The chief use of hydraulic cements, whether of the pozzuolanic or Portland class, is to act as an adhesive material in work which is to be exposed to water. No doubt in times of remote antiquity it was found that the jointing of masonry which was to be immersed required the use of a cement indifferent to the action of water. Ordinary mortarUses of hydraulic cements. failed in such positions; mortar made from lime prepared from limestones or chalks containing a little clay was found to stand; mortar made from lime mixed with trass or similar active silicious material was also found to stand. On this observation rests the whole of the present enormous employment of hydraulic cements. It was a natural transition to utilize these cements not merely for jointing masonry but also for making concrete, and the only reason why hydraulic cements, as distinct from cements which are not hydraulic (e.g. ordinary mortar), are used for the latter purpose is their great mechanical strength. Their use in above-water work is checked by the low price of common brick. Even in such work, where it would be thought that masses of burnt clay would be the cheapest conceivable material, concrete is at least on level terms with its rival. It must be remembered that one of the great advantages of concrete is that five-sixths of its total mass may be provided from local sand and gravel, on which no carriage has to be paid. The cement, on which alone freight is to be reckoned, converts these from loose incoherent material into a solid stone. Thus it comes about that the largest use of cement is for manufacturing concrete for dock and harbour work, and for the making of foundations. It is also employed for the building of light bridges, floors, and pipes constructed of cement mortar disposed round a skeleton of iron rods. Such composite structures take advantage at once of the high tensile strength of iron and of the high compressive strength of cement mortar. (See also Concrete.)
Good hydraulic cements are highly permanent materials provided certain conditions be observed. It might be supposed that hydraulic cements from their nature would be indifferent to the action of water, but this is only true if the structures of which they form part are sufficiently compact. In this case the action of the water is checked by the film of carbonate of lime which eventually forms oh the surface of calcareous cement. This, together with the compactness of the mortar, hinders the ingress and egress of water, and prevents the dissolution and ultimate destruction of the cement. But where the concrete or mortar is not well made and is porous, the continual passage of water through it will gradually break up and dissolve away the calcareous constituents of the cement until its strength is utterly destroyed. This destructive action is increased if the water contains sulphates or magnesium salts, both of which act chemically on the calcareous constituents of the cement. As sea-water contains both sulphates and magnesium salts, it is especially necessary in concrete for harbour work to take every care to produce an impervious structure. There are various minor external causes for the failure and ultimate destruction of cement mortar and concrete, but their discussion is a matter for the specialist. Failure from inherent vice in the cement has been already touched on; it can always be traced to want of skill and care in manufacture.
Calcium Sulphate Cements.—Under this term are comprehended all cements whose setting properties primarily depend on the hydration of calcium sulphate. They include plaster of Paris, Keene’s cement and many variants of these two types. The raw material is gypsum (q.v.). This may be almost chemically pure, when it is generally used for Keene’s cement; or it may contain smaller or greater quantities of impurities, in which case it is suitable for the preparation of cements of the plaster of Paris class. The mode of preparation is to calcine the gypsum at temperatures which depend on the class of cement to be produced. If plaster of Paris is to be made, calcination is carried out at about 204° C. (= 400° F.); at this temperature, gypsum, CaS04·2H20, loses three-quarters of its combined water and becomes 2CaSO4·H20. If a cement of the Keene’s cement class is to be prepared the temperature used is higher, e.g. 500° C. (＝932° F.), and the whole of the combined water of the gypsum is expelled, the anhydrous sulphate CaSO4 being obtained.
To produce plaster of Paris European practice consists in baking the mineral in ovens, and in America in heating it in kettles. Both processes are inferior in economy to calcination in rotatory kilns, a process which may be regarded as the method of the present and the immediate future. Keene’s cement and its congeners are made in fixed kilns so constructedPlaster of Paris; Keene’s cement. that only the gaseous products of combustion come into contact with the gypsum to be burnt, in order to avoid contamination with the ash of the fuel.
