So far everything in the treatment of the wool has been perfectly favourable for the subsequent operations of the felt-hat dyer, but now I come to a process which I consider I should be perfectly unwarranted in passing over before proceeding to the dyeing processes. In fact, were it not for this "proofing process" (see Lecture VII.) the dyeing of felt hats would be as simple and easy of attainment as the ordinary dyeing of whole-wool fabrics. Instead of this, however, I consider the hat manufacturer, as regards his dyeing processes as applied to the stiffer classes of felt hats, has difficulties to contend with fully comparable with those which present themselves to the dyer of mixed cotton and woollen or Bradford goods. You have heard that the purpose of the wool-scourer is to remove the dirt, grease, and so-called yolk, filling the pores and varnishing the fibres. Now the effect of the work of the felt or felt-hat proofer is to undo nearly all this for the sake of rendering the felt waterproof and stiff. The material used, also, is even more impervious and resisting to the action of aqueous solutions of dyes and mordants than the raw wool would be. In short, it is impossible to mordant and to dye shellac by any process that will dye wool. To give you an idea of what it is necessary to do in order to colour or dye shellac, take the case of coloured sealing-wax, which is mainly composed of shellac, four parts, and Venice turpentine, one part. To make red sealing-wax this mixture is melted, and three parts of vermilion, an insoluble metallic pigment, are stirred in. If black sealing-wax is required, lamp-black or ivory-black is stirred in. The fused material is then cast in moulds, from which the sticks are removed on cooling. That is how shellac may be coloured as sealing-wax, but it is a totally different method from that by which wool is dyed. The difficulty then is this—in proofing, your hat-forms are rendered impervious to the dye solutions of your dye-baths, all except a thin superficial layer, which then has to be rubbed down, polished, and finished. Thus in a short time, since the bulk of that superficially dyed wool or fur on the top of every hat is but small, and has been much reduced by polishing and rubbing, you soon hear of an appearance of bareness—I was going to say threadbareness—making itself manifest. This is simply because the colour or dye only penetrates a very little way down into the substance of the felt, until, in fact, it meets the proofing, which, being as it ought to be, a waterproofing, cannot be dyed. It cannot be dyed either by English or German methods; neither logwood black nor coal-tar blacks can make any really good impression on it. Cases have often been described to me illustrating the difficulty in preventing hats which have been dyed black with logwood, and which are at first a handsome deep black, becoming rather too soon of a rusty or brownish shade. Now my belief is that two causes may be found for this deterioration. One is the unscientific method adopted in many works of using the same bath practically for about a month together without complete renewal. During this time a large quantity of a muddy precipitate accumulates, rich in hydrated oxide of iron or basic iron salts of an insoluble kind. This mud amounts to no less than 25 per cent. of the weight of the copperas used. From time to time carbonate of ammonia is added to the bath, as it is said to throw up "dirt." The stuff or "dirt," chiefly an ochre-like mass stained black with the dye, and rich in iron and carbonate of iron, is skimmed off, and fresh verdigris and copperas added with another lot of hat-forms. No doubt on adding fresh copperas further precipitation of iron will take place, and so this ochre-like precipitate will accumulate, and will eventually come upon the hats like a kind of thin black mud. Now the effect of this will be that the dyestuff, partly in the fibre as a proper dye, and not a little on the fibre as if "smudged" on or painted on, will, on exposure to the weather, moisture, air, and so on, gradually oxidise, the great preponderance of iron on the fibre changing to a kind of iron-rust, corroding the fibres in the process, and thus at once accounting for the change to the ugly brownish shade, and to the rubbing off and rapid wearing away of the already too thin superficial coating of dyed felt fibre. In the final spells of dyeing in the dye-beck already referred to, tolerably thick with black precipitate or mud, the application of black to the hat-forms begins, I fear, to assume at length a too close analogy to another blacking process closely associated with a pair of brushes and the time-honoured name of Day & Martin. With that logwood black fibre, anyone could argue as to a considerable proportion of the dye rubbing, wearing, or washing off. Thus, then, we have the second cause of the deterioration of the black, for the colour could not go into the fibre, and so it was chiefly laid or plastered on. You can also see that a logwood black hat dyer may well make the boast, and with considerable appearance of truth, that for the purposes of the English hat manufacturers, logwood black dyeing is the most appropriate, i.e. for the dyeing of highly proofed and stiff goods, but as to the permanent character of the black colour on those stiff hats, there you have quite another question. I firmly believe that in order to get the best results either with logwood black or "aniline blacks," it is absolutely necessary to have in possession a more scientific and manageable process of proofing. Such a process is that invented by F.W. Cheetham (see Lecture VII. p. 66).
