nitrate Bath contains Nitrite of Silver, or Acetate of Silver; the image being frequently in such a case dark by reflected light, and red by transmitted light,—more nearly resembling in fact a photographic print, developed on paper prepared with Chloride of Silver. When Collodion plates are coated with honey without previously removing the free Nitrate of Silver, a slow reducing action is set up, which may give rise to the characteristic appearance above referred to, after development. Other organic substances, such as biliary matter, etc., will act in the same way. h. Certain conditions of the Bath which affect development.—Attention may be called to a peculiar state of the Nitrate Bath, in which the Collodion image developes unusually slowly, and has a dull grey metallic appearance, with an absence of intensity in the parts most acted on by the light. This condition, which occurs only when using a newly mixed solution, is thought by the Author to depend Commercial Nitrate of Silver has sometimes a fragrant smell, similar to that produced by pouring strong Nitric Acid upon Alcohol. When such is the case, it contains organic matter, and produces a Bath which yields red and misty pictures. Nitrate of Silver which has been sufficiently strongly fused to decompose the Salt, and produce a portion of the basic Nitrite of Silver exhibits great peculiarity of development, the image coming out instantaneously and with great force. This condition is exactly the reverse of that produced by the presence of acids, in which the development is slow and gradual. In summing up the different conditions of the Nitrate Bath which affect the development of the image, as many as four might be mentioned, each of which gives a more rapid reduction than the one which precedes it. These are—the acid Nitrate Bath, the neutral Bath, the Bath of strongly fused Nitrate of Silver, and the Bath containing Ammoniacal Nitrate of Silver, which is quite unmanageable, and produces an instantaneous and universal blackening of the film on the application of the developer. Greater intensity of image is commonly obtained in a Nitrate Bath which has been a long time in use, than in a newly mixed solution: this may be due to minute quantities of organic matter dissolved out of the Collodion film, which, having an affinity for Oxygen, partially reduce the Nitrate of Silver; and also to the accumulation of Alcohol and Ether in an old Bath producing a short and friable structure of the film. i. Effect of Temperature on Development.—Reduction of the oxides of noble metals proceeds more rapidly in On the other hand, if the heat of the atmosphere be excessive, the tendency to rapid reduction will be greatly increased, the solutions decomposing each other almost immediately on mixing. In this case the remedy will be to use Acetic Acid freely both in the Bath and in the developer, at the same time lessening the quantity of Pyrogallic Acid, and omitting the Nitrate of Silver which is sometimes added towards the end of the development. Also in the case of films which are to be kept for a long time in a sensitive condition by means of honey, etc., the modifying influence of temperature must be observed, and the quantity of free Nitrate of Silver left upon the film be reduced to a minimum if the thermometer stands higher than usual. SECTION IV. On certain Irregularities in the Developing Process. The characteristics of the proper development of a latent image are—that the action of the reducing agent should cause a blackening of the Iodide in the parts touched by light, but produce no effect upon those which have remained in shadow. In operating both on Collodion and paper however there is a liability to failure in this respect; the film beginning, after the application of the developer, to change in colour to a greater or less extent over the whole surface. There are two main causes which produce this state of things:—the first being due to an irregularity in the action of the light; the second to a faulty condition of the chemicals employed. If from a defect in the construction of the instrument, The luminous image of the Camera not being perfectly pure, mere over-exposure of the sensitive plate will usually have the same effect. In such a case, when the developer is poured on, a faint image first appears, and is followed by a general cloudiness. The clearness of the developed Collodion picture is much influenced by the condition of all the solutions employed, but particularly so by that of the Nitrate Bath. If this liquid be in the state termed alkaline (p. 88), it will be impossible to obtain a good picture; and even when neutral, care and avoidance of all disturbing causes will be required to prevent a deposition of Silver upon the shadows of the image: especially so when Nitrite of Silver or Acetate of Silver are present, both of these salts being more easily reduced than the Nitrate of Silver. The use of Acid is the principal resource in obviating cloudiness of the image. Acids lessen the facility of reduction of the Salts of Silver by developing agents (p. 98), and hence when they are present the metal is deposited more slowly, and only on the parts where the action of the light has so modified the particles of Iodide as to favour the decomposition: whereas if acids be absent or present in insufficient quantity, the equilibrium of the mixture of Nitrate of Silver and reducing agent which constitutes the developer is so unstable, that any rough point or sharp edge is likely to become a centre from which the chemical action, once started, radiates to all parts of the plate. Various acids have been employed, such as Acetic acid, Citric acid, Tartaric acid, etc. Nitric acid is the most effectual of all, but is seldom used, because, although the image can often be developed with great clearness when the Bath contains a small quantity of Nitric acid, yet such The state of the Collodion must be attended to as well as that of the bath; it should be either acid or neutral, not alkaline. Colourless Collodion may be used successfully as a rule, but sometimes a little free Iodine is advantageously added. Care should be taken in introducing organic substances, many of which dissolve out into the bath, and spoil it for giving clear pictures. Glycyrrhizine, however, which is recommended to produce intensity of Negatives, has no effect of that kind, and may be employed with safety. The condition of the developing agent is a point of importance in producing clear and distinct pictures. The Acetic acid, which is advised in the formulÆ, cannot be omitted or even lessened in quantity without danger. This is particularly the case in hot weather or under any other condition which favours reduction, such as neutrality of the bath, etc.; at all times, in fact, when the solutions of Pyrogallic acid and Nitrate of Silver decompose each other with unusual rapidity. In addition to the points now mentioned, viz. the state of the Bath, of the Collodion, and of the developer, the reader should also study the remarks made in the Third Section of Chapter III. on the effect of surface conditions in modifying the deposition of vapour and of metallic Silver: he will then in all probability experience but little difficulty in dealing with those numerous irregularities in the action of the developing fluid, which often prove the greatest hindrance to the successful practice of the Collodion process. |