The setting of plaster of Paris depends on the fact that when 2CaSO4·H2O is treated with water it dissolves, forming a supersaturated solution of CaSO4·2H2O. The excess held temporarily in solution is then deposited in crystals of CaSO4·2H2O. In the light of this knowledge the mode of setting of plaster of Paris becomes clear. The plaster is mixed with a quantity of water sufficient to make it into a smooth paste; this quantity of water is quite insufficient to dissolve the whole of it, but it dissolves a small part, and gives a supersaturated solution of CaSO4·2H2O. In a few minutes the surplus hydrated calcium sulphate is deposited from the solution, and the water is capable again of dissolving 2CaSO4·H2O, which in turn is fully hydrated and deposited as CaSO4·2H2O. The process goes on until a relatively small quantity of water has by instalments dissolved and hydrated the 2CaSO4·H2O, and has deposited CaSO4·2H2O in felted crystals forming a solid mass well cemented together. The setting is rapid, occupying only a few minutes, and is accompanied by a considerable expansion of the mass. There is reason to suppose that the change described takes place in two stages, the gypsum first forming orthorhombic crystals and then crystallizing in the monosymmetric system. Gypsum thus crystallized is in its normal monosymmetric form, more stable under ordinary conditions than the orthorhombic form. Correlatively in its process of dehydration to form plaster of Paris, monosymmetric gypsum is converted into the orthorhombic form before it begins to be dehydrated.
The principles which govern the preparation and setting of the other class of calcium sulphate cements, that is, cements of the Keene class, are not fully understood, but there is a fair amount of knowledge on the subject, both empirical and scientific. The essential difference between the setting of Keene’s cement and that of plaster of Paris is that the former takes place much more slowly, occupying hours instead of minutes, and the considerable heating and expansion which characterize the setting of plaster of Paris are much less marked.
It is the practice in Great Britain to burn pure gypsum at a low temperature so as to convert it into the hydrate 2CaSO4·H2O, to soak the lumps in a solution of alum or of aluminium sulphate, and to recalcine them at about 500° C. On grinding they give Keene’s cement. Instead of alum various other salts, e.g. borax, may be used. The quantity of these materials is so small that analyses of Keene’s cement show it to be almost pure anhydrous calcium sulphate, and make it difficult to explain what, if any, influence these minute amounts of alum and the like can exert on the setting of the cement. It seems probable that the effect of the salts is inconsiderable, and that the governing condition is the temperature at which the cement has been burnt. The setting of Keene’s cement takes place by the same sort of process which has been described for the setting of plaster of Paris, the chief differences being that the substance dissolved is anhydrous calcium sulphate and that the operation takes a longer time.
All cements having calcium sulphate as their base are suitable only for indoor work because of the solubility of this substance. They form excellent decorative plasters on account of their clean white colour and the sharpness of castings made from them, this latter quantity being due to their expansion when setting.
See D. B. Butler, Portland Cement (London, 1905); E. C. Eckel, Cements, Limes and Plasters (New York, 1905); G. R. Redgrave and Charles Spackman, Calcareous Cements (London, 1905); F. H. Lewis, “Manufacture of Hydraulic Cements in the United States,” The Mineral Industry (New York, 1898); W. H. Stanger and Bertram Blount, “Cement Manufacture in Great Britain,” The Mineral Industry, New York, 1897 and 1905; Id. “The Testing of Hydraulic Cements,” Journ. Soc. Chem. Ind., 1894, 13, p. 455; Id., Proc. Inst. Civ. Eng., 1901; B. Blount, “Recent Progress in the Cement Industry,” Journ. Soc. Chem. Ind., 1906, 25, p. 1020; H. L. le Chatelier, Recherches expérimentales sur la constitution des mortiers hydrauliques; Desch, Concrete, No. 2, pp. 101-102; Davis, Journ. Soc. Chem. Ind., 1905, 26, p. 727. (B. Bl.)
Adhesive Cements.—Mixtures of animal, vegetable and mineral substances are employed in great variety in the arts for making joints, mending broken china and other objects, &c. A strong cement for alabaster and marble, which sets in a day, may be prepared by mixing 12 parts of Portland cement, 8 of fine sand and 1 of infusorial earth, and making them into a thick paste with silicate of soda; the object to be cemented need not be heated. For stone, marble, and earthenware a strong cement, insoluble in water, can be made as follows:—skimmed-milk cheese is boiled in water till of a gluey consistency, washed, kneaded well in cold water, and incorporated