In the dyeing of wool and felt with coal-tar colours, it is in many cases sufficient to add the solution of the colouring matters to the cold or tepid water of the dye-bath, and, after introducing the woollen material, to raise the temperature of the bath. The bath is generally heated to the boiling-point, and kept there for some time. A large number of these coal-tar colours show a tendency of going so rapidly and greedily on to the fibre that it is necessary to find means to restrain them. This is done by adding a certain amount of Glauber's salts (sulphate of soda), in the solution of which coal-tar colours are not so soluble as in water alone, and so go more slowly, deliberately, and thus evenly upon the fibre. It is usually also best to dye in a bath slightly acid with sulphuric acid, or to add some bisulphate of soda. There is another point that needs good heed taking to, namely, in using different coal-tar colours to produce some mixed effect, or give some special shade, the colours to be so mixed must possess compatibility under like circumstances. For example, if you want a violet of a very blue shade, and you take Methyl Violet and dissolve it in water and then add Aniline Blue also in solution, you find that precipitation of the colour takes place in flocks. A colouring matter which requires, as some do, to be applied in an acid bath, ought not to be applied simultaneously with one that dyes best in a neutral bath. Numerous descriptions of methods of using coal-tar dyestuffs in hat-dyeing are available in different volumes of the Journal of the Society of Chemical Industry, and also tables for the detection of such dyestuffs on the fibre.
Now I will mention a process for dyeing felt a deep dead black with a coal-tar black dye which alone would not give a deep pure black, but one with a bluish-purple shade. To neutralise this purple effect, a small quantity of a yellow dyestuff and a trifle of indigotin are added. A deep black is thus produced, faster to light than logwood black it is stated, and one that goes on the fibre with the greatest ease. But I have referred to the use of small quantities of differently coloured dyes for the purpose of neutralising or destroying certain shades in the predominating colour. Now I am conscious that this matter is one that is wrapped in complete mystery, and far from the true ken of many of our dyers; but the rational treatment of such questions possesses such vast advantages, and pre-supposes a certain knowledge of the theory of colour, of application and advantage so equally important, that I am persuaded I should not close this course wisely without saying a few words on that subject, namely, the optical properties of colours.
Colour is merely an impression produced upon the retina, and therefore on the brain, by various surfaces or media when light falls upon them or passes through them. Remove the light, and colour ceases to exist. The colour of a substance does not depend so much on the chemical character of that substance, but rather and more directly upon the physical condition of the surface or medium upon which the light falls or through which it passes. I can illustrate this easily. For example, there is a bright-red paint known as Crooke's heat-indicating paint. If a piece of iron coated with this paint be heated to about 150° F., the paint at once turns chocolate brown, but it is the same chemical substance, for on cooling we get the colour back again, and this can be repeated any number of times. Thus we see that it is the peculiar physical structure of bodies which appear coloured that has a certain effect upon the light, and hence it must be from the light itself that colour really emanates. Originally all colour proceeds from the source of light, though it seems to come to the eye from the apparently coloured objects. But without some elucidation this statement would appear as an enigma, since it might be urged that the light of the sun as well as that of artificial light is white, and not coloured. I hope, however, to show you that that light is white, because it is so much coloured, so variously and evenly coloured, though I admit the term "coloured" here is used in a special sense. White light contains and is made up of all the differently coloured rainbow rays, which are continually vibrating, and whose wave-lengths and number of vibrations distinguish them from each other. We will take some white light from an electric lantern and throw it on a screen. In a prism of glass we have a simple instrument for unravelling those rays, and
Fig. 16.
instead of letting them all fall on the same spot and illumine it with a white light, it causes them to fall side by side; in fact they all fall apart, and the prism has actually analysed that light. We get now a coloured band, similar to that of the rainbow, and this band is called the spectrum (see Fig. 16). If we could now run all these coloured rays together again, we should simply reproduce white light. We can do this by catching the coloured band in another prism, when the light now emerging will be found to be white. Every part of that spectrum consists of homogeneous light, i.e. light that cannot be further split up. The way in which the white light is so unravelled by the prism is this: As the light passes through the prism its different component coloured rays are variously deflected from their normal course, so that on emerging we have each of these coloured rays travelling in its own direction, vibrating in its own plane. It is well to remember that the bending off, or deflection, or refraction, is towards the thick end of the prism always, and that those of the coloured rays in that analysed band, the spectrum, most bent away from the original line of direction of the white light striking the prism, are said to be the most refrangible rays, and consequently are situated in the most refrangible end or part of the spectrum, namely, that farthest from the original direction of the incident white light. These most refrangible rays are the violet, and we pass on to the least refrangible end, the red, through bluish-violet, blue, bluish-green, green, greenish-yellow, yellow, and orange. If you placed a prism say in the red part of the spectrum, and caught some of those red rays and allowed them to pass through your prism, and then either looked at the emerging light or let it fall on a white surface, you would find only red light would come through, only red rays. That light has been once analysed, and it cannot be further broken up. There is great diversity of shades, but only a