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 states[5] 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.
CHAPTER VI.
MINERALS: THEIR BEHAVIOUR IN THE KILN (continued).
CALCITE, ARAGONITE, &c.
Carbonate of lime may occur in a crystalline form, or as earthy substances, and many varieties of it are found in clays used by the brickmaker. The commonest are calcite, aragonite, and a white earth.
Calcite, known also as calc-spar, crystallises in the hexagonal system, though true hexagons are not very common. It occurs principally as rhombohedra and scalenohedra, with variations therefrom; also fibrous, lamellar, granular, compact, nodular, and stalactitic. When pure, calcite is colourless and usually transparent, but when mixed with iron or other mineral colouring matter it commonly assumes yellow and brown tints.
Aragonite is also a crystalline form of carbonate of lime, but is by no means as common in Nature as calcite. It crystallises in the rhombic system, which assists the mineralogist to distinguish it from the last-mentioned mineral, from which it differs also in being harder and of higher specific gravity. Aragonite may occur as globular masses, or as incrusting other substances, or in the stalactitic form. It is sometimes white, but more often yellowish, or grey, and it is not, commonly, as transparent as calcite, whilst it often possesses one to two per cent. of carbonate of strontia, or other impurity.
It is generally stated that carbonate of lime, when deposited from cold solutions, crystallizes in hexagonal (calcite), and when from warm solutions, in rhombic (aragonite) forms. No doubt, on the whole, that is the case; but we ought not to forget that many marine organisms make their hard parts of aragonite, which, under the circumstances, is certainly not obtained from warm solutions. These crystalline forms of carbonate of lime are both of them found in fossil shells and the like in clays, and in not a few instances the calcareous constituent found in the brick-earth is present almost exclusively in the fossils, which are ground up with the rest in preparing the material for the moulding machine.
When present as hard crystalline lumps or pebbles, they have been derived from the destruction of limestones, and are then the greatest nuisance imaginable to the brickmaker and the most dangerous constituent at the same time. With proper machinery these hard lumps may be ground down to fine particles, but they are even then only to be admitted into the earth on sufferance. The best plan, without doubt, is to remove them altogether from the raw earth. They are commonly met with in what the geologist calls “boulder clay”—a deposit owing its origin to glaciers and icebergs. Very often the pebbles alluded to are not crystalline, but of an earthy character, as is the case when made of chalk. In the semi-dry process of manufacture, it is next to impossible to incorporate the ground-up particles of carbonate lime sufficiently well to result in the production of such a homogeneous earth as is desirable for making a first-class brick.
In sandy clays or loams, and in a few stiff clays used for brickmaking, certain remarkable concretions called “race” are found, the deleterious properties whereof are so well known to the average brickmaker that he carefully avoids the particular strata in which they occur. It is fortunate that these concretions have a habit of being confined to narrow limits along definite horizons in the brickyard section, so that they may be readily discarded in working. But that is not always the case, and little nodules of “race” are usually more or less frequent also in the beds above and below the horizons referred to. They are composed wholly of carbonate of lime, and their general effect in the kiln, and afterwards, will presently be explained. Other forms of concretions are known as “septaria,”—tabular or rounded masses of argillaceous limestone found in practically all stiff clays. These are often of enormous size, and are disposed in regular lines which the field geologist takes to indicate bedding planes in the clay—otherwise often very difficult to make out. In certain stiff clays little pellets of the same substance are found. The larger septaria have commonly been cracked in various directions, the fissures being subsequently filled with calcite.
Coprolites are impure varieties of phosphate of lime, and the term should, properly speaking, be restricted to a substance of organic origin,—the fossilised excrement of animals. But the name is now loosely employed to designate phosphatic concretions in general, such as are commonly found in stiff clays, in certain “greensands,” and in other sedimentary deposits. The dark brown phosphate of lime has formed on and often completely envelopes many fossils; in certain cases it has in fact been utilised as a petrifying medium, in which form it ordinarily occurs in the thick black clays of Peterborough, Cambridge, the gault of Kent, Surrey, etc.
Summing up the effects of carbonates and other kinds of lime in the kiln, it may be at once said that when present in any other form than as extremely minute particles, they are distinctly to be avoided. The small pellets and large pebbles especially are to be avoided, for the following reasons. Carbonate of lime is made up of lime and carbonic acid; if a lump of this be subjected to great heat and thus calcined, the carbonic acid is driven off, escaping by means of flues, the open chimney, or kiln. The product is lime pure and simple—ordinary builders’ lime. Everyone knows that on the addition of water builders’ lime becomes “slacked,” and eventually, after a fashion, “sets.” Precisely the same thing occurs in the brick-kiln. The raw brick is often composed of pieces of chalk or other limestone, in limestone districts and in areas where boulder clays are largely employed for brickmaking. On being subjected to the heat of the kiln these pieces are promptly reduced to the condition of lime. During the process of conversion considerable expansion takes place, and subsequently contraction, leading to the formation of cracks radiating from the fragments of limestone, the homogeneity of the bricks being at once destroyed. Apart from this, when placed in the open air the lime becomes slacked, and the quality of the brick is seriously impaired.
Lime is a highly refractory substance, strongly basic in character, and forms fusible compounds with silica and other acid bodies. It is, therefore, useful as a flux in many earths used in brickmaking, being added to them expressly for that purpose, to the general improvement of the brick. The celebrated Dinas bricks, for instance, are composed of a highly refractory earth containing about 97 per cent. silica, the remainder being lime, oxide of iron, alumina, alkali and water. To render this material fusible and so as to make refractory bricks, from 1 to 3 per cent. of lime is added.
But what we more particularly desire to draw the reader’s attention to at the present stage, is not the employment of lime in making fire-bricks so much as its mixture with ordinary brick-earth, as in the manufacture of malm bricks. Sometimes the mixture has been effected by Nature, as is the case with true marls; but the brickmaker does not care so much for these, as without considerable and expensive artificial assistance they do not often make readily saleable bricks. The common practice is, briefly, to grind chalk or similar earthy limestone in the wet state, and then to introduce it to the brick-earth with which it is thoroughly incorporated; and there are many ways of doing this, which we shall not attempt to describe now. The object of adding chalk to the brick-earth is twofold; in the first place it assists in diminishing the contraction of the brick on drying, i.e., before burning; and secondly, it acts as a flux in the kiln by combining with the free silica, or the silicates, in the earth. Undoubtedly the second is, theoretically, its chief function; but its beneficial effects in that direction are largely marred by insufficient burning, whereby a large proportion of the chalk is not actively engaged, as may be seen on examining the majority of malm bricks with the microscope. Indeed, the eagerness to save fuel, and to turn out the bricks as rapidly as possible, often leads to the chalk particles being utterly useless. And, if we may judge from conversations with several brickmakers, it would seem that the real reason why the limestone is used at all is unknown to them, except that it produces bricks of a saleable colour. This question of colour is the all-predominating one with most malm brickmakers.
We said just now that the fragments of limestone in the raw brick are reduced to lime on being burnt; some of the latter, however, as may be anticipated from our subsequent remarks, is engaged in forming a flux wherever possible in the immediate neighbourhood of such fragments: it is the “kernel” that is left which becomes “slacked,” and weakens the brick. The object of utilising the smallest particles only of the carbonate of lime is thus obvious; and if it were possible to use ordinary builders’ lime instead of carbonate of lime, the result would be better still. The difficulty in utilising builders’ lime is, of course, its certainty of slacking during the preparation of the brick-earth with which it would have to be thoroughly incorporated.