Chapter 6

The tank is constructed as follows: Procure two pieces of best white plate glass, about 6 inches square; between these place a piece of rubber of the same size square, and about 3/8 of an inch thick. In the center of this rubber cut out a circle about 4 inches diameter, and from one of the corners to the center of the circle cut out a narrow strip ¼ inch wide; this serves as the mouth of the tank. The two pieces of glass and the rubber are cemented together with rubber cement; then, to hold it firmly together, two brass flanges are used as a clamp, with four screws at an equal distance apart; a thin sheet of rubber is on the glass side of the flanges to prevent direct contact with the glass, the center remaining clear for the rays of light to pass through solution and glass.

One of the best orthochromatic effects made through this tank is with a three-grains-to-the-ounce solution of bichromatic of ammonia or bichromate of potassium. In this method there is no preparation used on the plate. A common rapid dry plate is exposed through this solution; the exposure, however, is about twenty times longer than it would be if you removed the tank with the yellow solution, or, in other words, if a dry-plate is exposed one minute without the yellow solution it would have to be exposed twenty minutes through a three-grain solution of bichromate of potassium or ammonia. It produces wonderful results on an oil painting or any highly colored object.

Another method, and the one best adapted for landscapes, is to bathe the plate in erythrosine and then expose it through a yellow glass screen.

As an illustration, suppose we have before us a beautiful landscape. In the foreground beautiful foliage, in the center a lake, in the distance hills, with a bluish haze appearing pleasing to the eye, also a nice sky with light clouds. Now make a plain negative, and see what has become of your clouds, hills, and the distance--not visible! Some photographers have been led to think that by underexposing they retain the distance, but they sacrifice the foreground; besides, it does not produce an orthochromatic effect.

But it is a good idea to expose longer on the foreground than you do on the distance. This can be done by raising the cap of the lens skyward and gradually shut off, giving the foreground more exposure.

Plates are prepared for orthochromatic work as follows: Take any ordinary rapid dry plate, place it in a bath containing

Distilled water 200 c.c. Strong liquid ammonia 2 c.c.

Rock it for two minutes, work as dark as you possibly can. Now take it out, and place it in the second bath for one and one-fourth minutes and keep it rocking. Have on hand for use a stock solution of

Distilled water 1,000 parts. Erythrosine "Y" brand 1 part.

Prepare second bath as follows:

Erythrosine stock solution 25 c.c. Distilled water 175 c.c. Strong water ammonia 4 c.c.

After removing the plate, dip it again face down to rinse off any particles of scum, etc., that may get in the bath accidentally. This bath may be used for one dozen 8 by 10, when it should be thrown away and fresh bath used.

After the plates come out of the last bath, they should be stood on clean blotting paper to absorb the excess of solution. I would also advise to use clean fingers. Pyro. or hypo. on the fingers is a drawback to success.

After plates have been drained, place them in a cleaned rack in an absolutely light-tight closet, with air holes so constructed as to admit air but no light; the plates will dry in from eight to twelve hours. They are best prepared in the evening, and, if the closet is good, will be dry in the morning.

After the plates are dry they may be packed face to face with nothing between them, in a double-cover paper box, and put in a dark closet free from sulphureted hydrogen gas, until ready for use. I have kept plates for three months in this way, and they were in good condition. Great care should be used in developing these plates, as they are sensitive to the red; get used to developing in a dark part of the dark room; occasionally you may look at the process of development in a little stronger light.

The exposure through the yellow screen with an erythrosine plate is about the same as if you had no orthochromatic plate--a plain plate instead--provided you are not using too dark a yellow on your screen. This can only be determined by experience. I will give to a common plate about four seconds, an orthochromatic plate under the same conditions five seconds.

The yellow glass screen is prepared as follows: Take a piece of best plate glass--common cannot be used--clean it nicely; take another large plate glass, or anything that is level and true, level it with a small spirit-level. Now take the cleaned piece of glass and coat it with

AURENTIA COLLODION.

Ether 5 oz. Alcohol 5 oz. Cotton 60 grs.

The aurentia to be added to suit your judgment; it takes a very small quantity to make an intense yellowish-red collodion. Pour it on the center of the glass, flow it to the edges, and before it sets place it on the level glass and allow it to set; when set put it in a rack to dry.

Should it dry in ridges, the collodion may be too thick, and it must be thinned down with equal parts of alcohol and ether. A single piece of plate glass, about one-eighth inch thick, coated with aurentia collodion, is all that is required with an erythrosine plate. Or, after a piece has been successfully coated, another piece of the same plate glass, and the same size, may be cemented together with balsam, having the coated aurentia side between the two glasses; the edges may then be bound with paper.