limited number of primary impressions. Of these primary impressions there are only four—red, yellow, green, and blue, together with white and black. White is a collective effect, whilst black is the antithesis of white and the very negation of colour. The first four are called primary colours, for no human eye ever detected in them two different colours, while all of the other colours contain two or more primary colours. If we mix the following tints of the spectrum, i.e. the following rays of coloured light, we shall produce white light, red and greenish-yellow, orange and Prussian blue, yellow and indigo blue, greenish-yellow and violet. All those pairs of colours that unite to produce white are termed complementary colours. That is, one is complementary to the other. Thus if in white light you suppress any one coloured strip of rays, which, mingled uniformly with all the rest of the spectral rays, produces the white light, then that light no longer remains white, but is tinged with some particular tint. Whatever colour is thus suppressed, a particular other tint then pervades the residual light, and tinges it. That tint which thus makes its appearance is the one which, with the colour that was suppressed, gave white light, and the one is complementary to the other. Thus white can always be compounded of two tints, and these two tints are complementary colours. But it is important to remark here that I am now speaking of rays of coloured light proceeding to and striking the eye; for a question like this might be asked: "You say that blue and yellow are complementary colours, and together they produce white, but if we mix a yellow and a blue paint or dye we have as the result a green colour. How is this?" The cases are entirely different, as I shall proceed to show. In speaking of the first, the complementary colours, we speak of pure spectral colours, coloured rays of light; in the latter, of pigment or dye colours. As we shall see, in the first, we have an addition direct of coloured lights producing white; in the latter, the green colour, appearing as the result of the mixture of the blue and yellow pigments, is obtained by the subtraction of colours; it is due to the absorption, by the blue and yellow pigments, of all the spectrum, practically, except the green portion. In the case of coloured objects, we are then confronted with the fact that these objects appear coloured because of an absorption by the colouring matter of every part of the rays of light falling thereupon, except that of the colour of the object, which colour is thrown off or reflected. This will appear clearer as we proceed. Now let me point out a further fact and indicate another step which will show you the value of such knowledge as this if properly applied. I said that if we selected from the coloured light spectrum, separated from white light by a prism, say, the orange portion, and boring a hole in our screen, if we caught that orange light in another prism, it would emerge as orange light, and suffer no further analysis. It cannot be resolved into red and yellow, as some might have supposed, it is monochromatic light, i.e. light purely of one colour. But when a mixture of red and yellow light, which means, of course, a mixture of rays of greater and less refrangibility respectively than our spectral orange, the monochromatic orange—is allowed to strike the eye, then we have again the impression of orange. How are we to distinguish a pure and monochromatic orange colour from a colour produced by a mixture of red and yellow? In short, how are we to distinguish whether colours are homogeneous or mixed? The answer is, that this can only be done by the prism, apart from chemical analysis or testing of the substances.
The spectroscope is a convenient prism-arrangement, such that the analytical effect produced by that prism is looked at through a telescope, and the light that falls on the prism is carefully preserved from other light by passing it along a tube after only admitting a small quantity through a regulated slit.
Now all solid and liquid bodies when raised to a white heat give a continuous spectrum, one like the prismatic band already described, and one not interrupted by any dark lines or bands. The rays emitted from the white-hot substance of the sun have to pass, before reaching our earth, through the sun's atmosphere, and since the light emitted from any incandescent body is absorbed on passing through the vapour of that substance, and since the sun is surrounded by such an atmosphere of the vapours of various metals and substances, hence we have, on examining the sun's spectrum, instead of coloured bands or lines only, many dark ones amongst them, which are called Fraunhofer's lines. Ordinary incandescent vapours from highly heated substances give discontinuous spectra, i.e. spectra in which the rays of coloured light are quite limited, and they appear in the spectroscope only as lines of the breadth of the slit. These are called line-spectra, and every chemical element possesses in the incandescent gaseous state its own characteristic lines of certain colour and certain refrangibility, by means of which that element can be recognised. To observe this you place a Bunsen burner opposite the slit of the spectroscope, and introduce into its colourless flame on the end of a platinum wire a little of a volatile salt of the metal or element to be examined. The flame of the lamp itself is often coloured with a distinctiveness that is sufficient for a judgment to be made with the aid of the naked eye alone, as to the metal or element present. Thus soda and its salts give a yellow flame, which is absolutely yellow or monochromatic, and if you look through your prism or spectroscope at it, you do not see a coloured rainbow band or spectrum, as with daylight or gaslight, but only one yellow double line, just where the yellow would have been if the whole spectrum had been represented. I think it is now plain that for the sake of observations and exact discrimination, it is necessary to map out our spectrum, and accordingly, in one of the tubes, the third, the spectroscope is provided with a graduated scale, so adjusted that when we look at the spectrum we also see the graduations of the scale, and so our spectrum is mapped; the lines marked out and named with the large and small letters of the alphabet, are certain of the prominent Fraunhofer's lines (see A, B, C, a, d, etc., Fig. 16). We speak, for example, of the soda yellow-line as coinciding with D of the spectrum. These, then, are spectra produced by luminous bodies.