BOOK IV.
Gutta-Percha is destined to exert a very important influence in commerce and manufactures. Since its discovery it has made rapid strides as a useful and important agent in the arts. Its uses may be said to be innumerable, and although it was discovered but a few years since, it has completely superseded other substances, which were before regarded as indispensable. Our object is to give to manufacturers and all interested in the use, history, or application of this gum, as much insight as possible into the patents which have been issued in relation to it, both in England, France, and the United States. We have very carefully examined all the English works which treat upon the subject, and shall give a faithful history of all that has been written upon it which is ofpracticalimportance to the shoe manufacturer. A better knowledge of its properties and uses cannot, we think, be obtained than is set forth in the various patents and communications which have been issued.Here may be found, not only a general idea of gutta-percha as a gum, but the results of scientific investigation, application, and analysis. We have, therefore, carefully avoided all the superfluous technicalities connected with patent papers, except such as are important to the object proposed, and selected only such as will be of real importance to the shoe manufacturer, or the scientific enquirer.
The first patent ever issued in England, and which may be considered as the master patent, was taken out by Richard Archibald Brooman, of London. Patent dated March 11, 1845. Specification enrolled September 11, 1845.
After reciting the specification, the patent describes the properties of the gum.
First.It is of a highly combustible quality, being chiefly composed of carbon and hydrogen, while at the same time it inflames only at a very high degree of heat, and isnot injuriously affected by any known degree of atmospheric heat.
Second.It is soluble in essential oils, but resists, to a great extent the action of grease and unctuous oils.
Third.It mixes readily with paints, pigments, and most other coloring matter.
Fourth.It is repellent of, andunaffected by cold water or damp.
Fifth.It may be so softened by mere immersion in hot water, or by exposure to steam or hot air, as to be capable without further treatment, of being kneaded or moulded, or rolled out, or spread in any desired shape, and to any extent of tensity.
Sixth.It is of a strongly adhesive or agglutinating quality, and when dry is free from stickiness.
Seventh.In the dry or solid state it is flexible, of great tenacity, and to a slight degree elastic.
Eighth.It is impermeable to, and not injuriously affected by atmospheric air.
Ninth.It is, in a pure state, nearly inodorous.
Tenth.It is little, if at all injured by use, (except as fuel), and may, after it has been employed in a manufactured state, be recovered or renovated, and manufactured anew.
In some of these properties, namely, its adhesive, and water and air repellent properties, gutta-percha resembles caoutchouc, or India-rubber, but it is advantageously distinguished from it in its freedom from stickiness when dry, in its not being so affected by atmospheric heat, or by unctuous oils, and in its beingworkable by means of hot water alone.
[The patentee then described how this substance may be applied, either by itself, or in combination with other materials.]
1st.Artificial Fuels.—Five different sorts are described, the peculiarity in all of which consists in the substitution of the gutta-percha, in different forms or proportions, for the coal tar, or other agglutinizing substance ordinarily employed.
2d and 3d. Artificialmastics and cements.
The gutta-percha is directed to be first freed from the fibrous and foreign matters with which it is usually found intermixed, when first imported, after which it is to be applied in any one of the three states, namely, 1st, a plastic state; 2d, a granular or pulverized state; and 3d, a state of solution.
PLASTIC APPLICATIONS.
The kneading machinery is similar to that used in the manufacture of rubber. When it is desired to give to the mass of gutta-percha a greater degree of elasticity than is natural to it, I mix up and incorporate with it, while it is going through the kneading machine, either a portion of caoutchouc or a portion of sulphur, or portions both of caoutchouc and sulphur.
The following are good average proportions: about three parts caoutchouc for every six parts of gutta-percha, or one part of sulphur for every eight parts of gutta-percha, or two parts of caoutchouc, and one part of sulphur for every six parts of gutta-percha. When caoutchouc, however, is employed to increase the elasticity of the gutta-percha, a degree of heat, of not less than 150° Fahrenheit is necessary to effect the amalgamation of the two substances. The caoutchouc is most conveniently introduced into the machine at the same time with the gutta-percha, but the sulphur should be dropped into and upon the gutta percha from time to time, and in small quantities at a time. The gutta-percha takes up the other materials readily, and the whole are, at the end of the process, thoroughly amalgamated. Should it be desired to give any color to the mass, the requisite pigment or coloring matter is introduced in the same manner as the sulphur, and also in small quantities at a time. The coloring matter penetrates every part of the mass, and becomes perfectly amalgamated and identified with it. The gutta-percha may be also improved in smoothness, by incorporating with it some pulverized French or Turkey chalk, or othersoft powder, adding it in same way as the sulphur, or should it be desired to make it rough, and abrasive, it may be mixed up with some ground emery, sand, or other hard substance, in a granular state.
