CHAPTER I.

GUTTA-PERCHA PATENTS.

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 Its uses may be said to be innumerable, and although it was discovered but a few years since, it has completely superseded other substances, which were before regarded as indispensable.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 of _practical_ importance 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 is _not 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, and _unaffected 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 being _workable 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. Artificial _mastics 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 other soft 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.

APPLICATIONS IN STATE OF SOLUTION.

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. BROOMAN caused 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 together into 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-rubber _has 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, they were 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 do either 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 kneading machine (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 means of 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 of unsulphurized 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 by CHARLES 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 here describe the process of _making 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 consists _firstly_, 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, and _squeeze_ it 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 between heated 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 the _offensive 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 spongy and 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, and press 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 have _a 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 effectually shut 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 of _gutta-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 the case 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.”

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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 of ammonia, 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. For _blue_, those known in commerce as Victoria blue and ultramarine. For _red_, vermillion, carmine or rose lake. For _green_, Brunswick green or acetate of copper. For _yellow_, chrome yellow or oxide uranium. For _white_, the color known as satin white; and I prefer generally to use this color as a _ground_ for the colors above named, and I would here observe, that the coloring processes precede those for “the change.”

HANCOCK’S PATENT.

To CHARLES HANCOCK of 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 completely sulphuretted 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. * * *

The _fourth_ mode 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. * * *

The _sixth_ part 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.

The _seventh_ part of the invention consists in an improved combination of materials for _producing 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 or capable 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°.

The _ninth_ part 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.

RE-VULCANIZATION.

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, and REUBEN 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.

Footnote 2:

See London Mechanics Magazine, vol. xlii. pp. 112 and 150.

Footnote 3:

See London Mechanics Magazine, vol. xlv. p. 400.

The patentees desire to be understood, that when employing the term gutta-percha, or any of the varieties of caoutchouc, as referring to all those substances known to the Indians, or natives of the country where they are produced, under the names of saiknah, gutta-tuban, gutta-percha, jintawan, dollah, &c., in this country of bottle, root, sheet, scrap, India-rubber, &c. In operating upon any of these materials, which have previously undergone the vulcanizing or converting process, it is preferred to use the cuttings or waste of them, as being an _economical application_ of what _would otherwise be useless_. These cuttings or waste, are first submitted to the action of rollers, or other suitable machinery for reducing them to shreds, and then boiled in oil of turpentine until reduced to the requisite consistency. Other solvents may be employed, such as coal, naptha, &c., but in that case, in order that the solvents may attain to a degree of temperature sufficiently high to dissolve the material, close vessels must be employed, for which reason, oil of turpentine is preferred.

No fixed rule, it is stated, can be given for the guidance of the workman to enable him to determine the relative proportion of the material to the solvent, the time for conducting the operation, or the degree of temperature, on account of the varieties of the material, and the degree of vulcanization or conversion to which it has been subjected; for these and other details he must rely upon his own intelligence, and the result of actual experience.

The rule which the patentees, however, state that they have found to be the best, under ordinary circumstances, it is to just cover the material when prepared and placed in the vessel with the solvent, and then to add about one-third more, and maintain the mixture at the boiling point of oil of turpentine, for about from 15 to 30 minutes. The consistency of the mixture may subsequently be increased or diminished by evaporating, or by the addition of oil of turpentine, coal, naptha, or other solvent. When the material has been rendered hard or horny by vulcanization or conversion, the time necessary to dissolve it or reduce it to a soft pulpy state would be so long, as to render the preceding process worthless.

The mode of operating under the second head consists in mixing from eight to twelve parts of sulphur, with every one hundred parts of the solid material in solution, and then subjecting the mixture to the necessary degree of heat to produce the vulcanized or converted state.

The patentee mentions numerous applications of these solutions, among which may be cited water-proofing, and the employment of them as a medium for colors in painting, and in printing calico, &c.

The improvements in moulds consists in making them of a material easily soluble at low temperatures, such as D’Arcet’s metal, &c., so that they may be broken up, and easily removed from the moulded article without injury to them.

To ANTHONY LORIMIER, London, England. For improvements in combining gutta-percha and caoutchouc with other materials. (Sealed 10th of July, 1848.)

The first part of this invention consists in cutting gutta-percha into very thin shavings, (which the patentee prefers to effect by the use of certain described machinery, or any other suitable means may be employed); then drying the same by spreading them over any suitable surface, and afterwards subjecting the shavings of gutta-percha to the action of other machinery, by which they are bent in various directions and reduced or divided into smaller pieces; by this means the impurities will be separated without the use of heat or water, and the gutta-percha rendered suitable for use at a very small cost.

