Remarks.—It is desirable for every operator to use chemicals of uniform strength, and the better method to adopt is to employ those purchased from some one respectable manufactory, and not take those furnished by irresponsible and unconscientious parties. At least one-half of the failures experienced by beginners is from want of good chemicals. It is not economy to purchase a cheap article.
Alcohol is an article that can be procured in almost any small village in the United States, and is in general fit for collodion purposes. I have used 88 per cent, in the above proportions, also the intermediate varieties to 98 per cent., and have been quite successful; but feel convinced that the ordinary 98, as marked (which usually stands by actual test 95 to 97 per cent.), is preferable, except in cases where water is employed in dissolving the iodizing salts, when I would use fully 98 per cent.
Before concluding the subject on plain collodion, I will introduce the account given by Mr. E. A. Hadow of his interesting and valuable experiments, as published in Humphrey's Journal, Vol. VI, page 18.
"Having obtained good collodion-wool, the next point of inquiry was with regard to the solvent; to ascertain whether the addition of alcohol beyond what is necessary to cause the solution of the gun-cotton in ether, were beneficial or otherwise. For this purpose ether and alcohol were prepared perfectly pure, and mixtures were made of 1 of alcohol to 7 of ether, 2 to 6, 3 to 5, 4 to 4 and 5 to 3. In one ounce of each were dissolved 6 grains of gun-cotton and 4 grains of iodide of ammonium (iodide of potassium could not be employed, since it requires a certain amount both of water and alcohol to keep it in solution); they were then compared, using a 35-grain solution of nitrate of silver, both by pouring on separate glasses, and likewise by covering two halves of a plate with two samples, as in examining the gun cottons, thus placing them under the same circumstances during the same time; in this way the effect of adding alcohol was very clearly perceived, since the difference between the collodions was much greater than could have been anticipated.
"The first mixture containing only 1/8th of alcohol was quite unfit for photographic purposes, from its being almost impossible, even with the most rapid immersion, to obtain a film of uniform sensitiveness and opacity throughout, the surface generally exhibiting nearly transparent bands, having an iridescent appearance by reflected light.
"The second mixture with 1/4th of the alcohol is liable to great uncertainty, for if there be any delay in pouring off the collodion the same appearances are seen as in the first, and like it the surface is very insensitive to light, while if the plate be rapidly plunged in the bath, the collodion film becomes much more opaque than before, and is then very sensitive.
"The third proportion of 3 of alcohol to 5 of ether is decidedly the best, giving without the least difficulty a beautifully uniform and highly sensitive film, at the same time perfectly tough and easily removable from the glass if required. A further addition of alcohol, as in the two last collodions, was not attended with any corresponding advantage or increase of sensitiveness; on the contrary, the large proportion of alcohol rendered them less fluid, though with a smaller quantity of gun cotton they would produce very good collodions, capable of giving fine films: the cause of the weakness of the film, observed on adding much of the ordinary alcohol, is the large amount of water it usually contains.
"This surprising improvement, caused by the addition of a certain quantity of alcohol, is referable to causes partly chemical, partly mechanical, for, on examining the films, it will be found in the first, and occasionally in the second collodion, that the iodide of silver is formed on the surface, and can be removed entirely by friction without destroying the transparent collodion film below, while in those collodions that contain more than one-fourth of alcohol, the iodide of silver is wholly in the substance, and in this state possesses the utmost sensitiveness.
"This difference of condition is owing to the very sparing solubility of ether in water, which in the first case prevents the entrance of the nitrate of silver into the film, consequently the iodide and silver solutions meet on the surface; but on addition of alcohol, its solubility enables the two to interchange places, and thus the iodide of silver is precipitated throughout the substance in a state of the utmost division. This difference is clearly seen under the microscope, the precipitate being clotted in the one case, while in the other the particles are hardly discoverable from their fineness.
"The presence of a little water considerably modifies these results, since it in some degree supplies the place of alcohol, and is so far useful; but in other respects it is injurious, for, accumulating in quantity, if the collodion is often used, it makes the film weak and gelatinous, and what is worse, full of minute cracks on drying, which is never the case when pure ether and alcohol are used. Since the ether of the shops almost always contains alcohol, and frequently water, it is important to ascertain their amount before employing it for the preparation of collodion; the quantity of alcohol may be easily ascertained by agitating the ether in a graduated measure glass (a minim glass does very well) with half its bulk of a saturated solution of chloride of calcium; this should be poured in first, its height noted, and the ether then poured on its surface, the thumb then placed on the top, and the two agitated together; when separated, the increase of bulk acquired by the chloride of calcium indicates the quantity of alcohol present, and for this allowance should be made, in the addition of alcohol afterwards to the collodion.