There are other combinations in which the gutta-percha in its plastic state, intimately mixed or blended with other materials, as for example:—There may be added to the gutta-percha, while in the kneading machine, paper pulp, wood dust, leather dust, hair bristles, oakum, &c. (taking care when they are not in a comminuted state, to cut them up small) and compound fabrics will be thus produced very suitable for paring, roofing, sheathing, and other purposes.
As before stated the gutta-percha may be dissolved in most of the essential oils, and by the application of a gentle heat, the patentee states that he prefers using for the purpose, rectified naptha, or rectified oil of turpentine. It may also be applied in a state of solution to rendering water and air proof, or cementing the various articles to which gutta-percha has been before stated to be applicable for these purposes in a plastic state, when sulphur imposed upon or between the surfaces of articles. It may be applied in this fluid state, to the saturation of cordage of all sorts, in order to increase its strength, and render it water proof, and as a size for stiffening silks, ribbons, and other fabrics. And lastly, it may be employed in this liquid state mixed with colors, for printing silk, cotton, leather, and other fabrics.
R. A. Broomancaused another patent to be issued, under date of March 27, 1845.
The invention comprehended under this patent is stated to have for its object the “the manufacture of a thread of great strength and durability, and perfectly water-proof, from the substance called gutta-percha, and the application thereof to the manufacture of piece goods, ribbon, paper, and other articles.”
The specification then describes the manner in which this object is carried out. The machinery is very simple. It consists of a die-box kept hot by steam, from the bottom of which a number of small tubes project downwards into a tank filled with cold water; and a cylinder and piston mounted on the top of the box. The mode of operation is as follows:
A roll of the prepared gutta-percha is introduced into the cylinder immediately above the die-box. The piston is then replaced, and forced steadily downwards by hand or other suitable power upon the gutta-percha, which, becoming softened at the lower end by contact with the hot die-box, escapes from the pressure through the tubes in a series of threads, which, as they drop into and are cooled in the water in the tank, and carried around a roller, whence they are conducted to and wound upon a set of revolving reels, after the manner of hand-spinning, that is, by working the thread between the fingers and thumb, the thread may be stretched about four times the original length. The threads are then wound off on bobbins and ready for use.
I twist and spin two or more such threads togetherinto one round thread, by means of a bobbin and fly frame, such as is used in the manufacture of cotton. Besides giving to the gutta-percha threads the desired roundness, these whirling and twisting processes have the effect of greatly improving them, in point of elasticity.
A strong, and perfectly water-proof fabric is formed by simply laying a number of gutta-percha threads side by side upon a foundation of cotton or linen, or other textile fabric, and passing the two materials between heated rollers, which have the effect of cementing the threads firmly to the cloth and to one another; and such fabrics may, by using the threads of different sizes and color, have every nicety of striped appearance given them.
Articles resembling diaper, or mosaic work, are made of gutta-percha threads of different colors or shades, very rapidly and economically. In the manufacture of paper, an article very difficult to rend, and which will, therefore, be found extremely suitable for documents exposed to much tear and wear, as bills of exchange, certificates, also for wrappers, envelopes of all sorts is formed by interposing between two sheets of paper pulp threads of gutta-percha, laid cross-wise like net work, at distances of an inch or two apart, more or less, and combining the two sheets by any suitable machinery as heated rollers. The gutta-percha thread may also be plaited either in the naked or sheet state, into hats, cans, bonnets, or into bags, baskets, basket work, or into coverings for chairs as a substitute for cane, or into whips, bridles, reins,or into any other similar articles—and finally, cordage of great strength may be made by twining together threads of gutta-percha with threads of flax, or other durable fibrous material, by the same processes as are ordinarily followed in the manufacture of the different sorts of cordage.
