Henley's Twentieth Century Formulas, Recipes and Processes

by Unknown

CELLULOID

New Celluloid.

To put this process in practice, 1,000 parts of pyroxyline is prepared in the usual manner, and mixed with 65 parts of turpentine, or 250 parts of ketone and 250 parts of ether; 500 parts or 750 parts of methyl alcohol is added, and a colorant, such as desired. Instead of turpentine, rosins derived from it may be employed. If the employment of camphor is desired to a certain extent, it may be added to the mixture. The whole is shaken and left at rest for about 12 hours. It is then passed between hot rollers, and finally pressed, cut, and dried, like ordinary celluloid. {156}

The product thus obtained is without odor, when camphor is not employed; and in appearance and properties it cannot be distinguished from ordinary celluloid, while the expense of production is considerably reduced.

Formol Albumen For Preparation Of Celluloid.

I.—The albumen may be that of the egg or that of the blood, which are readily found in trade. The formolizing may be effected in the moist state or in the dry state. The dry or moist albumen is brought into contact with the solution of commercial formol diluted to 5 or 10 per cent for an hour. Care must be taken to pulverize the albumen, if it is dry. The formol penetrates rapidly into the albuminoid matter, and is filtered or decanted and washed with water until all the formol in excess has completely disappeared; this it is easy to ascertain by means of aniline water, which produces a turbid white as long as a trace of formic aldehyde remains.

The formol albumen is afterwards dried at low temperature by submitting it to the action of a current of dry air at a temperature not exceeding 107° F. Thus obtained, the product appears as a transparent corneous substance. On pulverizing, it becomes opaque and loses its transparency. It is completely insoluble in water, but swells in this liquid.

II.—The formol albumen is reduced to a perfectly homogeneous powder, and mixed intimately with the plastic matter before rolling. This cannot be considered an adequate means for effecting the mixture. It is necessary to introduce the formol albumen, in the course of the moistening, either by making an emulsion with camphor alcohol, or by mixing it thoroughly with nitro-cellulose, or by making simultaneously a thorough mixture of the three substances. When the mixture is accomplished, the paste is rolled according to the usual operation. The quantity of formol albumen to add is variable, being diminished according to the quantity of camphor.

Instead of adding the desiccated formol albumen, it may previously be swollen in water in order to render it more malleable.

Instead of simple water, alkalinized or acidified water may be taken for this purpose, or even alcoholized water. The albumen, then, should be pressed between paper or cloth, in order to remove the excess of moisture.

Plastic Substances Of Nitro-cellulose Base.

The plastic pulp thus obtained is rolled, cut, and dried like ordinary cellulose, and by the same processes and apparatus. The pulp may also be converted into tubes and other forms, like ordinary celluloid.

It is advisable to subject the improved plastic pulp to a treatment with formaldehyde for the purpose of rendering insoluble the casein incorporated in the celluloid. The plastic product of nitro-cellulose base, thus obtained, presents in employment the same general properties as ordinary celluloid. It may be applied to the various manufacturing processes in use for the preparation of articles of all kinds, and its cost price diminishes more or less according to the proportion of casein associated with the ordinary celluloid. In this plastic product various colorants may be incorporated, and the appearance of shell, pearl, wood, marble, or ivory may also be imparted.

Improved Celluloid.

The new product may be prepared in open air or in a closed vessel under pressure. When operated in the air, the gelatin is first immersed cold (in any form, and in a state more or less pure) in alcohol marking about 140° F., with the addition of a certain quantity (for example, 5 to 10 per cent) of crystallizable acetic acid. In a few hours the material has swollen considerably, and it is then introduced in alcohol of about 90 per cent, and at the same time the celluloid pulp (camphor and gun cotton), taking care to add a little acetone. The proportion of celluloid in the mixture may be 50 to 75 per cent of the weight of the gelatin, more or less, according to the result desired. After heating the mixture slightly, it is worked, cold, by the rollers ordinarily employed for celluloid and other similar pastes, or by any other suitable methods.

