THE SILICA GROUP.

Silica, the oxide of silicon, is found in brickmaking clays principally in two conditions when not combined with other substances: in one of these the free silica may be crystalline, when it is known as quartz; in the other it may be hard, but not crystalline, as flint. We may consider these in order.

Quartz.—When pure this mineral is perfectly white and transparent, like ordinary window glass. It is exceedingly hard, and this property is of much service as enabling us by the most elementary examination to distinguish it from certain other minerals, which it is not unlike at first sight. One of the latter is calcite, a crystalline form of carbonate of lime, also white and transparent. Quartz and calcite behave in a very different manner in the kiln, and as we shall see, they are both rather common constituents of brick-earth. The difference in hardness may easily be ascertained by the point of a good steel knife; the steel will not scratch the quartz, but it will, easily, the calcite.

When it has plenty of room wherein to crystallise, and is not hemmed in, as it were, by other hard crystalline matter, quartz often forms beautiful six-sided prisms surmounted by a six-sided pyramid, and, rarely, pyramids are found at both ends of a prism. There are no lines, or “planes of cleavage,” to interfere with the transparency, either in the extremely minute forms of the mineral as investigated by the microscope, or in the gigantic crystals occasionally found. Regular crystals of quartz, although by no means rare in Nature, are seldom met with entire in brick-earths. The most common form of the mineral is in irregular aggregates with other minerals, as in the rock granite, which is composed essentially, as previously mentioned, of quartz, felspar, and mica. We have traced the history of the felspar on the decomposition of that rock, and it may now be said that on complete disintegration of the granite a great part of the quartz present is simply resolved into fragments and dealt with by rain and other transporting agents. For quartz is practically imperishable; it is almost proof against the deleterious acids in the atmosphere, which so readily attack many other common minerals. In dealing with it, all Nature can do (at least at the surface of the earth) is to carry the small quartz grains and pieces about from place to place; She can, and does, in this process, reduce the quartzose fragments by causing them to continually knock against each other and against other mineral fragments and masses until the grains and pieces find a resting place; She may put them in a mill and grind them to powder, but the quartz is still there.

Another manner in which quartz occurs in Nature is as filling cracks in rocks, but this is comparatively unimportant for our present purposes. The purest quartz is known as rock crystal; but by far the commonest kinds of the mineral are impure; they may contain iron, schorl (a black needle-like crystal), and many other minerals. One of the most interesting points about it, and which undoubtedly in certain cases is of importance to the brick manufacturer as modifying its melting properties, is the presence of myriads of extremely minute so-called cavities, generally filled (or nearly filled) by liquids of different kinds, the precise nature of which is not as well-known as it might be, though in some instances it has been determined with tolerable certainty. In some cases these inclusions are so numerous as to obliterate the transparency of the quartz crystal, causing it to present a frosted appearance. The fluids in these cavities may have beautiful little crystals of other minerals, such as salt, floating about—but it must be remembered that we are referring to something infinitely little. These slight differences in the constitution of minerals, however, have their influence in the kiln. For instance, although the fluid present is usually water, that often contains carbon dioxide, which acts as a species of flux to the quartz when present in sufficient quantity.

In reference to the second form of silica present in brick-earths, flint, that is of precisely the same chemical composition as quartz, only that it is not crystalline, nor transparent, though thin pieces of flint are translucent. Flint is by no means as common in Nature as quartz; it is very hard, but brittle, and breaks with what is termed a conchoidal fracture, from the fact that the fractured surface frequently resembles the external appearance of the shell of a bivalve mollusc. It occurs in a variety of ways; (1) often as hard lumps or nodules running along in fairly regular layers in limestone rocks such as chalk, and (2) occasionally filling up cracks or joints in such rocks. It is hard to describe its origin in a few words, and we shall not attempt it; all that need be noted is that it is frequently full of the remains of extinct organisms of small size, which may, or may not, constitute an impurity depending on the particular organism and its present condition. When flint contains a fair proportion of iron it is called chert—an extremely common constituent of brick-earths in some localities—though that term refers to other rocks, such for instance, as those made up almost exclusively of the siliceous spicules (hard parts made of silica) of fossil sponges.

A more or less crystalline kind of silica is found, forming the skeletons of minute aquatic plants, and these accumulating to some depth, constitute the basis of such materials as Kieselguhr and the diatom earth of the Isle of Skye, both of which, especially the former, are used for making firebricks.

