The Chemistry of Hat Manufacturing.

by Watson Smith.

PREFACE

The subject-matter in this little book is the substance of a series of Lectures delivered before the Hat Manufacturers" a.s.sociation in the years 1887 and 1888.

About this period, owing to the increasing difficulties of compet.i.tion with the products of the German Hat Manufacturers, a deputation of Hat Manufacturers in and around Manchester consulted Sir Henry E. Roscoe, F.R.S., then the Professor of Chemistry in the Owens College, Manchester, and he advised the formation of an a.s.sociation, and the appointment of a Lecturer, who was to make a practical investigation of the art of Hat Manufacturing, and then to deliver a series of lectures on the applications of science to this industry. Sir Henry Roscoe recommended the writer, then the Lecturer on Chemical Technology in the Owens College, as lecturer, and he was accordingly appointed.

The lectures were delivered with copious experimental ill.u.s.trations through two sessions, and during the course a patent by one of the younger members became due, which proved to contain the solution of the chief difficulty of the British felt-hat manufacturer (see pages 66-68).

This remarkable coincidence served to give especial stress to the wisdom of the counsel of Sir Henry Roscoe, whose response to the appeal of the members of the deputation of 1887 was at once to point them to scientific light and training as their only resource. In a letter recently received from Sir Henry (1906), he writes: "I agree with you that this is a good instance of the _direct money value_ of scientific training, and in these days of "protection" and similar subterfuges, it is not amiss to emphasise the fact."

It is thus gratifying to the writer to think that the lectures have had some influence on the remarkable progress which the British Hat Industry has made in the twenty years that have elapsed since their delivery.

These lectures were in part printed and published in the _Hatters"

Gazette_, and in part in newspapers of Manchester and Stockport, and they have here been compiled and edited, and the necessary ill.u.s.trations added, etc., by Mr. Albert Shonk, to whom I would express my best thanks.

WATSON SMITH.

LONDON, _April_ 1906.

LECTURE I

TEXTILE FIBRES, PRINc.i.p.aLLY WOOL, FUR, AND HAIR

_Vegetable Fibres._--Textile fibres may be broadly distinguished as vegetable and animal fibres. It is absolutely necessary, in order to obtain a useful knowledge of the peculiarities and properties of animal fibres generally, or even specially, that we should be, at least to some extent, familiar with those of the vegetable fibres. I shall therefore have, in the first place, something to tell you of certain princ.i.p.al vegetable fibres before we commence the more special study of the animal fibres most interesting to you as hat manufacturers, namely, wool, fur, and hair. What cotton is as a vegetable product I shall not in detail describe, but I will refer you to the interesting and complete work of Dr. Bowman, _On the Structure of the Cotton Fibre_. Suffice it to say that in certain plants and trees the seeds or fruit are surrounded, in the pods in which they develop, with a downy substance, and that the cotton shrub belongs to this cla.s.s of plants. A fibre picked out from the ma.s.s of the downy substance referred to, and examined under the microscope, is found to be a spirally twisted band; or better, an irregular, more or less flattened and twisted tube (see Fig. 1). We know it is a tube, because on taking a thin, narrow slice across a fibre and examining the slice under the microscope, we can see the hole or perforation up the centre, forming the axis of the tube (see Fig. 2).

Mr. H. de Mosenthal, in an extremely interesting and valuable paper (see _J.S.C.I._,[1] 1904, vol. xxiii. p. 292), has recently shown that the cuticle of the cotton fibre is extremely porous, having, in addition to pores, what appear to be minute stomata, the latter being frequently arranged in oblique rows, as if they led into oblique lateral channels.

