This section is from the "Henley's Twentieth Century Formulas Recipes Processes" encyclopedia, by Norman W. Henley and others.
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 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.