The following described Patent for improvements in Boots, Shoes, Gaiters, &c., is of great importance, inasmuch as it fully describes the method of manufacture, the solution used, &c. It will be observed that Mr. Keene mixed caoutchouc or India-rubber with gutta-percha. This process is now found to be very detrimental to the durability of the boot, shoe or gaiter, inasmuch as a rubber mixture is sure to become decomposed by the oils in the upper stock or soles. It also renders the shoe a nasty, sticky mass, making it impossible to repair them. The process has been tried here, evidently a copy of the Keene patent. After an expenditure of thousands of dollars, the manufacture of boots and shoes by this admixture of India-rubberhas been abandoned as impracticable.
Gutta-percha, on the contrary, is not affected by oils, and here is the grand secret of the success and triumph of boots and shoes cemented by it. Goods of various descriptions, including boots and shoes, were largely manufactured in England, between 1845 and 1848, which, being made with a mixture of India-rubber and other foreign matter, were thus rendered valueless. In six months after many of these varieties of elegant fabrics were put into the market, theywere discovered to be a sticky mass of worthless trash, or where the rubber was omitted became brittle like glass.Whereas, goods that were manufactured from the pure gutta-percha, such as picture frames, &c., remained uninjured to the present day, and are now apparently as firm and indestructible as when first made.
Here follows the Patent.
Charles Keene, of Sussex Place, Regent’s Park, Esq., for improvements in Boots and Shoes, Gaiters, Overalls, and other like articles. Patent dated May 29th: Specification enrolled November 29th, 1845.
My improvements in boots, shoes, gaiters, overalls, and other like articles of apparel, consist in rendering the same more or less weather and water-proof, and more easy of wear, by the application of the same, in whole or in part, of the substance recently imported from the East Indies called gutta-percha.
First.I coat the pieces of leather, or other material, of which the boots, shoes, gaiters, overalls, or other articles of apparel, are made, on either one or both sides, with a solution of gutta-percha, or a solution of gutta-percha mixed with a portion or portions of caoutchouc, or sulphur, or coloring matter, or any other substance or thing which may be calculated to improve the quality of the said solution as directed and explained in the specification of certain letters patent, of date March 11th, 1845, granted to Richard Archibald Brooman, for “certain improvements in the preparation and application of artificial fuels, mastics, and cements,” and this I doeither once, twice, or oftener, according to the thickness of the solution, and the thickness desired to be given to the coating; and sometimes, instead of so coating the whole of the said pieces, I coat those pieces which are likely to be most exposed to the weather or wet, as for example, the outer sole and upper leathers only.
Second.I protect in like manner the said pieces of leather, or other material, some or all of them, by covering the same, either on one or both sides, with a layer or layers of gutta-percha in the plastic state, or of gutta-percha combined in the said plastic state with a portion or portions of caoutchouc, or sulphur, or coloring matter, or of French chalk, or other soft powder, as directed in the aforesaid specification of the patent of Richard Archibald Brooman, applying the said layer or layers by the means and in the mode also described in the said specification.
Third.Instead of either coating or covering, as aforesaid, the materials of which the boots and other articles before mentioned are made, I sometimes interpose between the same or certain portions of the same, as for example, between the inner and outer soles, or between the upper leathers and linings, pieces of gutta-percha in any of the sheet states in which it is manufactured under the said patent of Richard Archibald Brooman.
Fourth.I manufacture boots, shoes, gaiters, overalls, and other like articles, in whole or in part, of a compound fabric, formed and described by the specification of the said Richard Archibald Brooman, by adding to the gutta-percha while in the kneadingmachine (whether previously combined, or not combined with caoutchouc or sulphur, or coloring matter, or French chalk, or other soft powder, as aforesaid) a portion of leather, dust, or hair, or bristles, or ground cork, or woolen shearings, or other membranous or fibrous substances, in a finely comminuted state.
Fifth.I also manufacture boots, shoes, gaiters, and other like articles, in whole or in part, of a certain other fabric which is directed in the specification of the said Richard Archibald Brooman to be formed by saturating a bat or fleece of cotton wool, or other fibrous material, with a solution of gutta-percha, or a mixed solution of gutta-percha and caoutchouc; preferring, however, for the purpose of this part of my invention, such bats or fleeces, as have been saturated with a solution containing in it a portion more or less of sulphur and of some coloring matter.