In using different colored solutions, collodion, etc., I have found that one will change the focus and the other not. With some screens you must focus with them in their positions; take away the screen, and the picture appears out of focus. I cannot fully explain why it is, and for this reason will not make the attempt; experience alone can teach it.

Another thing that has been tried lately is to do away with the yellow screen by substituting a yellow coating direct on the plate. No doubt the focus on an object that requires absolute sharpness is somewhat affected by the use of a glass. We have been successful, on a small scale, to coat the plate with the following yellow solution:

Place in a tray enough of a saturated solution of tropæolin in wood alcohol to cover the plate; allow it to remain ten seconds. It is necessary that the plate should be bathed previously in erythrosine and dried. Before applying the tropæolin, which, being in alcohol, dries in a few minutes, have some blotting paper on hand, as the solution gathers in a pool and leaves bad marks on the end of the plate.

The plate can be developed in the usual way. Try it and see the results.--_Reported in the Beacon._

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PLATINOTYPE PRINTING.[1]

[Footnote 1: A communication to the North London Photographic Society.]

Platinotype, which may be considered to be the most artistic of photographic printing processes, may be separated into its three modifications--the hot bath and cold bath, in which a faintly visible image is developed, and the Pizzighelli printing-out paper. The hot bath process, again, may be divided into the black and white and sepia papers. I intend to give you a rough outline of the preparation of the paper and working of these modifications, concluding by demonstrating the hot bath method, and handing around prints by it.

Platinotype may almost be styled an iron printing process, for, while no trace of iron or its salts is found in the finished print, certain salts of iron are mixed with the platinum salt, which is platinum combined with two atoms of chlorine (PtCl2), as a means for readily reducing it; this, however, cannot be effected without the presence of neutral oxalate of potash, hence the use of the oxalate bath. There is no platinum in the paper for the cold bath process, it being coated with ferric oxalate mixed with a very small quantity of chloride of mercury--somewhere about one grain to an ounce of ferric oxalate solution. When dry it is ready for exposure, which is about three times less than with silver printing.

It is absolutely necessary to store all papers for platinum printing in an air-tight tin containing chloride of calcium, which must be dried by heating from time to time. For the cold bath, however, it is important to have moisture present during printing, or it may be after printing and before development. If the paper is left in a dampish room for fifteen minutes, it should be sufficient. Prints made by exposing damp paper, or damping dry paper just before development, must be developed within one hour if the maximum of vigor is desired; by delaying the development some hours, the prints in the meantime being stored in a drawer so that they may retain their moisture, an increase of half tone and warmth of color will be obtained. If it should be necessary to delay development for a day or two, the prints must be dried before a fire soon after being removed from the frames, and then stored in a calcium tube until wanted for development.

While printing, the lemon color of the paper receives a grayish colored image, which, although faint, can, with practice, be judged as easily as silver printing.

The developer consists of oxalate of potash and potassic chloro-platinite--about thirty grains of the platinum salt to half an ounce of oxalate forming about six ounces of solution; a great many variations, however, may be made in the proportions of platinum salt and oxalate, and different effects secured. Development is effected by sliding the print face downward on to the developer, which must be rocked after the development of each print to avoid scum marks. To clear the prints they are washed in three or four baths of a weak solution of hydrochloric acid after leaving the developer, to remove all traces of the iron salts, and finally washed for a quarter of an hour in three changes of water; they are then finished, and may be dried between clean blotting paper.

Pizzighelli's process differs from the above in being one that prints fully out in the frame without development; the paper contains the platinum and iron salts as well as the developer, and so prints and develops at the same time. Although excellent prints can be produced with it, for general work the results of the paper, as at present made, will not compare with the hot and cold bath processes. It is, however, excellent for printing from very dense negatives, and occasional negatives that seem extremely suitable for it. The paper should be breathed on before printing, as if it is quite dry the printing will be very slow and irregular. The best conditions for the preparation of the paper have scarcely been decided upon yet, and it is not quite fair to judge the process. The prints are cleared in the acid baths and washed for about a quarter of an hour.

The sepia and black hot bath processes are much alike in the general treatment. There are, however, some special precautions to be observed with the sepia paper, the chief being to protect it from any but the faintest rays of light; the prints, unlike the black ones, may be affected by light when in the acid bath. A special solution must be added to the developer to keep the lights pure. Over-exposure cannot be corrected by using a cooler bath, as is the case with the black prints, and the paper does not remain good so long.