A cotton fibre varies from 25 to 6 centimetres in length, and in breadth from 0017 to 005 millimetre. The characteristics mentioned make it very easy to distinguish cotton from other vegetable or animal fibres. For example, another vegetable fibre is flax, or linen, and this has a very different appearance under the microscope (_see_ Fig. 3). It has a bamboo-like, or jointed appearance; its tubes are not flattened, nor are they twisted. Flax belongs to a cla.s.s called the bast fibres, a name given to certain fibres obtained from the inner bark of different plants. Jute also is a bast fibre. The finer qualities of it look like flax, but, as we shall see, it is not chemically identical with cotton, as linen or flax is. Another vegetable fibre, termed "cotton-silk," from its beautiful, l.u.s.trous, silky appearance, has excited some attention, because it grows freely in the German colony called the Camaroons, and also on the Gold Coast. This fibre, under the microscope, differs entirely in appearance from both cotton and flax fibres. Its fibres resemble straight and thin, smooth, transparent, almost gla.s.sy tubes, with large axial bores; in fact, if wetted in water you can see the water and air bubbles in the tubes under the microscope. A more detailed account of "cotton-silk" appears in a paper read by me before the Society of Chemical Industry in 1886 (see _J.S.C.I._, 1886, vol. v. p.

642). Now the substance of the cotton, linen or flax, as well as that of the cotton-silk fibres, is termed, chemically, cellulose. Raw cotton consists of cellulose with about 5 per cent. of impurities. This cellulose is a chemical compound of carbon, hydrogen, and oxygen, and, according to the relative proportions of these const.i.tuents, it has had the chemical formula C_{6}H_{10}O_{5} a.s.signed to it. Each letter stands for an atom of each const.i.tuent named, and the numerals tell us the number of the const.i.tuent atoms in the whole compound atom of cellulose. This cellulose is closely allied in composition to starch, dextrin, and a form of sugar called glucose. It is possible to convert cotton rags into this form of sugar--glucose--by treating first with strong vitriol or sulphuric acid, and then boiling with dilute acid for a long time. Before we leave these vegetable or cellulose fibres, I will give you a means of testing them, so as to enable you to distinguish them broadly from the animal fibres, amongst which are silk, wool, fur, and hair. A good general test to distinguish a vegetable and an animal fibre is the following, which is known as Molisch"s test: To a very small quant.i.ty, about 001 gram, of the well-washed cotton fibre, 1 c.c.

of water is added, then two to three drops of a 15 to 20 per cent.

solution of alpha-naphthol in alcohol, and finally an excess of concentrated sulphuric acid; on agitating, a deep violet colour is developed. By using thymol in place of the alpha-naphthol, a red or scarlet colour is produced. If the fibre were one of an animal nature, merely a yellow or greenish-yellow coloured solution would result. I told you, however, that jute is not chemically identical with cotton and linen. The substance of its fibre has been termed "bastose"

by Cross and Bevan, who have investigated it. It is not identical with ordinary cellulose, for if we take a little of the jute, soak it in dilute acid, then in chloride of lime or hypochlorite of soda, and finally pa.s.s it through a bath of sulphite of soda, a beautiful crimson colour develops upon it, not developed in the case of cellulose (cotton, linen, etc.). It is certain that it is a kind of cellulose, but still not identical with true cellulose. All animal fibres, when burnt, emit a peculiar empyreumatic odour resembling that from burnt feathers, an odour which no vegetable fibre under like circ.u.mstances emits. Hence a good test is to burn a piece of the fibre in a lamp flame, and notice the odour. All vegetable fibres are easily tendered, or rendered rotten, by the action of even dilute mineral acids; with the additional action of steam, the effect is much more rapid, as also if the fibre is allowed to dry with the acid upon or in it. Animal fibres are not nearly so sensitive under these conditions. But whereas caustic alkalis have not much effect on vegetable fibres, if kept out of contact with the air, the animal fibres are very quickly attacked. Superheated steam alone has but little effect on cotton or vegetable fibres, but it would fuse or melt wool. Based on these differences, methods have been devised and patented for treating mixed woollen and cotton tissues--(1) with hydrochloric acid gas, or moistening with dilute hydrochloric acid and steaming, to remove all the cotton fibre; or (2) with a jet of superheated steam, under a pressure of 5 atmospheres (75 lb. per square inch), when the woollen fibre is simply melted out of the tissue, and sinks to the bottom of the vessel, a vegetable tissue remaining (Heddebault). If we write on paper with dilute sulphuric acid, and dry and then heat the place written upon, the cellulose is destroyed and charred, and we get black writing produced. The principle involved is the same as in the separation of cotton from mixed woollen and cotton goods by means of sulphuric acid or vitriol. The fabric containing cotton, or let us say cellulose particles, is treated with dilute vitriol, pressed or squeezed, and then roughly dried. That cellulose then becomes mere dust, and is simply beaten out of the intact woollen texture. The cellulose is, in a pure state, a white powder, of specific gravity 15, _i.e._ one and a half times as heavy as water, and is quite insoluble in such solvents as water, alcohol, ether; but it does dissolve in a solution of hydrated oxide of copper in ammonia. On adding acids to the cupric-ammonium solution, the cellulose is reprecipitated in the form of a gelatinous ma.s.s. Cotton and linen are scarcely dissolved at all by a solution of basic zinc chloride.