* * * * *

The second part of the invention consists in combining gutta-percha with burned clay, burned flint, broken articles of earthen ware and china, marble, Portland, Cornish, or other stones, crushed and sifted, likewise oxide of zinc, oxide of copper, hydrate of lime, oxalate of lime, and also a compound of lime slaked with oxalic acid dissolved in water; in preparing this compound, about three pounds of acid are used to each bushel of lime; the acid is first dissolved in a sufficient quantity of water for slaking that quantity of lime; and after the solution has been added to the lime, the product is well dried and sifted. Any one or more of these materials may be combined with gutta-percha, with or without other materials, so as to produce new compounds of gutta-percha, useful for moulding articles, or for making sheets, _suitable to be cut into soles for boots and shoes_, straps, bands and other articles.

The above matters are to be ground very fine and sifted; and the gutta-percha may be combined therewith, by any convenient means; but the patentee prefers to lay the gutta-percha on a heated plate, and roll it into a sheet, then to sift the materials over the sheet, and fold and re-fold the same, and to repeat the rolling, folding and sifting of the materials, until the desired compound is produced; or he rolls the gutta-percha between two smooth heated rollers, then dusts on the powder and folds the sheets, and again and again rolls the same till the desired mixture is obtained. He further states that in place of using the “welding machine,” he can employ like means to those just described for combining the small pieces or shavings of gutta-percha into a mass. The compound of gutta-percha may, whilst still in a heated state, be moulded to any desired form, or rolled into sheets. When great _elasticity is required_, caoutchouc (India-rubber) is mixed with such compounds of gutta-percha.

CHARLES HANCOCK, of Broughton, gentleman. For “certain improved preparations and compounds of gutta-percha, and certain improvements in the manufacture of articles and fabrics composed of gutta-percha alone, and in combination with other substances.” Patent, dated May 11, 1848; specification enrolled Nov. 11, 1848.

_Specification._—In making water-proof shoes and galoshoes of gutta-percha, I begin with casting the gutta-percha in moulds into pieces or blocks, of a form suitable for the purpose. * * * * I next take a last of the form desired to be given to the shoe or galosh, and draw upon, or otherwise fit closely to it, some elastic or flexible material which may serve as a lining for the gutta-percha, such as cotton or woolen cloth, or knitted silk, or worsted, or cotton. I then coat the outside of this intended lining, with a solution of gutta-percha or caoutchouc, and leave it to dry. I next select a gutta-percha block of the best form, adapted in its general outline to the said last, and, by heating it in any convenient way, bring it to such a plastic state that it may be readily moulded by the hand. I warm also the last, with its elastic or flexible covering, but not to such a degree as to decompose the gutta-percha or caoutchouc solution spread over it; and these preparations having been made, I place the last upon the block, adjust by hand the one to the other, and press the gutta-percha, of which the block consists, into as close combination as may be, with the elastic or flexible covering of the last. But, as in the course of the preceding manipulations some inequalities of surface may have been unavoidably produced, or the limits between the sole and the upper not have been sufficiently defined, I once more bring the whole into a warm or plastic state, by dipping the shoe or galosh (with the last still inside of it) into hot water, or by exposing it to steam or hot air, and then smooth it carefully all over. When it becomes cold and hard, I run a revolving stile or other suitable instrument over the contour lines, after which the last is withdrawn, which leaves the shoe or galosh complete. Sometimes I use _hollow lasts_ made of _metal_, glass, or earthen ware, and heated by steam, hot air, or hot water.

When made in the manner just described, the article, though water-tight, is of a dull appearance; but it may have a _high polish_ given to it, or to any part of it, by applying glass or porcelain moulds to it, after it has undergone the process last hereinbefore mentioned, and while it is yet in a warm and impressible state; each of these moulds being a fac simile in reverse, in some portion only of the last, (as for example, the sole or the upper) and not removed, after being so applied, till the materials beneath have become quite cold. Shoes made of gutta-percha, on foundations of elastic or flexible materials, in the manner before described, possess this great advantage over others, that the foundations take up and disperse the perspiration of the foot, and prevent it from condensing, to the injury of the health and comfort of the wearer.

Exception has been taken to gutta-percha shoes and galoshoes on account of their want of or deficiency in springiness. I remedy this, (when desired) by making the block out of which the sole and upper is formed, of two sheets or pieces of gutta-percha, and interposing between them, while they are yet in a warm and plastic state, a thin plate of steel, slightly bent in the direction from heel to tip, and press the whole closely together, so that the metallic spring may become permanently fixed, embodied in, and combined with other materials.