The paper for the black prints by the hot bath process is washed with a mixture of potassic platinous chloride and ferric oxalate, the proportion being about sixty grains of the platinum salt to one ounce of the iron solution. It will not keep good longer than twenty minutes or so, and must be applied to the paper directly after mixing. The ferric oxalate in the paper is reduced by the action of light to ferrous oxalate, which forms the faint visible image; this, when the paper is floated on the oxalate of potash bath, is capable of reducing the platinum salt in contact with it into metallic platinum; but the ferric salt, which remains unaltered, has no action on the platinum salt, leaving these parts, which represent the high lights of the print, untouched. The ferric oxalate is removed by the acid baths which follow the development. A good temperature for development is 150° Fahr., and when using this so much detail should not be apparent as when printing for the cold bath process, in which all the detail desired should be very faintly visible. There are, however, many methods of exposing the paper and developing it, and no fixed rule can be made, but the development must in every case be suited to the exposure or the result will be a failure. For instance, the paper may be printed until all detail is visible, but a very much cooler development must be used, say 80° or 90°; on the other hand, a slightly short exposure may be given, and a temperature of 180° to 200° used. 150° should be taken as the normal temperature, and kept to until some experience has been gained, as employing all temperatures will lead to confusion, and nothing will be learned. Some negatives require a special treatment, and both printing and development must be altered, while for a very dense negative the paper may be left out in a dampish room for some time. It will then print with less contrast and more half tone. A thin negative is better printed by the cold bath process, but negatives should be good and brilliant for platinotype printing. Any one taking up platinotype and getting only weak prints would do well to look to his negatives instead of blaming the paper, as the high lights should be fairly dense, and the deep shadows nearly clear glass.

Time for complete development should always be allowed; with a hot bath fifteen seconds will be sufficient, but if a cooler development is used, or the prints are solarized in the shadows, more time should be allowed. When the deep shadows are solarized, or appear lighter than surrounding parts, a hot and prolonged development is required to obtain sufficient blackness, as they have a tendency to look like brown paper. I have found breathing on solarized shadows useful, as in the presence of slight moisture they begin to print out and become dark before development, getting black almost directly the print is floated on the oxalate. Three or four acid baths of about ten minutes each are used, and the prints are washed as before. The process throughout takes much less time than silver printing, and can be kept on all the winter, when it is nearly impossible to print in silver. Prints can be developed in weak daylight or gaslight, and prolonged washing is dispensed with.--_N.P. Fox, reported in Br. Jour. of Photo._

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[Continued from Supplement, No. 706, page 11283.]

ON ALLOTROPIC FORMS OF SILVER.

By M. CAREY LEA.

In the first part of this paper were described certain forms of silver; among them a lilac blue substance, very soluble in water, with a deep red color. After undergoing purification, it was shown to be nearly pure silver. During the purification by washing it seemed to change somewhat, and, consequently, some uncertainty existed as to whether or not the purified substance was essentially the same as the first product; it seemed possible that the extreme solubility of the product in its first condition might be due to a combination in some way with citric acid, the acid separating during the washing. Many attempts were made to get a decisive indication, and two series of analyses, one a long one, to determine the ratio between the silver and the citric acid present, without obtaining a wholly satisfactory result, inasmuch as even these determinations of mere ratio involved a certain degree of previous purification which might have caused a separation.

This question has since been settled in an extremely simple way, and the fact established that the soluble blue substance contains not a trace of combined citric acid.

The precipitated lilac blue substance (obtained by reducing silver citrate by ferrous citrate) was thrown on a filter and cleared of mother water as far as possible with a filter pump. Pure water was then poured on in successive portions until more than half the substance was dissolved. The residue, evidently quite unchanged, was, of course, tolerably free from mother water. It was found that by evaporating it to dryness over a water bath, most of the silver separated out as bright white normal silver; by adding water and evaporating a second time, the separation was complete, and water added dissolved no silver. _The solution thus obtained was neutral._ It must have been acid had any citric acid been combined originally with the silver. This experiment, repeated with every precaution, seems conclusive. The ferrous solution, used for reducing the silver citrate, had been brought to exact neutrality with sodium hydroxide. After the reduction had been effected, the mother water over the lilac blue precipitate was neutral or faintly acid.

A corroborating indication is the following: The portions of the lilac blue substance which were dissolved on the filter (see above) were received into a dilute solution of magnesium sulphate, which throws down insoluble allotropic silver of the form I have called B (see previous paper). This form has already been shown to be nearly pure silver. The magnesia solution, neutral before use, was also neutral after it had effected the precipitation, indicating that no citric acid had been set free in the precipitation of the silver.