There is very little to be said concerning the behaviour of free silica—quartz and flint—in the kiln. It is infusible except at higher temperatures than are employed by the brickmaker. But, as we have already remarked, the impurities often present in the minerals form a species of flux which naturally brings them into the range of fusible substances, though even then the temperature required is far beyond what is usually attained in the majority of brickyards, though it might be frequently arrived at in the manufacture of certain fire-bricks. For all ordinary purposes, therefore, quartz and flint may be regarded as infusible. In presence of much lime, iron, or similar substances, however, both of them are readily melted, and it is part of the science of brickmaking to know exactly how much lime, &c., to add to yield the best results. Many brick-earths contain large quantities of the calcareous and ferruginous substances alluded to, and are then capable of being made into bricks direct, without any addition. But although such natural brickmaking earths are frequently employed by the manufacturer, nearly all of them could be made to yield a better brick by a little artificial mixing. We must keep urging this point; there is room for great improvement all round. As with the majority of comparatively refractory substances, the size of the grains and pieces of quartz and flint makes a difference in their readiness to become fusible. The larger the grain the more difficult it is to break down; fusion commences at the outside of a quartz grain, the centre of which may at the same time be comparatively unaffected. By arresting the fusing process, the microscope shows the outside of the grain to have become softened (so much so as to affect its doubly refracting properties), whilst the innermost parts still retain their usual optical characters.

MICA.

The different varieties of mica are important as rock-forming minerals, but they are not as often met with in brick-earths as is generally supposed, except in insignificant quantity. Some of the purest clays, however, contain a great deal of mica, derived almost directly from the destruction of granite. The two commonest varieties of the mineral are biotite and muscovite.

Biotite Mica.—This mineral, usually known as ferro-magnesian mica, is composed of silicates of magnesia, alumina, iron, and alkalies in variable proportions. It occurs as six-sided plates or irregular scales, usually of a bronze-black colour. Biotite weathers with comparative facility, hence the reason why it is not more commonly met with in brown and other impure clays.

Muscovite Mica.—This is sometimes called potash- or alumino-alkaline mica, composed of the silicates of alumina, alkalies, iron, and magnesia; the proportion of silica ranges from 45 to 50 per cent. It may usually be distinguished at sight from biotite by its silvery white or light brown colour. When large enough, both the micas mentioned may be split up into thin plates, muscovite yielding large transparent sheets. Compared with all other constituents of brick-earth, the micas are bright and of semi-metallic lustre. Muscovite is more durable than biotite, and is much more frequently met with in brick-earths, especially in the sandy varieties.

The influence of mica in the kiln is not of much importance in ordinary brickmaking; in general its alkaline character renders it fusible, though a high temperature is necessary at all times to effect that. In china-clay mica is regarded as a nuisance, and in breaking down the material it is separated in the washing process by running water, the mineral collecting in depressions or basins, called “micas.” When muscovite contains much fluorine, as it frequently does, it is very undesirable in clays for high-class purposes. At the best of times the proportion of iron in mica is sufficient to mar the quality of the otherwise most excellent clays. In the kiln, or porcelain furnace, the presence of mica (more particularly biotite) is apt to create yellow and brown specks, or a species of mottling. It is highly satisfactory, therefore, to note that these little shiny flakes may be easily floated off by a moderate amount of care in washing, and thus separated from the other constituents of the clay.

IRON.

Except in regard to white kaolin clays, nearly all earths used in brickmaking contain more or less iron, which is usually present as protoxide in many mineral constituents. The colouring matter of clays is generally iron in some form, and blue clays weather into brown by the alteration of that mineral. It is unnecessary for us to consider the various minerals of the iron group; all we need do is to state the mode of occurrence of iron oxides in clays and earths, to consider a variety known as iron-pyrite, and the general effects of ferruginous minerals in the kiln.

Iron may occur in clays simply as a stain, when it is usually not in large quantity, or it may occur combined with some mineral or minerals present—as for instance certain felspars and micas. The brown, yellow, or blue appearance of the clay is due to it. In loam it may be found also as a species of ochreous earth, and in thin bedded loams (as the upper part of the Woolwich and Reading series of the London basin) each layer frequently varies in the proportion of iron present. In the more arenaceous parts of these loamy deposits, little grains of iron sometimes make their appearance, as also in certain sands employed in brickmaking; on careful examination, however, many of these grains are found to be other mineral substances coated with iron. Certain horizons in what are known as the Jurassic rocks contain great quantities of ferruginous matter in little pellets.