[Footnote 1: _J.S.C.I. = Journal of the Society of Chemical Industry._]

[Ill.u.s.tration: FIG. 1.]

[Ill.u.s.tration: FIG. 2.]

[Ill.u.s.tration: FIG. 3.]

[Ill.u.s.tration: FIG. 4.]

_Silk._--We now pa.s.s on to the animal fibres, and of these we must first consider silk. This is one of the most perfect substances for use in the textile arts. A silk fibre may be considered as a kind of rod of solidified flexible gum, secreted in and exuded from glands placed on the side of the body of the silk-worm. In Fig. 4 are shown the forms of the silk fibre, in which there are no central cavities or axial bores as in cotton and flax, and no signs of any cellular structure or external markings, but a comparatively smooth, gla.s.sy surface. There is, however, a longitudinal groove of more or less depth. The fibre is semi-transparent, the beautiful pearly l.u.s.tre being due to the smoothness of the outer layer and its reflection of the light. In the silk fibre there are two distinct parts: first, the central portion, or, as we may regard it, the true fibre, chemically termed _fibron_; and secondly, an envelope composed of a substance or substances, chemically termed _sericin_, and often "silk-glue" or "silk-gum." Both the latter and _fibron_ are composed of carbon, hydrogen, nitrogen, and oxygen.

Here there is thus one element more than in the vegetable fibres previously referred to, namely, nitrogen; and this nitrogen is contained in all the animal fibres. The outer envelope of silk-glue or sericin can be dissolved off the inner fibron fibre by means of hot water, or warm water with a little soap. Warm dilute (that is, weak) acids, such as sulphuric acid, etc., also dissolve this silk-glue, and can be used like soap solutions for ungumming silk. Dilute nitric acid only slightly attacks silk, and colours it yellow; it would not so colour vegetable fibres, and this forms a good test to distinguish silk from a vegetable fibre. Cold strong acetic acid, so-called glacial acetic acid, removes the yellowish colouring matter from raw silk without dissolving the sericin or silk-gum. By heating under pressure with acetic acid, however, silk is completely dissolved. Silk is also dissolved by strong sulphuric acid, forming a brown thick liquid. If we add water to this thick liquid, a clear solution is obtained, and then on adding tannic acid the fibron is precipitated. Strong caustic potash or soda dissolves silk; more easily if warm. Dilute caustic alkalis, if sufficiently dilute, will dissolve off the sericin and leave the inner fibre of fibron; but they are not so good for ungumming silk as soap solutions are, as the fibre after treatment with them is deficient in whiteness and brilliancy. Silk dissolves completely in hot basic zinc chloride solution, and also in an alkaline solution of copper and glycerin, which solutions do not dissolve vegetable fibres or wool.