The preparation in a closed vessel does not differ from that which has been described, except for the introduction of the mixture of gelatin, celluloid, alcohol, and acetone, at the moment when the heating is to be accomplished in an autoclave heated with steam, capable of supporting a pressure of 2 to 5 pounds, and furnished with a mechanical agitator. This method of proceeding abridges the operation considerably; the paste comes from the autoclave well mingled, and is then submitted to the action of rollers. There is but little work in distilling the alcohol and acetic acid in the autoclave. These may be recovered, and on account of their evaporation the mass presents the desired consistency when it reaches the rollers. Whichever of the two methods of preparation may be employed, the substance may be rolled as in the ordinary process, if a boiler with agitator is made use of; the mass may be produced in any form.

Preparation Of Uninflammable Celluloid.

Before cooling, the mixture is passed through a sieve in order to retain the pieces which may not have been dissolved. After swelling, and the dissolution and purification by means of the sieve, it is allowed to rest still in the same position, with access of air. The films formed while cooling may be removed. The treatment of celluloid necessitates employing a solution completely colorless and clear. The celluloid to be treated while it is still in the pasty state should be in a receiver of glass, porcelain, or similar material.

The mass containing the fish glue is poured in, drop by drop, while stirring carefully, taking care to pour it in the middle of the celluloid and to increase the surface of contact.

When the mixture is complete, the celluloid is ready to be employed and does not produce flame when exposed.

The solution of fish glue may be prepared by allowing 200 parts of it to swell for 48 hours in 1,000 parts of cold distilled water. It is then passed through the sieve, and the pieces which may remain are broken up, in order to mingle them thoroughly with the water. Ten parts of kitchen salt are then added, and the whole mass passed through the sieve.

This product may be utilized for the preparation of photographic films or for those used for cinematographs, or for replacing hard caoutchouc for the insulation of electric conductors, and for the preparation of plastic objects.

Substitute For Camphor In The Preparation Of Celluloid And Applicable To Other Purposes.

In an autoclave constructed for the purpose, camphene and water strongly mixed with sulphuric acid are introduced and heated so as to attain 9 pounds of pressure. Then an electric current is applied, capable of producing the decomposition of water. The mass is constantly stirred, either mechanically or more simply by allowing a little of the steam to escape by a tap. In an hour, at least, the material is drawn from the apparatus, washed and dried, sublimed according to need, and is then suitable for replacing camphor in its industrial employments, for the camphene is converted entirely or in greater part into camphor, either right-hand camphor, or a product optically inactive, according to the origin of the oil of turpentine made use of.

In the electrolytic oxidation of the camphene, instead of using acidulated water, whatever is capable of furnishing, under the influence of the electric current, the oxygen necessary for the reaction, such as oxygenized water, barium bioxide, and the permanganates, may be employed.

Plastic And Elastic Composition.

Production Of Substances Resembling Celluloid.

Callenberg has found that the halogenous derivatives of etherized oils, principally oil of turpentine, and especially the solid chloride of turpentine, which is of a snowy and brilliant white, and of agreeable odor, are suitable for yielding, either alone or mixed with camphor or one of its substitutes, and combined by ordinary means with nitrated cellulose, or other ethers of cellulose, treated with acetic ether, a celluloidic product, which, it is said, is not inferior to ordinary celluloid and has the advantage of reduced cost.

Elastic Substitute For Celluloid.

I.—Melt together 1 part of acetate of cellulose and 1 ¹/₂ parts of phenol at about the temperature of 104° to 122° F. When a clear solution is obtained place the mass of reaction on plates of glass or metal slightly heated and allow it to cool gradually. After a rest of several days the mass, which at the outset is similar to caoutchouc, is hard and forms flexible plates, which can be worked like celluloid.