Sixth.I make boots and shoes, and the other articles aforesaid, of gutta-percha, or of a mixture of gutta-percha and caoutchouc, either sulphurized or not sulphurized, all in one piece, without sewing or stitching, as usual, by casting the same in cored moulds, made of the required form of the boot, shoe or other article. I either fill the mould with the material in a state of hot solution, and leave it to cool, or I fill it with the material in a granular state; heat the mould till its contents become in a pulpy state, and then set it to cool. I sometimes use a single matrix only, and cause the material in a sheet or in a plastic state, to assume the state of that matrix by forcing it into the recesses thereof, by meansof the pressure of water or air, and sometimes in order to give greater springiness to the boot or shoe, or other article, instead of casting it all in one piece, I cast it in two or more pieces; as for example, I cast the front part in one piece, and the heel or back part in another piece, and unite the two parts by means of an interposed piece or pieces of leather or of gutta-percha in the sheet, and sulphurized state, or some other like flexible material.
Seventh.Instead of uniting the different parts of which boots and shoes, and other articles aforesaid are made, by stitching or sewing, as usual, whenever any two of these parts, or any one or two parts consists of gutta-percha, or of a mixture of gutta-percha and caoutchouc in any of the sheet states aforesaid, I pass a hot iron over the joint or joints, which causes the two surfaces to adhere firmly together.
Eighth.I take boots, shoes, gaiters, overalls, and other articles as they are now ordinarily made of unsulphurized caoutchouc, and greatly improve the same in point of smoothness of texture, and capability of resisting variations of temperature by exposing them for from thirty to sixty minutes to the fumes of sulphur, in a close vessel, heated to a temperature of 210 to 250 degrees more or less, or immersing them for the same length of time in a bath of melted sulphur. In either case, in order to prevent the articles from sticking to one another, they should be done over with a paste made of French chalk, flour and water, and that paste allowed to dry before subjecting them to the action of the sulphur. Boots, shoes, and other articles made in whole, or in part ofunsulphurized gutta-percha, may be treated in the same way, but I prefer incorporating the sulphur in the first instance with the gutta-percha, when it is in the state of solution, or in the plastic state, or in any of the other states of preparation and combination aforesaid.
Lastly.I improve the shoes of horses by laying upon and securing to the upper part of the same, a sheet, or layer of sulphurized gutta-percha, or of sulphurized caoutchouc, or by making the same wholly of either of the said materials. In the former case, the sheet or layer of sulphurized gutta-percha, and sulphurized caoutchouc, may be either attached to the shoe by rivets, before it is applied to the foot, or it may be laid loosely between the shoe and foot when the horse is being shod, and be made fast by passing the shoe nails through it. It affords a soft and yet firm footing to the animal, and resists, without injury to its shape, very high degrees of heat and pressure.
The following described patent was taken out byCharles Hancock, of Grosvenor Place, for “certain improvements in the manufacture of gutta-percha, and its application alone, and its combination with other substances.” Patent dated Jan. 12, 1846.
In copying these patents our aim is to make perfectly plain and clear to all interested, certain chemical facts, compounds and the like, which produce desired results, and which have thus far been preserved, as profound secrets. For example, in selecting certain claims or descriptions in the Hancock Patent, we heredescribe the process ofmaking and applying varnishes to India-rubber shoes, etc., which varnishes are perfectly sweet, “shutting in” all disagreeable odors, from sulphur and other combinations.
These varnishes may be applied to leather or cloth, giving them a beautiful glossy exterior, also rendering them water-proof.
The inventor says—“My invention consistsfirstly, in certain improved methods of preparing gutta-percha for manufacturing purposes. If the gutta-percha to be operated upon, is not very impure, it may be at once submitted to the process hereafter described. * * * * If impure, the gutta-percha may be cleansed by the process as laid down by R. A. Brooman, March 11, 1845.”
Mr. Hancock continues—“According to one of my improved methods of preparing gutta-percha, I place it in a plastic state in a cylindrical screw press, kept hot by a steam jacket, or otherwise, and having the bottom perforated with numerous holes, andsqueezeit through the strainer and perforated bottom, from which it falls in a much purified state.
“This operation may, if necessary, be repeated; I then transfer the gutta-percha in this purified state, to a masticating machine, such as is commonly employed in the preparation of caoutchouc, and kept hot by any suitable means, and work and knead the gutta-percha until it is brought to the consistence of dough or putty. According to another of my modes of preparing gutta-percha, instead of passing it through the screw-press, as before described, I take the plastic mass and pass it a number of times betweenheated rollers, kept hot by hot water, steam, or any other convenient means. Or, thirdly, I take the gutta-percha as imported, and dissolve it by means of rectified oil of turpentine, or any other suitable solvent, and filter the solution while warm, through flannel, or felt, or fine wire gauze, after which I distil off the solvent, and evaporate the residuum to the consistence of dough or putty.”
