Part 137

II.—It has been observed that when gluten dried at an ordinary temperature, hence capable of absorbing water, is mixed with glycerine and heated, it becomes water-repelling and suitable for a waterproof paint. One part of gluten is mixed with parts of glycerine, whereby a slimy mass is obtained which is applied on fabrics subsequently subjected to a heat of 248° F. The heating should not last until all glycerine has evaporated, otherwise the coating becomes brittle and peels off.

«Waterproofing Canvas.»—I.—The canvas is coated with a mixture of the three solutions named below:

1. Gelatin, 50 parts; by weight, boiled in 3,000 parts of water free from lime. 2. Alum, 100 parts, dissolved in 3,000 parts of water. 3. Soda soap dissolved in 2,000 parts of water.

II.—Prepare a zinc soap by entirely dissolving 56 parts of soft soap in 125 to 150 parts of water. To the boiling liquid add, with constant stirring, 28 to 33 parts of zinc vitriol (white vitriol). The zinc soap floats on top and forms, after cooling, a hard white mass, which is taken out. In order to clean it of admixed carbonic alkali, it must be remelted in boiling fresh water. Next place 232.5 parts of raw linseed oil (free from mucus) in a kettle with 2.5 parts of best potash, and 5 parts of water. This mass is boiled until it has become white and opaque and forms a liquid, soap-like compound. Now, add sugar of lead, 1.25 parts; litharge, 1 part; red lead, 2 parts; and brown rosin, 10.5 parts. The whole is boiled together about 1 hour, the temperature not being allowed to exceed 212° F., and stirring well from time to time. After this add 15 parts of zinc soap and stir the whole until the metal soap has combined with the oil, the temperature not exceeding 212° F. When the mixture is complete, add a solution of caoutchouc, 1.2 parts, and oil of turpentine, 8.56 parts, which must be well incorporated by stirring. The material is first coated on one side by means of a brush with this composition, which must have a temperature of 158° F. Thereupon hang it up to dry, then apply a second layer of composition possessing the same temperature, which is likewise allowed to dry. The fiber is now filled out, so that the canvas is waterproof.

«Waterproofing Corks.»—For the purpose of making corks as impervious as possible, while at the same time keeping them elastic, saturate them with caoutchouc solution. Dissolve caoutchouc in benzine in the ratio of 1 part of caoutchouc to 19 parts of benzine. Into this liquid lay the corks to be impregnated and subject them to a pressure of 150 to 180 pounds by means of a force pump, so that the liquid can thoroughly enter. The corks thus treated must next be exposed to a strong draught of air until all trace of benzine has entirely evaporated and no more smell is noticeable.

«WATERPROOFING FABRICS.»

It will be convenient to divide waterproof fabrics into two classes, viz., those which are _impervious_ to water, and those which are _water-repellent_. It is important to make this distinction, for, although all waterproof material is made for the purpose of resisting water, there is a vast difference between the two classes. The physical difference between them can be briefly summed up as follows: Fabrics which are completely impervious to water comprise oil-skins, mackintoshes, and all materials having a water-resisting film on one or both sides, or in the interior of the fabric. Those coming under the second heading of water-repellent materials do not possess {743} this film, but have their fibers so treated as to offer less attraction to the water than the water molecules have for themselves.

The principal members of the first group are the rubber-proofed goods; in these the agent employed is rubber in greater or less quantity, together with other bodies of varying properties. Before enlarging on this class, it will be necessary to give a short description of the chemical and physical properties of rubber.