_Third._ I paint and print articles and fabrics made in whole or in part of gutta-percha, and also other articles and fabrics of any color or colors, and of any design or pattern, by using as a vehicle for the pigments or other coloring matters, the following compound: I take one part of caoutchouc and one part of gutta-percha, each dissolved in spirits of turpentine, (or other suitable solvent,) add thereto four parts of gold-oil size; mix the whole of these materials together in a bath of hot water, and then thin with spirits of turpentine, it being of advantage to use this compound in a very thin state. The pigments or other coloring matters should be well ground up in turpentine before they are mixed with the vehicle. The proportions such as I have given, are such as I find to answer, on the whole, best in practice.

In carrying out the different improvements which I have hereinbefore specified, I uniformly prefer employing such gutta-percha, or compound of gutta-percha, as has been prepared by boiling or by masticating it in a bath of water and muriate of lime, but to this mode of preparation I do not here lay any claim.

To make a compound preferable to any yet in use for casting and moulding purposes, for water-proofing cloth, leather, and other articles and fabrics, and for coating ships’ bottoms, lining tanks and cisterns, &c., I mix with gutta-percha which has been first boiled in a bath of muriate of lime, and then masticated thoroughly, and while it is yet undergoing the process of mastication, a compound of shellac and borax, adding the same little by little as the mastication proceeds, and using more or less, according as it is desired to make the compound more or less tenacious. The compound of shellac and borax is prepared by boiling in a steam kettle over a common fire, five parts stick lac, or shell lac, or seed lac, with one part of borax, in so much water as will just cover these materials, and evaporating the water according to the thickness desired to be given to the compound. Any desired color may be given to this mixture of gutta-percha, shellac and borax, by mixing the requisite pigment or coloring matter with the shellac and borax compounds.

The improvements which I claim in my invention are as follows:

_First._ I claim the mode of making shoes and galoshoes of gutta-percha, combined with other materials first before described, in so far as regards the combination of elastic or flexible foundations with gutta-percha soles and uppers.

_Second._ I claim the employment of glass moulds to give a polish to the exterior or parts of the exterior of shoes and galoshoes made in whole or in part of gutta-percha, as before described.

_Third._ I claim the making of backs and stocks for brushes in whole or in part of gutta-percha, in order to give springiness to the same.

_Fourth._ I claim the making of backs and stocks for brushes in whole or in part of gutta-percha, as before described and exemplified.

_Fifth._ I claim the employment for painting, printing, or otherwise applying colors to articles and fabrics made in whole or in part of gutta-percha, and also to other articles and fabrics of the particular compound or vehicle hereinbefore specified, but without limiting myself to the exact proportions in which each of the materials has been directed to be used in such compound or vehicle, inasmuch as the said proportions may be varied without affecting the general result.

_Sixth._ I claim the employment, for all manufacturing purposes to which the same are applicable, of the several other improved preparations and compounds of gutta-percha specified under the fourth head of this specification, each in the peculiar combination of materials of which the same consists, and the peculiar process or processes by which it is prepared.

JAMES CARTLEY, of Harpenden, Hertford, manufacturing chemist, _for improvement in the manufacture of varnishes from resinous substances_. Patent dated January 11, 1849.

This invention consists,

_First._ In manufacturing in manner following, from resin spirit, and the gum resin called gutta-percha or gutta taban, a new compound or varnish which possesses the properties of being strongly adhesive and perfectly _water repellent_. The patentee puts into a pot three parts, by weight, of the gutta-percha or gutta taban, as imported or as it may be bought in the home market, and adds nine parts of crude resin spirit, (obtained by the destructive distillation of common resin) and subject them to a heat of from 120° to 140° Fah., stirring the mixture occasionally. The resulting solution forms a varnish which answers well for the coating of all coarse fabrics, such as tarpaulings, rick cloth, &c. But to obtain a varnish of a purer and better quality, suitable for fine articles, he rectified resin spirit, which he obtains by passing a current of steam through the crude resin spirit until the condensed product which comes over exhibits a specific gravity of about 0.870, at which point the process of distillation must be stopped, all products of a higher specific gravity being injurious to the quality of the spirit.

_Claim 1st._ The manufacture of the new varnish compounded of gutta-percha and resin spirit, (crude, rectified, or purified,) as before described.

_Second._ The manufacture of the new varnishes compounded of gum damar and resin spirit, or of gum mastic and resin spirit, whether such spirit is rectified and decolorized or rectified only, as before described.

WILLIAM HENRY BURKE, Tottenham, manufacturer. For improvements in the manufacture of air-proof and water-proof fabrics, and in the preparation of caoutchouc and gutta-percha, either alone, or in combination with other materials, the same to be applicable to articles of wearing apparel, bands, straps, and other similar useful purposes. Patent dated April 26, 1849.