Secondly, “My invention consists in making a compound, elastic, water-repellent substance for manufacturing purposes, by combining gutta-percha with an elastic and water-repellent substance, called “jintawan.” I combine the two substances in a masticator, and then operate upon the two materials by that machine; at the same time adding any coloring matter that may be desired, continuing the operation of the machine, until they are intimately blended together. And I make the triple combination of ‘gutta-percha,’ ‘jintawan,’ and ‘caoutchouc,’ and by means of a masticator, in the same manner. For the purpose of making these combinations. I vary the proportions of the two, or of the three substances which I combine according to the quality which it is desired that the combined substance shall possess.”
Thirdly, “My invention consists in combining gutta-percha, or gutta-percha, caoutchouc, and “jintawan” with orpiment, liver of sulphur or other sulphurets, having like chemical properties, which will enable it to combine effectually with the other articles above mentioned, and afterwards subjecting the compound substance to heat, as herein described. * *A good compound for bands or tapes, is found by combining 50 parts of gutta-percha, 24 parts of “jintawan,” 20 parts of caoutchouc, and 6 parts of orpiment. I may state as a general rule, deduced from the experiments which I have made, that the proportion of orpiment, or other sulphuret used, ought not to exceed 25 per cent.
“When jintawan, or caoutchouc is used in making this compound article, the combination of the materials will be much facilitated by previously moistening the jintawan and caoutchouc, or such of them as are used, with rectified oil of turpentine, or some other solvent, so that they may be softened in the manner aforesaid. The orpimented, or sulphureted compound is next to be exposed to a heat of from 300° to 340°, for a period varying according as the temperature is higher or lower. With a heat of 300° Fahrenheit, I keep the article exposed to it for about sixty minutes; with a heat of 340°, for about fifteen minutes only. The required heat may be obtained by means either of high pressure steam, or water heated under pressure, or of hot air.
“I consider the use of sulphur to be objectionable, because of theoffensive smell which it imparts to the article, and of the tendency which sulphur has to effervesce, or exude from the surface of it. And therefore I prefer the use of orpiment or some other sulphuret which will combine more effectually with the other component parts of the article.”
Fourthly, “My invention consists in a mode of rendering gutta-percha, or a combination of that substance with ‘jintawan’ and caoutchouc, or either of them, of a light, porous, and spongy texture, forming a species of artificial sponge, suitable for stuffing or forming the seats of chairs, cushions, mattresses, saddles, horse collars, buffers, and for many other useful purposes.
“To gutta-percha, which is intended to be made porous or spongy, for such purposes as aforesaid, must be added about 10 per cent. of rectified spirit of turpentine, or other proper solvent, and the whole mixed together by any convenient means. And if any of the above-mentioned compounds of gutta-percha is intended to be similarly treated, the caoutchouc or “jintawan” used therein, must be previously dissolved in from 100 to 200 per cent. of a similar solvent, the quantity of solvent being more or less, according as the product is intended to be more or less spongy and elastic. To the article which is intended to be made porous and spongy, must be added alum or carbonate of ammonia, or some other description of volatilizable substance.
“If the article which is intended to be made porous and spongy, is required to be made more permanently soft and elastic, it should be combined orpiment, liver of sulphur, or a sulphuret, in the same way as described in the third part of my invention. A portion of sulphur may, in such a case, be used, but I prefer orpiment, liver of sulphur, or a sulphuret, for the reasons I have before stated.
“The article which is intended to be made spongyand porous must then be thoroughly mixed with from ten to twenty per cent. of alum, carbonate of ammonia, or some readily-volatilizable substance, either in the masticating machine, or by any other convenient means. The material thus prepared, may be put into moulds, or forms, or upon trays, or confined in such a way as to cause it to assume the form which it is intended to possess. The material is then put into an oven or chamber, heated by steam or other convenient means, to a temperature of from 250° to 260° of Fahrenheit, at which temperature the article must be kept from one to two hours, according to the desired result. The effect of the exposure of the article to this high temperature will be to drive off the solvent with which it has been mixed, and at the same time, the alum, carbonate of ammonia, or other volatilizable substance before mentioned, cause the article to swell, and will render it porous and spongy. When the article has been exposed to this temperature for about one hour, it will be in the most porous and spongy state, and if the operation is further prolonged, the effect will be to render it less elastic and more rigid.”