Iron, in large proportion, acts as a flux to other constituents when the brick-earth is subjected to great heat in the kiln, and on that account must be carefully watched. But, to the average brickmaker, the ferruginous constituent is far more interesting as a colouring medium. At a later stage we shall have something to say concerning the colouring of bricks, &c., but it may now be remarked that red bricks, in practically all cases, owe their colour to the effects of firing on iron. It is a great mistake to imagine, however, that a large percentage of iron in a clay will necessarily produce a good red tint. In the first place, a great deal depends on the way the clay has been mixed or prepared; and in the second, the method of burning and the temperature employed, taken in conjunction with the general composition of the earth, are all important. This much may be said, however, that without the iron (or some mineral colouring matter possessing similar properties in the kiln) a red brick would not result. An even colour is the effect of thorough and homogeneous incorporation of the iron with the brick-earth; that may have been brought about by natural processes, but it is most frequently obtained in the careful preparation and mixing of the clays. A very essential point is that the earths must be of such a character as to withstand the requisite heat in the kiln without becoming vitreous, or twisting or warping. It must not be forgotten that a certain proportion of the iron, under great temperatures, may be carried away out of the kiln in union with other things, in the form of vapour. To successfully treat a raw earth, so that all these points may be taken into account, and to produce a thoroughly uniform red brick, that shall not vary in tint from kiln to kiln, is a matter requiring considerable skill and attention, though fairly good bricks of that character have been produced by sheer accident in burning natural earths fairly rich in thoroughly disseminated iron oxides.

Two minerals commonly met with in earths used for brickmaking are pyrite and marcasite, both of which are of the same chemical composition, namely, iron disulphide. We may first consider them separately, for they are of great importance to the brickmaker.

Iron pyrite occurs as regular cubic crystals, or irregular streaks, or as nodules or lumps; in clay, the last-mentioned is its commonest form. It is a good petrifying medium, so that it is frequently associated with organic remains, as is exemplified in almost any yard where stiff clay is being worked. The nodules, on being broken open, ordinarily exhibit a radiating structure of brassy lustre and extremely beautiful appearance, though often marred by brown iron stains due to decomposition of the mineral. In the refuse of slates, now so largely used in several parts of the world for brickmaking, pyrite is most frequently found as fine cubic crystals of a durable nature.

Marcasite, on the other hand, crystallizes in a different manner (in the rhombic system of mineralogists), but is chiefly found in fibrous masses or dirty-brown nodules, the last-mentioned being common in clays. When bright it is paler in tint than pyrite, though this is not a constant character. It occurs abundantly in almost all sedimentary rocks diffused as minute particles, but sometimes in irregular layers. Sir Archibald Geikie states5 that this form of the sulphide is especially characteristic of stratified rocks, and more particularly of those of Secondary and Tertiary age. That it is not abundant in Primary rocks is not to be wondered at when we consider its liability to rapid decomposition; indeed, for it to be preserved at all it must be well shielded from atmospheric agents by Nature. Exposure even for a short time to the air causes it to become brown, free sulphuric acid is produced, which may attack surrounding minerals, sometimes at once forming sulphates, at other times decomposing aluminous silicates and dissolving them in considerable quantity. It plays even a larger part than pyrite as a petrifying medium, at any rate in the younger rocks. Both pyrite and marcasite are abundant in many other rocks than those of special interest to the brickmaker; the former, in fact, is almost universal in its occurrence. It will be convenient to consider the behaviour of these two minerals in the kiln together, as the difference between them from that point of view is practically nil. Under the action of the intense heat met with there, they become partially decomposed; oxide of iron and basic sulphides of iron remain. When, at a subsequent period, bricks containing these substances are exposed to the action of the weather, oxidation takes place, sulphate of iron and sometimes of lime are formed, which on crystallizing expand with considerable force and split or crack the brick. From this it is evident that sulphide of iron in any form is not to be tolerated in brick manufacture, and if the earth used in the first place contains much, it must be removed in the preparing process. If permitted to remain, it is impossible to obtain either a durable, or a good coloured brick.