_First._ Mr. Burke proposes to employ a compound of antimony instead of sulphur, for the purpose of rendering caoutchouc, gutta-percha, or their compounds permanently elastic, and unaffected by changes of temperature. The compound is prepared by mixing 1 part of crude antimony with 25 parts of crystallized carbonate of soda, or 20 parts of carbonate of potash, and 250 or 300 parts of water. The mixture is boiled from half an hour to three-quarters, and allowed to precipitate, when the supernatant liquid is run off. The precipitate is then dried and incorporated with the caoutchouc in a masticating machine in the proportion of from five to fifteen per cent. When bands or other articles are to be cut from blocks of caoutchouc, it is taken, while warm, from the masticating machine, and subjected to pressure for one or two days.

_Second._ It is also proposed to manufacture driving bands, by spreading the material dissolved in a suitable menstrum, with calender rollers, upon pieces of calico or other fabric, powdered with French chalk, to allow of the easy separation of the two, and to increase the rigidity and durability of gutta-percha driving bands, stripes of some fabric are to be affixed to the wearing parts, and both surfaces coated with the antimonized caoutchouc.

_Third._ To remove the shiny appearance of single texture garments, &c., Mr. Burke coats them with the antimonized caoutchouc, dissolved in some suitable menstrum, and mixed with ground silk or cotton, which is stated to have the effect of giving the article the appearance of cloth.

_Fourth._ Gutta percha soles and heels are proposed to be defended at the edges, where they are exposed to great wear and tear, with metal tips, shields, and guards.

CLAIMS.

_First._ The treating caoutchouc, gutta-percha, or their compounds, with the antimony compound.

_Second._ The mode of manufacturing driving bands.

_Third._ Coating water proof articles with antimonized caoutchouc, mixed with ground silk, cotton, or wool.

_Fourth._ The manufacture of gutta-percha soles and heels with metal tips, shields, and guards.

DESCRIPTION OF HANCOCK AND CO.’S PATENT GUTTA-PERCHA HEEL TIPS.

_From the London Mechanics’ Magazine, Vol. LI._

SIR:—We are reminded weekly by the advertisement in your Number, that gutta-percha “must be regarded as one of the blessings of a gracious Providence.” Doubtless this, as well as every other natural production, should be so regarded, although in the state in which it is left by Providence it would be of little use were it not for the additional blessings of ingenious-minded men, (as the Hancocks and others) by whose skill the crude gifts of Providence are manipulated and presented to our acceptance in a thousand beautiful and highly useful forms.

As weather-proof, and consequently _health-preserving soles_ for boots and shoes, gutta-percha most assuredly stands unrivalled. The application of this material to _heels_ has not hitherto been equally successful, from its being unequal to withstand the vast amount of wear and tear, to which this part of our understanding is subjected, one consequence of which is liability to spread, and become worn and ragged on its edges. For this defect, however, an efficient remedy has been provided in the compound heel tips, invented by Mr. B. Tyler, of Sheffield, and manufactured under Messrs. Hancock & Co.’s patent. The frame or border of this improved steel tip consists of a rim of cast iron or steel, furnished with tangs or projections. This frame is filled up with a tough compound of gutta-percha and cork, which encloses the tangs. The heel thus formed, requires no nailing to affix it to the boot or shoe, a coating of solution being sufficient for that purpose. Thus arranged, the metal and gutta-percha mutually aid and support each other; no spreading can take place, nor can the edges become worn or ragged. These tips never become loose, neither are they liable to become slippery. Having worn them for more than two years, I can with confidence assert them to be the best contrivance extant for the purpose. * * *

I am, Sir, yours &c. WILLIAM BADDELEY, _29 Alfred Street, Islington_.

EDWARD JOHN PAINE, Chancery Lane, London. For improvements in marine vessels, in apparatus for the preservation of human life, and moulding, joining and finishing hollow and solid figures, composed wholly or in part of a certain gum, or a combination of a certain gum; also for improvements in dissolving the aforesaid gums, and in apparatus or machinery to be used for the purposes above mentioned. Patent dated June 7, 1849.

* * * * *

A WATER PROOF VARNISH.—Mix together 1 lb. gutta-percha, 3 oz. gum opal, ½ lb. linseed oil, 8 oz. sugar of lead, 2 lbs. spirits of turpentine. Place the mixture in a tincture press, the cylinder of which is heated by a sand bath, and the produce is the varnish required.

A VARNISH WITH WHICH COLORS MAY BE MIXED, AND VERY SUITABLE FOR COATING ARTICLES IN GUTTA-PERCHA.—Take 100 lbs. gutta-percha, 18 lbs. 12 oz. gum opal, 50 lbs. linseed oil, 200 lbs. spirits of turpentine, and mix the whole together.

A VARNISH FOR UNPAINTED ARTICLES IN ROUGH WOOD.—Take 50 lbs. India-rubber, 100 lbs. gutta-percha, 30 lbs. gum opal, 70 lbs. gum damar, 150 lbs. linseed oil, 75 lbs. sugar of lead, 500 lbs. spirits of turpentine.