Fifthly, “My invention consists in imparting, by the following process, to gutta-percha and its various combinations with caoutchouc and “jintawan,” when orpimented or sulphureted as aforesaid, almost any degree of hardness and tenacity, without injury to its water-repellent properties. I take the gutta-percha, or gutta-percha compound, after it has gone through the process described under the third head of this specification, and while it is yet in a plastic state, andpress it into moulds, which I bind tightly together with iron plates, screws and nuts. I then place these moulds in a chamber or vessel raised by steam or hot air to a temperature of from 300° to 380°, for from one to five or six days, varying the degree of heat and the time of exposure to it, according to the degree of hardness and tenacity required, after which I set the moulds aside to cool slowly. The gutta-percha and gutta-percha compounds may be so hardened by this means, as to be turned in the lathe, like wood or ivory. And they are thus rendered applicable to a great variety of purposes, for which they could not in any other state be suitable, such as picture-frames, knife and sword handles, door-handles and panels, walking-sticks, chess-men, seal-holders, paper-cutters, combs, flutes, musical-keys, buttons, pulleys, ornamental and architectural decorations, &c.
“The material may be either at once formed into any of these articles, by making the moulds of the form and figure of the articles; or it may be produced in the first instance in plain blocks, and afterwards cut up and fashioned at pleasure, by such tools and instruments as are ordinarily used for like purposes.”
Eighthly, “My invention consists in forming in manner certain varnishes which may be applied to the water-proofing of leather or cloth, and in applying them either alone or mixed, without coloring matter, to gutta-percha or its compounds, or to articles made from them, they may havea fine, glossy exterior given to them, and the smell of any ingredient which may have been mixed up with them, and which may be of an offensive nature, (such as sulphur) may be effectuallyshut in. For this purpose I take the gutta-percha, or gutta-percha combined with “jintawan” and caoutchouc, or either of them, orpimented or sulphureted as before described, or sulphurize and dissolve it by confining the mass in a steam-tight vessel, and by placing that vessel in a chamber heated by steam or other convenient means to a temperature of 300° to 380° Fah., or I mix gutta-percha and caoutchouc, or gutta-percha and “jintawan” (using the substance indifferently, so far as the proportion one bears to the other,) with sulphur or orpiment, or other sulphuret, in the proportion before directed to be observed, where these substances are introduced with about eight to ten parts of animal or vegetable wax, or of animal or vegetable fatty matter, and then dissolved in rectified spirits of turpentine, and evaporate as before. As these varnishes combine readily with colors, they afford the means of rendering a numerous class of articles, such as elastic rings, bands, bandages, straps, &c., much more extensively, suitable and vendible than before. These varnishes mixed with colors, may also be used for the purpose of painting or printing cloth, leather, or any other fabric. These varnishes will also be found very useful as cements, particularly in combining gutta-percha and its compound, with silk, cotton, and other textile fabrics.”
Eleventhly, “My invention consists in making cards for carding cotton and other fibrous materials, in manner following—I make the backs either ofgutta-percha alone, spread in a plastic state to a sufficient thickness on a cloth, or felt, or other suitable foundation,or of any of the gutta-percha compounds which are of sufficient flexibility and consistence for the purpose. And I insert the metal teeth in these backs, according to any of the known methods followed in the manufacture of such cards.”
Twelfthly, “My invention consists in mixing with the gutta-percha prepared in the manner first hereinbefore described and exemplified in the masticating machine, shellac, or resin, or asphalt, or some other resinous or bituminous matter; and when the materials are thoroughly amalgamated, I spread the mixture while in a fluid state, upon cloth or leather, or any other suitable foundation.
“For low priced articles, I sometimes combine caoutchouc and sulphur with vegetable or Stockholm pitch; and when spread into sheets or made up into other forms, I vulcanize the compound. The proportions may be varied very considerably, as well as the temperatures at which they are vulcanized; but I find the following to answer well: 8 parts caoutchouc, 2 sulphur, 3 pitch; or 8 parts caoutchouc, 2 sulphur, 1 pitch, submitted to a temperature of 290° for an hour. To prevent blistering and porosity, if necessary, I employ pressure by means of screw cramps and plates, or otherwise, during the vulcanizing. This material is applicable to railway packing, and other rough uses.