Chlorine and bleaching-powder solutions soon attack and destroy silk, and so another and milder agent, namely, sulphurous acid, is used to bleach this fibre. Silk is easily dyed by the aniline and coal-tar colours, and with beautiful effect, but it has little attraction for the mineral colours.

_Wool_.--Next to silk as an animal fibre we come to wool and different varieties of fur and hair covering certain cla.s.ses of animals, such as sheep, goats, rabbits, and hares. Generally, and without going at all deeply into the subject, we may say that wool differs from fur and hair, of which we may regard it as a variety, by being usually more elastic, flexible, and curly, and because it possesses certain features of surface structure which confer upon it the property of being more easily matted together than fur and hair are. We must first shortly consider the manner of growth of hair without spending too much time on this part of the subject. The accompanying figure (see Fig. 5) shows a section of the skin with a hair or wool fibre rooted in it. Here we may see that the ground work, if we may so term it, is four-fold in structure.

Proceeding downwards, we have--(first) the outer skin, scarf-skin or cuticle; (second) a second layer or skin called the _rete mucosum_, forming the epidermis; (third) papillary layer; (fourth) the corium layer, forming the dermis. The peculiar, globular, cellular ma.s.ses below in the corium are called adipose cells, and these throw off perspiration or moisture, which is carried away to the surface by the glands shown (called sudoriparous glands), which, as is seen, pa.s.s independently off to the surface. Other glands terminate under the skin in the hair follicles, which follicles or hair sockets contain or enclose the hair roots. These glands terminating in the hair follicles secrete an oily substance, which bathes and lubricates as well as nourishes the hair.

With respect to the origin of the hair or wool fibre, this is formed inside the follicle by the exuding therefrom of a plastic liquid or lymph; this latter gradually becomes granular, and is then formed into cells, which, as the growth proceeds, are elongated into fibres, which form the central portion of the hair. Just as with the trunk of a tree, we have an outer dense portion, the bark, an inner less dense and more cellular layer, and an inmost portion which is most cellular and porous; so with a hair, the central portion is loose and porous, the outer more and more dense. On glancing at the figure (Fig. 6) of the longitudinal section of a human hair, we see first the outer portion, like the bark of a tree, consisting of a dense sheath of flattened scales, then comes an inner lining of closely-packed fibrous cells, and frequently an inner well-marked central bundle of larger and rounder cells, forming a medullary axis. The transverse section (Fig. 7) shows this exceedingly well. The end of a hair is generally pointed, sometimes filamentous. The lower extremity is larger than the shaft, and terminates in a conical bulb, or ma.s.s of cells, which forms the root of the hair. In the next figure (Fig. 8) we are supposed to have separated these cells, and above, (a), we see some of the cells from the central pith or medulla, and fat globules; between, (b), some of the intermediate elongated or angular cells; and below, (c), two flattened, compressed, structureless, and h.o.r.n.y scales from the outer portion of the hair. Now these latter flattened scales are of great importance.

Their character and mode of connection with the stratum, or cortical substance, below, not only make all the difference between wool and hair, but also determine the extent and degree of that peculiar property of interlocking of the hairs known as felting. Let us now again look at a human hair. The light was reflected from this hair as it lay under the microscope, and now we see the reason of the saw-like edge in the longitudinal section, for just as the tiles lie on the roof of a house, or the scales on the back of a fish, so the whole surface of the hair is externally coated with a firmly adhering layer of flat overlying scales, with not very even upper edges, as you see. The upper or free edges of these scales are all directed towards the end of the hair, and away from the root. But when you look at a hair in its natural state you cannot see these scales, so flat do they lie on the hair-shaft. What you see are only irregular transverse lines across it. Now I come to a matter of great importance, as will later on appear in connection with means for promoting felting properties. If a hair such as described, with the scales lying flat on the shaft, be treated with certain substances or reagents which act upon and dissolve, or decompose or disintegrate its parts, then the free edges of these scales rise up, they "set their backs up," so to say. They, in fact, stand off like the scales of a fir-cone, and at length act like the fir-cone in ripening, at last becoming entirely loose. As regards wool and fur, these scales are of the utmost importance, for very marked differences exist even in the wool of a single sheep, or the fur of a single hare. It is the duty of the wool-sorter to distinguish and separate the various qualities in each fleece, and of the furrier to do the same in the case of each fur.