II.—Compress an intimate mixture of equal parts of acetic cellulose and hydrate of chloride or of aniline, at a temperature of 122° to 140° F., and proceed as in the previous case.

In the same way a ketone may be employed, as acetophenone, or an acid amide, as acetamide.

III.—A transparent, celluloid-like substance which is useful for the {159} production of plates, tubes, and other articles, but especially as an underlay for sensitive films in photography, is produced by dissolving 1.8 parts, by weight, of nitro-cellulose in 16 parts of glacial acetic acid, with heating and stirring and addition of 5 parts of gelatin. After this has swelled up, add 7.5 parts, by weight, of alcohol (96 per cent), stirring constantly. The syrupy product may be pressed into molds or poured, after further dilution with the said solvents in the stated proportion, upon glass plates to form thin layers. The dried articles are well washed with water, which may contain a trace of soda lye, and dried again. Photographic foundations produced in this manner do not change, nor attack the layers sensitive to light, nor do they become electric, and in developing they remain flat.

IV.—Viscose is the name of a new product of the class of substances like celluloid, pegamoid, etc., substances having most varied and valuable applications. It is obtained directly from cellulose by mascerating this substance in a 1 per cent dilution of hydrochloric acid. The maceration is allowed to continue for several hours, and at its close the liquid is decanted and the residue is pressed off and washed thoroughly. The mass (of which we will suppose there is 100 grams) is then treated with a 20 per cent aqueous solution of sodium hydrate, which dissolves it. The solution is allowed to stand for 3 days in a tightly closed vessel; 100 grams carbon disulphide are then added, the vessel closed and allowed to stand for 12 hours longer, when it is ready for purification. Viscose thus formed is soluble in water, cold or tepid, and yields a solution of a pale brownish color, from which it is precipitated by alcohol and sodium chloride, which purifies it, but at the expense of much of its solubility. A solution of the precipitated article is colorless, or of a slightly pale yellow. Under the action of heat, long continued, viscose is decomposed, yielding cellulose, caustic soda, and carbon disulphide.

See also Casein for Celluloid Substitutes.

Celluloid Of Reduced Inflammability.

When the ether derivative is in the solid form, such, for instance, as ethyl disilicate, it is brought to the liquid state by means of any of the solvents. The union of the solvent and of the derivative is accomplished by mixing the two liquids and shaking out the air as much as possible. The incorporation of this mixture with the celluloid, previously divided or reduced to the state of chips, is effected by pouring the mixture on the chips, or inversely, shaking or stirring as free from the air as possible. The usual methods are employed for the desiccation of the mass. A good result is obtained by drying very slowly, preferably at a temperature not above 10° C. (50° F.). The resulting residue is a new product scarcely distinguished from ordinary celluloid, except that the inherent inflammability is considerably reduced. It is not important to employ any individual silicate or derivative. A mixture of the silicates or derivatives mentioned will accomplish the same results.

II.—Any ignited body is extinguished in a gaseous medium which is unsuitable for combustion; the attempt has therefore been made to find products capable of producing an uninflammable gas; and products have been selected that yield chlorine, and others producing bromine; it is also necessary that these bodies should be soluble in a solvent of celluloid; therefore, among chlorated products, ferric chloride has been taken; this is soluble in the ether-alcohol mixture.

This is the process: An ether-alcohol solution of celluloid is made; then an ether-alcohol solution of ferric perchloride. The two solutions are mingled, and a clear, syrupy liquid of yellow color, yielding no precipitate, is obtained. The liquid is poured into a cup or any suitable vessel; it is left for spontaneous evaporation, and a substance of shell-color is produced, which, after washing and drying, effects the desired result. The celluloid thus treated loses none of its properties in pliability and transparency, and is not only uninflammable, but also incombustible. {160}

Of bromated compounds, calcium bromide has been selected, which produces nearly the same result; the product obtained fuses in the flame; outside, it is extinguished, without the power of ignition.