Rubber, or caoutchouc, is a natural gum exuding from a large number of plants, those of the _Euphorbiaceæ_ being the chief source for the commercial variety. The raw material appears on the market in the shape of blocks, cakes, or bottle-shaped masses, according to the manner in which it has been collected. It possesses a dark-brown—sometimes nearly black-exterior; the interior of the mass is of a lighter shade, and varies from a dingy brown to a dirty white, the color depending on the different brands and sources. In the raw state its properties are very different from what they are after going through the various manufacturing processes, and it has only a few of the characteristics which are generally associated with India rubber. Chemically it is a complex hydrocarbon with the formula C_〈45〉H_〈36〉, and appears to consist of a highly porous network of cells having several different rosins in their interstices. It is perfectly soluble in no single solvent, but will yield some of its constituents to many different solvents. At a temperature of 10° C. (50° F.) raw caoutchouc is a solid body and possesses very little elasticity. At 36° C. (97° F.) it is soft and elastic to a high degree, and is capable of being stretched 16 times its length. Further increase of temperature lessens its elastic properties, and at 120° C. (248° F.) it melts. While in the raw condition it has several peculiar properties, one of which is: After stretching, and cooling suddenly while stretched, it retains its new form, and only regains its former shape on being warmed. Another striking feature is its strong adhesive capacity; this property is so powerful that the rubber cannot be cut with a knife unless the blade is wet; and freshly cut portions, if pressed together, will adhere and form a homogeneous mass. From these facts it will be seen how it differs from rubber in the shape of a cycle tire or other manufactured form.

The most valuable property possessed by raw caoutchouc is that of entering into chemical combination with sulphur, after which its elasticity is much increased; it will then bear far greater gradations of heat and cold. This chemical treatment of caoutchouc with sulphur is known as “vulcanizing,” and, if properly carried out, will yield either soft vulcanized rubber or the hard variety known as vulcanite. On the other hand, caoutchouc, after vulcanizing, has lost its plastic nature, and can no longer be molded into various shapes, so that in the production of stamped or molded objects, the customary method is to form them in unvulcanized rubber and then to vulcanize them.

Raw caoutchouc contains a number of natural impurities, such as sand, twigs, soil, etc.; these require removing before the manufacturing processes can be carried out. The first operation, after rough washing, is to shred the raw material into small strips, so as to enable the impurities to be washed out. This process is carried out by pressing the rubber against the surface of a revolving drum (_A_, Fig. 1), carrying a number of diagonally arranged knives, _B_, on its surface. A lever, _C_, presses the rubber against the knives; _D_ is the fulcrum on which _C_ works, _E_ being a weight which throws back the lever on the pressure being removed. During {744} this operation a jet of water is kept playing onto the knives to cool and enable them to cut.

Following this comes the passage between a pair of corrugated steel rollers (as shown in Fig. 2). These rollers have each a different speed, so that the rubber gets stretched and squeezed at the same time. Immediately over the rollers a water pipe is fixed, so that a steady stream of water washes out all the sand and other extraneous matter. In Fig. 2, _AA_ are the steel rollers, while _B_ is a screw working springs which regulate the pressure between the rollers. The power is transmitted from below from the pulley, _C_, and thence to the gearing.

The next operation, after well drying, is to thoroughly masticate the shredded rubber between hot steel rollers, which resemble those already described, but usually have a screw-thread cut on their surfaces. Fig. 3 shows the front view of this masticating machine, _A_ being the rollers, while the steam pipe for heating is shown at _B_. Fig. 3_a_ gives a top view of the same machine, showing the two rollers.

After passing several times through these, the rubber will be in the form of homogeneous strips, and is then ready either for molding or dissolving. As we are dealing solely with waterproofed textiles, the next process which concerns us is the dissolving of the rubber in a suitable solvent. Benzol, carbon bisulphide, oil of turpentine, ether, and absolute alcohol, will each dissolve a certain amount of rubber, but no one of them used alone gives a thorough solution. The agent commonly employed is carbon bisulphide, together with 10 per cent of absolute alcohol. Whatever solvent is used, after being steeped in it for some hours the caoutchouc swells out enormously, and then requires the addition of some other solvent to effect a complete solution. A general method is to place the finely shredded rubber in a closed vessel, to cover it with carbon bisulphide, and allow to stand for some hours. Toward the end of the time the vessel is warmed by means of a steam coil or jacket, and 10 parts absolute alcohol are added for every 100 parts of carbon bisulphide. The whole is then kept gently stirred for a few hours. Fig. 4 shows a common type of the vessel used for dissolving rubber. In this diagram _A_ is the interior of the vessel, and _B_ a revolving mixer in the same. The whole vessel is surrounded by a steam jacket, _C_, with a steam inlet at _D_ and a tap for condensed water at _E_. _F_ is the cock by which the solution is drawn off.