In short, upon the nature and arrangement and conformation of the scales on the hair-shafts, especially as regards those free upper edges, depends the distinction of the value of many cla.s.ses of wool and fur.

These scales vary both as to nature and arrangement in the case of the hairs of different animals, so that by the aid of the microscope we have often a means of determining from what kind of animal the hair has been derived. It is on the nature of this outside scaly covering of the shaft, and in the manner of attachment of these scaly plates, that the true distinction between wool and hair rests. The princ.i.p.al epidermal characteristic of a true wool is the capacity of its fibres to felt or mat together. This arises from the greater looseness of the scaly covering of the hair, so that when opposing hairs come into contact, the scales interlock (see Fig. 9), and thus the fibres are held together.

Just as with hair, the scales of which have their free edges pointing upwards away from the root, and towards the extremity of the hair, so with wool. When the wool is on the back of the sheep, the scales of the woolly hair all point in the same direction, so that while maintained in that att.i.tude the individual hairs slide over one another, and do not tend to felt or mat; if they did, woe betide the animal. The fact of the peculiar serrated, scaly structure of hair and wool is easily proved by working a hair between the fingers. If, for instance, a human hair be placed between finger and thumb, and gently rubbed by the alternate motion of finger and thumb together, it will then invariably move in the direction of the root, quite independently of the will of the person performing the test. A glance at the form of the typical wool fibres shown (see Fig. 10), will show the considerable difference between a wool and a hair fibre. You will observe that the scales of the wool fibre are rather pointed than rounded at their free edges, and that at intervals we have a kind of composite and jagged-edged funnels, fitting into each other, and thus making up the covering of the cylindrical portion of the fibre. The sharpened, jagged edges enable these scales more easily to get under the opposing scales, and to penetrate inwards and downwards according to the pressure exerted. The free edges of the scales of wool are much longer and deeper than in the case of hair. In hair the overlapping scales are attached to the under layer up to the edges of those scales, and at this extremity can only be detached by the use of certain reagents. But this is not so with wool, for here the ends of the scales are, for nearly two-thirds of their length, free, and are, moreover, partially turned outwards. One of the fibres shown in Fig. 10 is that of the merino sheep, and is one of the most valuable and beautiful wools grown. There you have the type of a fibre best suited for textile purposes, and the more closely different hairs approach this, the more suitable and valuable they become for those purposes, and _vice versa_. With regard to the curly structure of wool, which increases the matting tendency, though the true cause of this curl is not known, there appears to be a close relationship between the tendency to curl, the fineness of the fibre, and the number of scales per linear inch upon the surface. With regard to hair and fur, I have already shown that serrated fibres are not specially peculiar to sheep, but are much more widely diffused. Most of the higher members of the mammalia family possess a hairy covering of some sort, and in by far the larger number is found a tendency to produce an undergrowth of fine woolly fibre, especially in the winter time. The differences of human hair and hairs generally, from the higher to the lower forms of mammalia, consist only in variations of size and arrangement as regards the cells composing the different parts of the fibre, as well as in a greater or less development of the scales on the covering or external hair surface.

Thus, under the microscope, the wool and hairs of various animals, as also even hairs from different parts of the same animal, show a great variety of structure, development, and appearance.

[Ill.u.s.tration: FIG. 5.]

[Ill.u.s.tration: FIG. 6.]

[Ill.u.s.tration: FIG. 7.]

[Ill.u.s.tration: FIG. 8.]

[Ill.u.s.tration: FIG. 9.]

[Ill.u.s.tration:

Finest merino wool fibre.