“I also combine and vulcanize in the same manner caoutchouc, sulphur, and resins, preferring on account of its cheapness the common resin of commerce. The proportions and temperature, as in thecase of pitch, may be varied; but the following I find to be useful for many purposes: 16 parts caoutchouc, 2 parts sulphur, 6 parts resin; or 16 caoutchouc, 4 sulphur, 2 resin. These compounds may be submitted to the same treatment as in the case of pitch, and are applicable to similar uses. For some purposes, I also combine caoutchouc and sulphur with wood or cork dust, or fibrous substances, such as hemp and flax, or any other suitable material cut into short lengths, and vulcanize such compounds, either in blocks, or spread, or otherwise wrought into sheets, or formed into figures, or embossed, or ornamented as before described.”
The following account of “Parke’s Improvements in Dyeing” will be found to be very important:
I will now proceed to describe another part of my invention, which consists in dyeing caoutchouc and gutta-percha alone, or in combination; and afterwards, when desired, treating those matters by changing agents, according to either of the methods herein described.
To dye caoutchouc, or gutta-percha, or their compounds, black, I boil the same from a quarter of an hour to half an hour in the following preparation: I take one pound of sulphate of copper dissolved in one gallon of water, one pound of caustic ammonia, or muriate of ammonia; or I take and boil one pound of sulphate or bisulphate of potash, and half a pound of sulphate of copper with one gallon of water. To dye caoutchouc, or gutta-percha, or their compounds, green, I take one pound of muriate ofammonia, half a pound of sulphate of copper, two pounds of caustic lime, and one gallon of water, and boil as before, from quarter to half an hour. Another dye producing a purple tinge, I obtain by using one pound of sulphate or bisulphate of potash, a quarter of a pound of sulphate of copper, and a quarter of a pound of sulphate of indigo, and boil the caoutchouc, or gutta-percha, or compounds, from one quarter to half an hour. The depth of color may be varied by varying the proportion of the ingredients used. When it is wished to color caoutchouc, or gutta-percha, or their compounds, I employ the following colors, but do not confine myself thereto, nor do I make any claim to the same. Forblue, those known in commerce as Victoria blue and ultramarine. Forred, vermillion, carmine or rose lake. Forgreen, Brunswick green or acetate of copper. Foryellow, chrome yellow or oxide uranium. Forwhite, the color known as satin white; and I prefer generally to use this color as agroundfor the colors above named, and I would here observe, that the coloring processes precede those for “the change.”
ToCharles Hancockof Grosvenor Place, Middlesex, London, for certain improvements in the preparation of gutta-percha, and in the application thereof, alone and in combination with other materials, to manufacturing purposes; which improvements are also applicable to other substances. Sealed, February 10th, 1847.
This invention relates,firstly, to the methods and machinery employed for preparing gutta-percha for manufacturing purposes.
Secondly, to certain improvements or processes previously secured to the present patentee, and consisting in sulphuretting gutta-percha, (since called metallo-thionizing) and in applying these improvements to the sulphuretting of caoutchouc and jintawan.
In the last-mentioned specification, the patentee recommends that the sulphuretting of the gutta-percha should be effected by means of sulphurets, such as orpiment or liver of sulphur, in preference to sulphur itself; and he there states that though a portion of sulphur might be used in place of an equal portion of sulphuret, yet he conceives the use of sulphur to be altogether objectionable, because of its offensive smell and tendency to effervesce. He has since ascertained that if a minute portion of sulphur be used along with a sulphuret, a better result is obtained from a combination of the two than from either substance alone. The proportions which he finds to be the best are, 6 parts of sulphuret of antimony, or hydrosulphate of lime, or some analogous sulphuret, and 1 part of sulphur to 48 parts of gutta-percha: when these materials have been mixed, the compound is to be put into a boiler and heated (under pressure) to a temperature of from 260° to 300° Fah.; and it is to be left in this state for a period varying from half an hour to two hours, according to the thickness of the materials; by which times the gutta-percha becomes completelysulphuretted or metallo-thionized. The patentee applies precisely the same combination of materials (i. e., a sulphuret and a small quantity of sulphur) to the sulphuretting of India-rubber and jintawan, and in the same way. * * *
Thefourthmode consists in making a paste of the sulphuret and sulphur with the addition of a small quantity of gutta-percha or caoutchouc solution, brushing it over the material to be sulphuretted, and then subjecting the same to one of the three processes as described.