After the rubber is dissolved, about 12 to 24 per cent of sulphur is added, and thoroughly incorporated with the solution. The sulphur may be in the form of chloride of sulphur, or as sulphur pure and simple. A very small quantity of sulphur is required to give the necessary result, 2 to 3 per cent being sufficient to effect vulcanization; but a large quantity is always added to hasten the operation.

Even after prolonged treatment with the two solvents, a solution of uniform consistency is never obtained: clots of a thicker nature will be found floating in the solution, and the next operation is to knead it up so as to obtain equal {745} density throughout. Fig. 5 will give an idea of how this mixing is done.

At the top of a closed wooden chamber is a covered reservoir, _A_, containing the solution of rubber. A long slit at the base of this reservoir allows the solution to fall between sets of metal rollers, _BBB_ below. Neighboring rollers are revolving in opposite directions, and at different speeds, so that, after passing all three sets of rollers, and emerging at the bottom, the solution should be of uniform consistency. _CCC_ are the guiding funnels, and _EE_ are scrapers to clear the solution from the rollers. _D_ is a wedge-shaped plug worked by a rack and pinion, and regulates the flow of the solution.

It now remains to apply the rubber to the fabric and vulcanize it. Up to this stage the sulphur has only been mechanically mixed with the rubber; the aid of heat is now required to bring about chemical combination between the two. This process, which is known as “burning,” consists in subjecting the rubber-covered fabric to a temperature of about 248° F. Sulphur itself melts at 239° F., and the temperature at which combination takes place must be above this. Fig. 6 shows one of the methods of spreading the rubber on the cloth. _A_ is the tank containing the solution with an outlet at the bottom arranged so as to regulate the flow of solution. The fabric passes slowly underneath this, receiving as it travels a thin coating of the waterproofing. The two rollers at _B_ press the solution into the fabric and distribute the proofing evenly over the entire surface.

After leaving the two squeezing rollers, the cloth travels slowly through a covered chamber, _C_, having a series of steam pipes, _EE_, underneath, to evaporate the solvent; this condenses on the upper portion of the chamber, which is kept cooled, and flows down the sides into suitable receptacles. After this the proofed cloth is vulcanized by passing round metal cylinders heated to the necessary temperature, or by passing through a heated chamber. Fig. 7 shows the spreading of rubber between two fabrics. The two cloths are wound evenly on the rollers, _BB_; from this they are drawn conjointly through the rollers, _D_, the stream of proofing solution flowing down between the rollers, which then press the two fabrics together with the rubber inside. The lower rollers marked _CC_ are heated to the necessary degree, and cause the rubber and sulphur to combine in chemical union.

So far the operation of proofing has been described as though pure rubber only was used; in practice the rubber forms only a small percentage of the proofing material, its place being taken by cheaper bodies. One of the common ingredients of proofing mixtures is boiled linseed oil, together with a small quantity of litharge; this dries very quickly, and forms a glassy flexible film. Coal tar, shellac, colophony, etc., are all used, together with India-rubber varnish, to make {746} different waterproof compositions. Oil of turpentine and benzol form good solvents for rubber, but it is absolutely essential that both rubber and solvent be perfectly anhydrous before mixing. Oil of turpentine, alcohol, etc., can be best deprived of water by mixing with either sulphuric acid or dehydrated copper sulphate, and allowing to stand. The acid or the copper salt will absorb the water and sink to the bottom, leaving a supernatant layer of dehydrated turpentine or whatever solvent is used. All the sulphur in a rubber-proofed cloth is not in combination with the rubber; it is frequently found that, after a lapse of time, rubber-proofed material shows an efflorescence of sulphur on the surface, due to excess of sulphur, and occasionally the fabric becomes stiff and the proofing scales off. Whenever a large proportion of sulphur is present, there is always the danger of the rubbers forming slowly into the hard vulcanite state, as the substance commonly called vulcanite consists only of ordinary vulcanized rubber carried a stage further by more sulphur being used and extra heat applied. If after vulcanizing, rubber is treated with caustic soda, all this superfluous sulphur can be extracted; if it is then well washed the rubber will retain its elasticity for a long period. With the old methods of proofing, a sheet of vulcanized rubber was cemented to a fabric with rubber varnish, and frequently this desulphurizing was performed before cementing together. The result was a flexible and durable cloth, but of great weight and thickness, and expensive to produce.