A VARNISH FOR ARTICLES OF METAL.—Take 100 lbs. gutta-percha, 20 lbs. gum opal, 75 lbs. linseed oil, 25 lbs. sugar of lead, 200 lbs. spirits of turpentine.

W. JOHNSON. Improvements in the treatment, preparation, or manufacture of sheet caoutchouc, and in the combination thereof with cloth and other fabrics. (A communication.) Dated October 3, 1856.

This relates to a mode of preparing sheets of caoutchouc, and combining them firmly with cloth and other fabrics, to produce goods for the manufacture of articles of various degrees of elasticity, and consists in preparing sheets of vulcanized caoutchouc, by desulphurizing their surfaces by first boiling the sheets in caustic alkali, and afterwards in salt pickle, to neutralize the alkali remaining on the sheet, and then washing the same. These sheets are then roughed on their surfaces, and the fabric to which they are to be applied is prepared by coating the surfaces thinly with a solution of caoutchouc dissolved in some solvent, and then thoroughly evaporating the solvent.

F. C. JEUNE. An improved manufacture of floor cloth. Dated May 26, 1856.

The patentee mixes in a masticating machine, India-rubber, (partly the waste of vulcanized rubber) and gutta percha, to produce a binding substance, and throws in ground cedar wood, or other vegetable dust, for increasing the bulk, and reducing the cost. When the mixing is effected, he adds fibrous substances in length, to impart toughness, and rolls the compound between rollers into sheets, which he submits to steam or hot air, to complete the adhesion of the particles.

C. GOODYEAR. An improvement in combining gutta-percha and asphalt or pitch. Dated August 30, 1856.

This consists in combining gutta-percha with asphalt or pitch, by the aid of hot water. They are, when desired, further combined with sulphur, with India-rubber, or other matters; and compounds are, when required, subjected to high temperature.

A. LORIMIER. An improvement in re-working vulcanized India-rubber. Dated October 20, 1856.

This consists in preparing the waste of vulcanized India-rubber by crushing the same between pressing rollers, then subjecting it to a considerable degree of heat, and whilst so heated causing it to be stirred, by which means the mass is progressively brought into a fluid state. It is then allowed to cool, but before becoming cold, a solvent of India-rubber is added, by which an India-rubber cement is produced.

GEORGE SIMPSON, Newington, Butts, chemist, and THOMAS FOSTER, Stratham, manufacturer. For improvement in manufacturing, or treating solvents of India-rubber, and of other gums or substances. Patent dated April 26, 1849.

_First._ Bisulphuret of carbon is placed in an iron still, the top of which opens into an earthen ware vessel containing pentuchloride of antimony, and a pipe leads from the top of this vessel, to the worm of an earthen-ware condensor. The still and first vessel are heated by steam jackets. The resulting product flows from the condensor to a reservoir, after which, it is rectified by lime and is then ready for use as a solvent. Before rectification, the India-rubber, gutta-percha, or other gum may be immersed in it, or exposed to its fumes and thereby rendered less liable to injury from the effects of cold or heat.

_Second._ Coal is purified and rendered applicable as a solvent of these gums by being subjected to a similar process, chloride of lime in solution being substituted for the pentuchloride of antimony.

_Claims._ 1st, The manufacture of chloride and bichloride of carbon, and its application as a solvent of India-rubber, gutta-percha, and other gums not soluble in water, and the mode of treating rubber, as described.

_Second._ The mode of treating coal oil with chloride of lime, for the purpose of obtaining a solvent of the before mentioned gums.

TO GUSTAVE EUGENE MICHEL GERARD, of Paris, in the Republic of France. For improvements in dissolving caoutchouc (India-rubber), and gutta-percha. [Sealed May 7, 1850.]

This invention consists in certain improved means of dissolving India-rubber and gutta-percha.

The patentee commences his specification by remarking that heretofore all solutions of India-rubber, whether clear or thick, have possessed great coherence and elasticity; the solvent, whatever it may have been, has always expanded the gum to a great extent; and as it is not until after this has taken place that the real act of dissolving the gum commences, a large quantity of the solvent is consequently required. * * *

The new process consists in mixing with the solvent (of whatever nature it may be) a certain quantity of alcohol, and macerating therein the India-rubber or gutta-percha, which will expand very little, and at the end of twenty-four hours, it will be in the state of paste, suitable for being moulded into any desired form. The patentee prefers to employ as a solvent, sulphuret of carbon, chloroform, sulphuric ether, naptha, essential oils of coal, or turpentine, and to add thereto from five to fifty per cent. of alcohol. The caoutchouc is mixed with the alcoholized solvents in all proportions, varying from equal parts to thirty parts of the latter, to one of the former, according to the thickness of the solution required, and after one or two days, the paste is submitted to the ordinary process of masticating, if the solution is made of equal parts, or when it is made of small quantities of the solvent; in other cases it is not necessary. The patentee adopts the same system when treating gutta-percha. He dissolves it in the alcoholized sulphuret of carbon, and dilutes it until it arrives at the consistence of thick syrup of sugar. In this state he permits it to remain three or four days, during which time, the impurities will be precipitated or rise to the surface; and then he draws off the gutta-percha in a state of complete purity.