It seems, therefore, clear that the lilac blue substance contains no combined citric acid. Had the solubility of the silver been due to combination with either acid or alkali, the liquid from which it was separated by digestion at or below 100° C. must have been acid or alkaline; it could not have been neutral.

We have, therefore, this alternative: In the lilac blue substance we have either pure silver in a soluble form or else a compound of silver, with a perfectly neutral substance generated from citric acid in the reaction which leads to the formation of the lilac blue substance. If this last should prove the true explanation, then we have to do with a combination of silver of a quite different nature from any silver compounds hitherto known. A neutral substance generated from citric acid must have one or more atoms of hydrogen replaced by silver. This possibility recalls the recent observations of Ballo, who, by acting with a ferrous salt on tartaric acid, obtained a neutral colloid substance having the constitution of arabin, C6 H10 O6.

To appreciate the difficulty of arriving at a correct conclusion, it must be remembered that the silver precipitate is obtained saturated with strong solutions of ferric and ferrous citrate, sodium citrate, sulphate, etc. These cannot be removed by washing with pure water, in which the substance itself is very soluble, but must be got rid of by washing with saline solutions, under the influence of which the substance itself slowly but continually changes. Next, the saline solution used for washing must be removed by alcohol. During this treatment, the substance, at first very soluble, gradually loses its solubility, and, when ready for analysis, has become wholly insoluble. It is impossible at present to say whether it may not have undergone other change; this is a matter as to which I hope to speak more positively later. It is to be remarked, however, that these allotropic forms of silver acquire and lose solubility from very slight causes, as an instance of which may be mentioned the ease with which the insoluble form B recovers its solubility under the influence of sodium sulphate and borate, and other salts, as described in the previous part of this paper.

The two insoluble forms of allotropic silver which I have described as B and C--B, bluish green; C, rich golden color--show the following curious reaction. A film of B, spread on glass and heated in a water stove to 100° C. for a few minutes becomes superficially bright yellow. A similar film of the gold colored substance, C, treated in the same way, acquires a blue bloom. In both cases it is the surface only that changes.

_Sensitiveness to Light._--All these forms of silver are acted upon by light. A and B acquire a brownish tinge by some hours' exposure to sunlight. With C the case is quite different, the color changes from that of red gold to that of pure yellow gold. The experiment is an interesting one. The exposed portion retains its full metallic brilliancy, giving an additional proof that the color depends upon molecular arrangement, and this with the allotropic forms of silver is subject to change from almost any influence.

_Stability._--These substances vary greatly in stability under influences difficult to appreciate. I have two specimens of the gold yellow substance, C, both made in December, 1886, with the same proportions, under the same conditions. One has passed to dazzling white, normal silver, without falling to powder, or undergoing disaggregation of any sort; the fragments have retained their shape, simply changing to a pure frosted white, remaining apparently as solid as before; the other is unchanged, and still shows its deep yellow color and golden luster. Another specimen made within a few months and supposed to be permanent has changed to brown. Complete exclusion of air and light is certainly favorable to permanence.

_Physical Condition._--The brittleness of the substances B and C, the facility with which they can be reduced to the finest powder, makes a striking point of difference between allotropic and normal silver. It is probable that normal silver, precipitated in fine powder and set aside moist to dry gradually, may cohere into brittle lumps, but these would be mere aggregations of discontinuous material. With allotropic silver the case is very different, the particles dry in optical contact with each other, the surfaces are brilliant, and the material evidently continuous. That this should be brittle indicates a totally different state of molecular constitution from that of normal silver.

_Specific Gravities._--The allotropic forms of silver show a lower specific gravity than that of normal silver.

In determining the specific gravities it was found essential to keep the sp. gr. bottle after placing the material in it for some hours under the bell of an air pump. Films of air attach themselves obstinately to the surfaces, and escape but slowly even in vacuo.

Taken with this precaution, the blue substance, B, gave specific gravity 9.58, and the yellow substance, C, specific gravity 8.51. The specific gravity of normal silver, after melting, was found by G. Rose to be 10.5. That of finely divided silver obtained by precipitation is stated to be 10.62.[1]

[Footnote 1: Watts' Dict., orig. ed., v. 277.]

I believe these determinations to be exact for the specimens employed. But the condition of aggregation may not improbably vary somewhat in different specimens. It seems, however, clear that these forms of silver have a lower specific gravity than the normal, and this is what would be expected.

Chestnut Hill, Philadelphia, May, 1889.

--_Amer. Jour. of Science._

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TURPENTINE AND ITS PRODUCTS.[1]

[Footnote 1: Read at a meeting of the Liverpool Chemists' Association.]

By EDWARD DAVIES, F.C.S., F.I.C.