The chemistry of rubber is very little understood; as mentioned previously, rubber is a highly complex body, liable to go through many changes. These changes are likely to be greater in rubber varnish, consisting of half a dozen or more ingredients, than in the case of rubber alone. The action of sunlight has a powerful effect on rubber, much to its detriment, and appears to increase its tendency to oxidize. Vulcanized rubber keeps its properties better under water than when exposed to the air, and changes more slowly if kept away from the light. It appears as though a slight decomposition always takes place even with pure rubber; but the presence of so many differently constituted substances as sometimes occur in rubber solutions no doubt makes things worse. Whenever a number of different bodies with varying properties are consolidated together by heat, as in the case of rubber compositions, it is only reasonable to expect there will be some molecular rearrangement going on in the mass; and this can be assigned as the reason why some proofings last as long again as others. Some metallic salts have a very injurious action on rubber, one of the worst being copper sulphate. Dyers are frequently warned that goods for rubber-proofing must be free from this metal, as its action on rubber is very powerful, though but little understood. As is generally known, grease in any form is exceedingly destructive to rubber, and it should never be allowed in contact in the smallest proportion. Some compositions are made up by dissolving rubber in turpentine and coal tar; but in this case some of the rubber’s most valuable properties are destroyed, and it is doubtful if it can be properly vulcanized. Owing to rubber being a bad conductor of heat, it requires considerable care to vulcanize it in any thickness. A high degree of heat applied during a short period would tend to form a layer of hard vulcanite on the surface, while that immediately below would be softer and would gradually merge into raw rubber in the center.

The different brands of rubber vary so much, especially with regard to solubility, that it is always advisable to treat each brand by itself, and not to make a solution of two or more kinds. Oilskins and tarpaulins, etc., are mostly proofed by boiled linseed oil, with or without thickening bodies added. They are not of sufficient interest to enlarge upon in this article, so the second, or “water-repellent,” class has now to be dealt with.

All the shower-proof fabrics come under this heading, as well as every cloth which is pervious to air and repulsive to water. The most time-honored recipe for proofing woollen goods is a mixture of sugar of lead and alum, and dates back hundreds of years. The system of using this is as follows: The two ingredients are dissolved separately, and the solutions mixed together. A mutual decomposition results, the base of the lead salt uniting with the sulphuric acid out of the alum to form lead sulphate, which precipitates to the bottom. The clear solution contains alumina in the form of acetate, and this supplies the proofing quality to the fabric. It is applied in a form of machine shown in Fig. 8, which will be seen to consist of a trough containing the proofing solution, _C_, with a pair of squeezing rollers, _A_, over the top. The fabric is drawn down through the solution and up through the squeezers in the direction of the arrows. At the {747} back of the machine the cloth automatically winds itself onto a roll, _B_, and then only requires drying to develop the water-resisting power. _D_ is a weight acting on a lever which presses the two rollers, _A_, together. The water-repelling property is gained as follows:

Drying the fabric, which is impregnated with acetate of alumina, drives off some of the volatile acetic acid, leaving a film of basic acetate of alumina on each wool fiber. This basic salt is very difficult to wet, and has so little attraction for moisture that in a shower of rain the drops remain in a spheroidal state, and fall off. In a strong wind, or under pressure, water eventually penetrates through fabrics proofed in this manner; but they will effectually resist a sharp shower. Unfortunately, shower-proofed goods, with wear, gradually lose this property of repelling water. The equation representing the change between alum and sugar of lead is given below. In the case of common alum there would, of course, be potassium acetate in solution besides the alumina.