It will be seen that the character of the invention is the mixture of alcohol with the solvent used for dissolving caoutchouc, and gutta-percha. As alcohol is the liquid which most quickly precipitates India-rubber from its solutions, the patentee avails himself of this property, by causing the alcohol, by means of a solvent, to enter into the interior parts of the India-rubber, or to detach all the adherent atoms which form the mass of the caoutchouc. By the addition of the alcohol, the particles are rendered less adherent among themselves, and are easily separated by pressure, retaining the form resulting from this pressure, and not returning to their ordinary form. On the solvent and the alcohol being evaporated, the caoutchouc will return to its original state. All liquids which possess the properties of alcohol may be mixed with the solvents. The principle of this invention is the causing matters which are not of a solvent nature, to be introduced into the body of the India-rubber by means of a solvent, such matters having the property to disunite the parts constituting the mass of India-rubber, and destroy the adherence of the particles, whether these matters are combined with the solvents, or introduced by themselves.

TO WILLIAM EDWARD NEWTON, of the Office of Patents, 66 Chancery Lane, London, England. For improvements applicable to Boots, Shoes and other coverings for, or appliances to the feet. [Sealed 6th of June, 1850.]

The first part of this invention consists in providing the under surface of India-rubber shoes, buskins, gaiters, boots, and over-shoes, with projecting metallic points, permanently secured in or to the soles, so as to render the same less liable to slip or slide, when used in walking over snow, ice, or other smooth or slippery surfaces.

In carrying out this improvement, the inventor procures short metallic points, in the form of headed rivets, in length very slightly exceeding the thickness of the sole, having a head of any convenient size. The diameter of the head is not material, but it should not be less than an ordinary rivet-head; and the size of the projecting portion should be, for light shoes, about 1/20 of an inch in diameter, which may be increased according to the size of the shoe,—care being taken not to render the shoe burdensome. Before the sole is applied to the shoe, these rivets or points are inserted through perforations in the sole, so that the heads shall rest upon the inner surface, and the points project through and beyond the outer surface, but so slightly that they can scarcely be felt in passing the hand over the surface. The sole thus prepared, is then applied in the usual manner, to the shoe. Another mode of providing the sole with such points, differs from the foregoing, in this respect only;—instead of using a number of headed rivets, the patentee takes a metallic plate, with projecting points, which may be cast for the purpose, so that when the points are inserted in the sole, the projecting points on the outer surface will be similar to those prepared with rivets as above described; while, on the inner surface, instead of presenting several heads, there will be one plate, which may be treated as one connecting head for all the rivets.

The third part of the invention relates to a method of making that kind of shoes known as clogs, and consists in making them of India-rubber, or the compounds thereof, and of what the inventor denominates India-rubber sponge, moulded of the desired form, with the upper part of the sole, which comes in contact with the sole of the shoe or boot, formed with a ring all around, and protuberances, so as to give the desired elevation with little weight.

The operator mixes sugar or resin with the India-rubber, prepared in the usual manner for vulcanizing, in the proportion of one-quarter of a pound of sugar or resin to each pound of India-rubber; and after the compound has been worked and treated in the usual manner, he forms the clog thereof, in a mould, and subjects it to the curing or vulcanizing process, by which it is rendered spongy and light. The mould is so formed as to make the sole thin, with a rim all round and protuberances within, for the boot or shoe to rest on, to give the foot the required elevation from the ground. The sole thus prepared, can be provided with a toe-piece and heel-strap, as described under the second part of the invention, or it may be provided with any other means of securing it to the foot.

The last part of the invention relates to a mode or modes of making India-rubber shoes or coverings for the feet pervious to perspiration, and yet impervious, under ordinary circumstances, to water or damp. This object may be effected by taking a quantity of India-rubber sponge and rolling it into thin sheets, which sheets may be made into boots, shoes, or coverings for the feet, and as they will be found to be covered with a great number of very fine holes, they will allow the perspiration to pass through, but will effectually keep out the wet.