Typical wool fibre.

Fibre of wool from Chinese sheep.

FIG. 10.]

[Ill.u.s.tration: FIG. 11.]

[Ill.u.s.tration: FIG. 12.]

We have already observed that hair, if needed for felting, is all the better--provided, of course, no injury is done to the fibre itself--for some treatment, by which the scales otherwise lying flatter on the hair-shafts than in the case of the hairs of wool, are made to stand up somewhat, extending outwards their free edges. This brings me to the consideration of a practice pursued by furriers for this purpose, and known as the _secretage_ or "carrotting" process; it consists in a treatment with a solution of mercuric nitrate in nitric acid, in order to improve the felting qualities of the fur. This acid mixture is brushed on to the fur, which is cut from the skin by a suitable sharp cutting or shearing machine. A Manchester furrier, who gave me specimens of some fur untreated by the process, and also some of the same fur that had been treated, informed me that others of his line of business use more mercury than he does, _i.e._ leave less free nitric acid in their mixture; but he prefers his own method, and thinks it answers best for the promotion of felting. The treated fur he gave me was turned yellow with the nitric acid, in parts brown, and here and there the hairs were slightly matted with the acid. In my opinion the fur must suffer from such unequal treatment with such strong acid, and in the final process of finishing I should not be surprised if difficulty were found in getting a high degree of l.u.s.tre and finish upon hairs thus roughened or partially disintegrated. Figs. 11 and 12 respectively ill.u.s.trate fur fibres from different parts of the same hare before and after the treatment. In examining one of these fibres from the side of a hare, you see what the cause of this roughness is, and what is also the cause of the difficulty in giving a polish or finish. The free edges are partially disintegrated, etched as it were, besides being caused to stand out. A weaker acid ought to be used, or more mercury and less acid. As we shall afterwards see, another dangerous agent, if not carefully used, is bichrome (bichromate of pota.s.sium), which is also liable to roughen and injure the fibre, and thus interfere with the final production of a good finish.

LECTURE II

TEXTILE FIBRES, PRINc.i.p.aLLY WOOL, FUR, AND HAIR--_Continued_

With regard to the preparation of fur by acid mixtures for felting, mentioned in the last lecture, I will tell you what I think I should recommend. In all wool and fur there is a certain amount of grease, and this may vary in different parts of the material. Where there is most, however, the acid, nitric acid, or nitric acid solution of nitrate of mercury, will wet, and so act on the fur, least. But the action ought to be uniform, and I feel sure it cannot be until the grease is removed. I should therefore first wash the felts on the fur side with a weak alkaline solution, one of carbonate of soda, free from any caustic, to remove all grease, then with water to remove alkali; and my belief is that a weaker and less acid solution of nitric acid and nitrate of mercury, and a smaller quant.i.ty of it, would then do the work required, and do it more uniformly.

A question frequently asked is: "Why will dead wool not felt?" Answer: If the animal become weak and diseased, the wool suffers degradation; also, with improvement in health follows _pari pa.s.su_, improvement in the wool structure, which means increase both in number and vigour of the scales on the wool fibres, increase of the serrated ends of these, and of their regularity. In weakness and disease the number of scales in a given hair-shaft diminishes, and these become finer and less p.r.o.nounced. The fibres themselves also become attenuated. Hence when disease becomes death, we have considerably degraded fibres. This is seen clearly in the subjoined figures (see Fig. 13), which are of wool fibres from animals that have died of disease. The fibres are attenuated and irregular, the scale markings and edges have almost disappeared in some places, and are generally scanty and meagre in development. It is no wonder that such "dead wool" will be badly adapted for felting. "Dead wool" is nearly as bad as "kempy" wool, in which malformation of fibre has occurred. In such "kemps," as Dr. Bowman has shown, scales have disappeared, and the fibre has become, in part or whole, a dense, non-cellular structure, resisting dye-penetration and felting (see Fig.

14).