The invention consists,fourthly, in the following means of improving gutta-percha, both in a sulphuretted and unsulphuretted state, and in the application of the same to caoutchouc and jintawan in the like conditions.
The patentee either exposes the material for a minute or two to the action of binoxide of nitrogen gas, (obtained by the usual method of dissolving a metal, such as zinc, copper, mercury, in nitric acid) or he immerses it in a boiling and concentrated solution of chloride of zinc, for a period varying from one to five minutes, according to the strength of the solution; and in either case, he afterwards washes the material with some alkaline solution, or with soft water. The material may be subjected to the action of the binoxide of nitrogen gas, either by putting it into the acid while the metal is in the course of being dissolved and the gas evolved, or by introducing it into a chamber in which the gas has been collected for the purpose.
Gutta-percha which has been thus treated (whether sulphuretted or unsulphuretted), becomes exceedingly smooth and of a lustre approaching to metallic: so also does common unsulphuretted caoutchouc (rubber) with the addition of being entirely freed from that stickiness peculiar to it, while sulphuretted caoutchouc acquires under such treatment, all the downy softness of velvet. * * *
Thesixthpart of the invention consists in producing a new compound of gutta-percha by mixing, in a masticating machine, six parts thereof with one part of chloride of zinc; and in forming new compounds of caoutchouc and jintawan by a like proportional combination. All these compounds admit of being afterwards sulphuretted or sulphurized.
Theseventhpart of the invention consists in an improved combination of materials forproducing a porous and spongy gutta-percha, fit for stuffing or forming the seats of chairs, cushions, mattresses, saddles, horse-collars, railway carriage-buffers, and other like articles, similar to that described in the specification before alluded to; and in the application of the said improved combination of materials to the rendering of caoutchouc and jintawan similarly porous and spongy. The patentee takes 40 parts of gutta-percha, India-rubber or jintawan (moistened when a very light product is desired, with oil of turpentine, naptha, bi-sulphuret of carbon, or other proper solvent), 6 parts of hydrosulphuret of lime, sulphuret of antimony, or any other analogous sulphuret, 10 parts of carbonate of ammonia, carbonate of lime, or other substance that is either volatile orcapable of yielding a volatile product, and one part of sulphur. He mixes these materials together in a masticator, and then subjects them to a high degree of heat, observing the same conditions in respect thereof, which are set forth in the specifications alluded to; except only that the heat may be pushed with advantage several degrees higher, say to from 260 to 300°.
Theninthpart of the invention consists in producing by the combination of gutta-percha, caoutchouc and jintawan, with other materials, a fabric of a permanent lustre, resembling that of japanned goods, and in giving the like lustre to articles made of any of these materials in a sulphuretted state. The patentee takes the gutta-percha, caoutchouc, or jintawan after it has been sulphuretted, and either before or after it has been made into an article of use, and brushes it over with a solution of resin in boiling oil; he then places it for from two to five hours in a chamber heated to from 75 to 100° Fahrenheit; and afterwards polishes it by the means and in the manner usually adopted by Japanners. In some instances coloring matters are mixed with the Japanning materials, which are to be applied by blocks, cylinders, or rollers, in the usual way of floor cloth printing.
Patent dated December 30th, 1847, for “Improvement in the Treating and Manufacture of Gutta-percha, or any of the varieties of Caoutchouc.” Patentees,Thomas Hancock, of Stoke Newington, andReuben Phillips, of Islington, chemists. Specifications enrolled June 30, 1847.
The patentees state that their improvements consist in the dissolving of gutta-percha, or any of the varieties of caoutchouc, or of reducing any of them to a soft, pulpy, and gelatinous state after they have undergone the process of “vulcanization or conversion;” also in preparing or treating unvulcanized, or unconverted solutions of any of these substances, so as to bring them into a vulcanized or converted state; and, lastly, in the moulds employed in the manufacture of articles therefrom. The term “vulcanized” or “converted” are used to designate certain processes by which these substances are rendered less liable to be injuriously affected by exposure to comparatively high temperatures, and which were described, the first in the specification of a patent granted to Mr. Thomas Hancock,[2]November 21, 1843, and the record in that of a patent granted to Mr. Alexander Parker,[3]August 25, 1846.
2. See London Mechanics Magazine, vol. xlii. pp. 112 and 150.
2. See London Mechanics Magazine, vol. xlii. pp. 112 and 150.