It is preferred, however, to perforate the India-rubber by mechanical means, as a greater amount of regularity may be thereby attained, and the perforating process will be more under command. When the sheet rubber is made up into boots or coverings for the feet, it will be necessary either to leave those parts of the boot nearest to the sole, and most exposed to the wet, unperforated and impervious, or to cover those parts with an impervious material, leaving only the upper part pervious to perspiration. Under this head of the invention the claim is for making boots, shoes, and other coverings for the feet, pervious to the perspiration of the wearer, by making such articles of sheet rubber, previously perforated with minute holes.

TO ALFRED VINCENT NEWTON, of the Office of Patents, in Chancery Lane, London, England. For improvements in the preparation of materials for the production of a composition or compositions applicable to the manufacture of buttons, knife and razor handles, inkstands, door-knobs, and other articles, where hardness, strength and durability are required. (Sealed 4th of March, 1851.)[4]

Footnote 4:

This is one of the most important patents ever taken out, _being of great practical utility_.

This invention relates to the preparation and treatment of caoutchouc and gutta-percha, either alone or in combination, for the purpose of producing a new manufacture or composition, applicable to various uses where hardness, strength and durability are required. The composition designed to be produced, will possess some of the characteristics of horn, ivory, jet, and may, according to the color imparted to it, be employed in place thereof; or it may be used as a substitute for costly woods, and be applied to furniture in the form of veneer.

In treating caoutchouc (India-rubber) for this purpose, it is combined with sulphur,—the best proportion being about equal parts, by weight, of each ingredient. By combining sulphur in this proportion, with the caoutchouc, and subjecting the compound to the curing operation, (hereafter to be described) a hard substance will be produced, but a still better result will be obtained by the introduction of magnesia or lime, or of carbonate, or sulphate of magnesia, or carbonate or sulphate of lime, or calcined French chalk, or other magnesian earth, into the composition, in which case, the following proportions will be found highly advantageous, viz.; one pound of caoutchouc, half a pound of sulphur, and half a pound of magnesia, or lime, or carbonate or sulphate of magnesia, or carbonate or sulphate of lime, or calcined French chalk, or other magnesian earth. The proportions specified in both of these compounds, may be considerably varied without materially changing the result; but in no case is it desirable to use a much less quantity of sulphur than four ounces to every pound of caoutchouc. With either of these compounds just described, gum lac, or gum shellac, may be combined to great advantage,—say, in the proportion of from four to eight ounces of gum lac to every pound of caoutchouc. Rosin, oxides or salts of lead or zinc, of all colors, and other similar substances, both mineral and vegetable, may be added in small quantities, to either of the compounds, for the purpose of imparting a polish, or a color thereto, and for making the mixture work more easily; but no precise rule for these additions can be given; nor, indeed, is it necessary, as the taste and judgment of the operator will be his guide in this particular.

The compounds produced according to the above plans, are next treated in the manner to be presently described; but, as this process is equally applicable to the treatment of other compositions included in this invention, the patentee first explains of what these compositions consist. When using gutta-percha in lieu of India-rubber, the inventor takes certain proportions of gutta-percha, sulphur and magnesia, or lime, or a carbonate, or a sulphate of magnesia or lime, or calcined French chalk, or other magnesian earth, and mixes them in a convenient manner.

The portions preferred are the following, viz.—one pound of gutta-percha, six ounces of sulphur, and from six to eight ounces of either magnesia or lime, or a carbonate, or a sulphate of magnesia or of lime, or calcined French chalk, or other magnesian earth. Instead of using the specified proportion of the magnesia or lime, or of the carbonate or sulphate of magnesia or lime, or of calcine French chalk or other magnesian earth, the same proportion of any two or more of these substances combined, may be employed, care being taken that the quantity of this third ingredient in the composition does not vary from the proportion of six or eight ounces. These proportions may, however, be slightly varied, without materially changing the result.

To the composition above specified, a fourth ingredient may be added, viz., gum shellac, by which a still better article will be produced—the body thus obtained being stronger and more easily worked. The quantity of shellac, in such case, should be about four ounces to every pound of gutta-percha.

Resin, oxide or salts of lead or zinc, of all colors, and other like substances, both mineral and vegetable may be added, in small quantities, to either of the above compositions, for the purposes before stated with respect to the India-rubber composition.

The compounds described may be mixed by a masticating machine or other means, until the several ingredients are thoroughly incorporated. The mineral ingredients should be finely divided, and good results are obtained by reducing them before mixture, to an impalpable powder.