Alum. Sugar of lead. Al_〈2〉K_〈2〉(So_〈4〉)_〈4〉 + 4 Pb(C_〈2〉H_〈3〉O_〈2〉)_〈2〉

Lead Potassium Aluminum sulphate. acetate. acetate. = 4 PbSo_〈4〉 + 2 KC_〈2〉H_〈3〉O_〈2〉 + Al_〈2〉(C_〈2〉H_〈3〉O_〈2〉)_〈6〉

Now that sulphate of alumina is in common use, alum need not be used, as the potash in it serves no purpose in proofing.

There are many compositions conferring water resisting powers upon textiles, but unfortunately they either affect the general handle of the material and make it stiff, or they stain and discolor it, which is equally bad. A large range of waterproof compositions can be got by using stearates of the metals; these, in nearly every case, are insoluble bodies, and when deposited in the interior of a fabric form a water-resisting “filling” which is very effective. As a rule these stearates are deposited on the material by means of double baths; for example, by passing the fabric through (say) a bath of aluminum acetate, and then, after squeezing out the excess of liquid, passing it through a bath of soap. The aluminum salt on the fabric decomposes the soap, resulting in a deposit of insoluble stearate of alumina. This system of proofing in two baths is cleaner and more economical than adding all the ingredients together, as the stearate formed is just where it is required “on the fibers,” and not at the bottom of the bath.

One of the most important patents now worked for waterproofing purposes is on the lines of the old alumina process. In this case the factor used is rosin, dissolved in a very large bulk of petroleum spirit. The fabrics to be proofed (usually dress materials) are passed through a bath of this solution, and carefully dried to drive off the solvent. Following this, the goods are treated by pressing with hot polished metal rollers. This last process melts the small quantity of rosin, which is deposited on the cloth, and leaves each single fiber with an exceedingly thin film of rosin on it. It will be understood that only a very attenuated solution of rosin is permissible, so that the fibers of the threads and not the threads themselves are coated with it. If the solution contains too much rosin the fabric is stiffened, and the threads cemented together; whereas if used at the correct strength (or, rather, weakness) neither fabric nor dye suffers, and there is no evidence of stickiness of any description.

Fig. 9 shows a machine used for spreading a coat of either proofing or any other fluid on one side of the fabric. {748} This is done by means of a roller, _A_, running in the proofing solution, the material to be coated traveling slowly over the top and just in contact with the roller, _A_, which transfers the proofing to it. Should the solution used be of a thick nature, then a smooth metal roller will transfer sufficient to the fabric. If the reverse is the case, and the liquid used is very thin, then the roller is covered with felt, which very materially adds to its carrying power. As shown in Fig. 9, after leaving the two squeezing rollers, _BB_, the fabric passes slowly round a large steam-heated cylinder, _C_, with the coated side uppermost. This dries the proofing and fastens it, and the cloth is taken off at _D_.

Besides stearates of the metals, glues and gelatins have been used for proofing purposes, but owing to their stiffening effect, they are only of use in some few isolated cases. With glue and gelatin the fixing agent is either tannic acid or some metallic salt. Tannic acid converts gelatin into an insoluble leather-like body; this can be deposited in the interstices of the fabric by passing the latter through a gelatin bath first, and then squeezing and passing through the tannic acid. Bichromate of potash also possesses the property of fixing the proteid bodies and rendering them insoluble.

The following are special processes used to advantage in the manufacture of waterproof fabrics:

I.—Ordinary Fabrics, Dressing Apparel, etc.—Immerse in a vat of acetate of alumina (5° Bé.) for 12 hours, lift, dry, and let evaporate at a temperature of from 140° to 149° F.