It may be objected that ferric perchloride and calcium bromide, being soluble in water, may present to the celluloid a surface capable of being affected by moist air; but the mass of celluloid, not being liable to penetration by water, fixes the chlorinated or brominated product. Still, as the celluloid undergoes a slight decomposition, on exposure to the light, allowing small quantities of camphor to evaporate, the surface of the perchlorinated celluloid may be fixed by immersion in albuminous water, after previous treatment with a solution of oxalic acid, if a light yellow product is desired.

For preventing the calcium bromide from eventually oozing on the surface of the celluloid, by reason of its deliquescence, it may be fixed by immersing the celluloid in water acidulated with sulphuric acid. For industrial products, such as toilet articles, celluloid with ferric perchloride may be employed.

Another method of preparing an uninflammable celluloid, based on the principle above mentioned, consists in mixing bromide of camphor with cotton powder, adding castor oil to soften the product, in order that it may be less brittle. The latter product is not incombustible, but it is uninflammable, and its facility of preparation reduces at least one-half the apparatus ordinarily made use of in the manufacture of celluloid. The manufacture of this product is not at all dangerous, for the camphor bromide is strictly uninflammable, and may be melted without any danger of dissolving the gun cotton.

III.—Dissolve 25 parts of ordinary celluloidin in 250 parts of acetone and add a solution of 50 parts of magnesium chloride in 150 parts of alcohol, until a paste results, which occurs with a proportion of about 100 parts of the former solution to 20 parts of the latter solution. This paste is carefully mixed and worked through, then dried, and gives an absolutely incombustible material.

IV.—Glass-like plates which are impervious to acids, salts, and alkalies, flexible, odorless, and infrangible, and still possess a transparency similar to ordinary glass, are said to be obtained by dissolving 4 to 8 per cent of collodion wool (soluble pyroxylin) in 1 per cent of ether or alcohol and mixing the solution with 2 to 4 per cent of castor oil, or a similar non-resinifying oil, and with 4 to 6 per cent of Canada balsam. The inflammability of these plates is claimed to be much less than with others of collodion, and may be almost entirely obviated by admixture of magnesium chloride. An addition of zinc white produces the appearance of ivory.

Solvents For Celluloid.

I.—	Celluloid	5 parts
	Amyl acetate	10 parts
	Acetone	16 parts
	Sulphuric ether	16 parts
II.—	Celluloid	10 parts
	Sulphuric ether	30 parts
	Acetone	30 parts
	Amyl acetate	30 parts
	Camphor	3 parts
III.—	Celluloid	5 parts
	Alcohol	50 parts
	Camphor	5 parts
IV.—	Celluloid	5 parts
	Amyl acetate	50 parts
V.—	Celluloid	5 parts
	Amyl acetate	25 parts
	Acetone	25 parts

Softening And Cementing Celluloid.

It is often desirable to soften celluloid so that it will not break when hammered. Dipping it in water warmed to 40° C. (104° F.) will suffice for this.

Mending Celluloid.

See also Adhesives for Methods of Mending Celluloid.

Printing On Celluloid.

Colored Celluloid.—

Black: First dip into pure water, then into a solution of nitrate of silver; let dry in the light.

Yellow: First immerse in a solution of nitrate of lead, then in a concentrated solution of chromate of potash.

Brown: Dip into a solution of permanganate of potash made strongly alkaline by the addition of soda.

Blue: Dip into a solution of indigo neutralized by the addition of soda.

Red: First dip into a diluted bath of nitric acid; then into an ammoniacal solution of carmine.

Green: Dip into a solution of verdigris.

Aniline colors may also be employed but they are less permanent.

Bleaching Celluloid.

Process Of Impregnating Fabrics With Celluloid.

CELLULOID CEMENTS AND GLUES: See Adhesives.

CELLULOID LACQUER: See Lacquer.

CELLULOID PUTTY: See Cements.