When rolled or moulded, the compounds are then to be “cured.” This is effected by exposing the compound to a high degree of artificial heat, using for this purpose either steam, hot water, or hot air. The degree of heat to which this compound is to be exposed, and the duration of its exposure, will depend somewhat upon the size and thickness of the article; but in ordinary cases the heat should be raised to about 260° or 270°, Fah., and the compound exposed to such heat for about four hours; as a general rule, however, it may be stated that the heat should range from 250° to 300°, Fah., and the time of exposure from two to six hours. The compounds or compositions by undergoing this heating or curing operation, will become of a hard, stiff character, in many respects resembling tortoise-shell, horn, bone, ivory, and jet. In the compounds described as compositions of caoutchouc, considerable proportions of gutta-percha may be substituted for caoutchouc (rubber) without injury; and, in the compounds described as compositions of gutta-percha, considerable proportions of caoutchouc may also be substituted for gutta-percha without injury * * * *

The compositions, when hardened, may be worked like wood or bone; but, in some instances, it is proposed to mould, shape, or otherwise treat the compositions so as to render them better suited to the purpose for which they are intended, prior to submitting them to the hardening process. Thus when it is desired to use these new compositions in combination with common flexible vulcanized caoutchouc, the parts intended to be hardened may be united to a connecting band, or connecting pieces of flexible vulcanized caoutchouc, by cementing or pressing together the surfaces required to be joined, before the heating or curing process has been effected; by which means, during the process of curing, the abutting elastic and non-elastic surfaces will become firmly united together.

* * * * *

Another mode of applying the composition consists in uniting them in their plastic or green state with iron, or other metals or rigid substances, which will bear a high degree of artificial heat without alteration or damage, roughened in such portions of its surface as are intended to be brought into contact with the compound of caoutchouc or gutta-percha, and the compound is then applied to the roughened surface of the article. When it is desired that the compound of caoutchouc or gutta-percha shall serve as a covering to the iron or other substance, a thin sheet of the compound (sometimes one thirty-second part of an inch in thickness or less) is pressed with great care, upon the iron or other substance, so as to expel all air from between the adjoining surfaces, and to cause the most perfect union and adhesion, as the coated article is bound with strips or ribbons of cloth, or other suitable material, whereby the compound is kept in close contact with the article during the process of hardening. The combined materials thus treated, will be found to possess the qualities desired—the iron or other substance giving strength and the compound giving a hard and durable surface. In this way may be produced many articles used in and about harnesses or carriages, such as saddle trees, buckles, terrels, bits, stirrups, martingale rings, dasher-irons, and articles intended to be used as furniture, either in whole or in part, and a great variety of other useful objects.

A. FORD. _Preparing and dissolving in naptha or oil of turpentine, vulcanized India-rubber for the purpose of water-proofing, and for all or any of the other purposes for which the same not so prepared and dissolved is now applicable, and expressly for the coating of iron ships’ bottoms._ Dated June 27th, 1856.

The inventor first cuts the vulcanized India-rubber into small pieces, and places it in a boiler, having within it an agitator or stirrer, kept in constant motion during the process. The only openings into this boiler are a main hole with a screw top; a safety-valve which comes into action only when the pressure on the inner surface of the boiler exceeds 25 lbs. to the square inch, and the opening occasioned by the passage of the stem of the agitator, which passes in at the summit. He then applies heat in such a manner as that three-fourths of the outer surface of the boiler shall be at once exposed to its influence, and at a temperature of never more than 300° Fah.; and he continues the same until the India-rubber shall be reduced to the consistence of dough, when he takes it out, and having mixed with it a sufficient portion of French chalk in powder to remove its adhesiveness, passes it a few times through metal rollers, after which it is capable of being dissolved in naptha or oil of turpentine in the manner of ordinary India-rubber. The _rationale_ of the process is, that by means of the heat applied to the boiler, he decomposes a small portion of the vulcanized India-rubber, whereby a gas is generated which, filling the interior of the boiler, acts upon the remaining portion, and softens it. The not allowing the gas to escape is, therefore, a very important feature.

N. S. DODGE. _Improvements in treating vulcanized India-rubber or gutta-percha._ Dated January 18th, 1856.

This invention relates to a mode of treating vulcanized India-rubber, for rendering scraps or waste pieces, such as old shoes, &c., fit to be re-used without requiring to be vulcanized. The material is reduced into small pieces, and placed in a vessel hermetically closed, and to it is added pure alcohol and bisulphate of carbon (¼lb. of the former, and 10 lbs. of the latter, to 100 lbs. of the material,) the alcohol and the bisulphate being previously mixed together, and then poured over the material to be treated. The vessel is then closed air-tight for two hours, at the end of which the process is complete.

W. A. TURNER. _Improvements in the manufacture of elastic tubing._ Dated February 29th, 1856.

The invention relates to tubing made of India-rubber and gutta-percha, either separately or in combination, and is designed for rendering such tubing capable of withstanding a pressure of from 50 to 100 lbs. on every square inch of surface. The novelty consists in combining with the aforesaid material a rigid substance, such as a helix or a series of rings of metal or other material.