its setting time is calcium sulphate, naturally formed from the sulphur in the raw materials or fuel, or intentionally added to the finished cement as gypsum or plaster of Paris. It has a remarkable retarding effect on the hydration of the calcium aluminate, and consequently on the setting of the cement; thus it is that a little gypsum is often added to convert a naturally quick-setting cement into one which sets slowly. It will be observed that in the hydration of tricalcium silicate, the main constituent of Portland cement, a large portion of the lime appears as calcium hydroxide, i.e. slaked lime. It is evident that this will form a pozzuolanic cement if a suitable silicious material such as trass is added to the cement. The ultimate product when set may be regarded as a mixed Portland and pozzuolanic cement. The use of trass in this manner as an adjunct to Portland cement has been advocated by W. Michaelis, and undoubtedly increases the strength of the material, but it has not become general.
The quality of Portland cement is ascertained by its analysis and by determining its specific gravity, fineness, mechanical strength and soundness. A good sample will usually have a composition within the limits cited above and approximating to the typical figures given above. It will be ground so finely that not more than 3% will be left on a sieve of 76 × 76 meshes per sq. in.,Testing. the wires of the sieve being 0·005 in. in diameter. It will have, when freshly burned, a specific gravity not lower than 3·15, and briquettes made from it and kept in water will possess a tensile strength of 400-500 ℔ per sq. in. seven days after they are made, while briquettes made from a mixture of 3 parts by weight of sand and 1 of cement will give about 225 ℔ per sq. in. at twenty-eight days. Formerly the soundness of cement was determined by keeping thin pats of the cement in cold water for twenty-eight days, or in warm water (110°-120° F.) for twenty-four hours, and examining for cracks or other signs of expansion. Modern practice is to measure the expansion of a test piece of cement kept in water at a temperature of 212° F. The simplest and most generally used method is due to H. L. le Châtelier, and consists in measuring the increase in circumference of a cylinder of cement 30 mm. in diameter by means of a split ring encircling the cylinder, the motion of which is magnified by two light rods extending radially. Another quantitative test for soundness is that formulated by L. Deval, who has shown that briquettes of 3 of sand and 1 of cement kept in water for two days at 80° C.＝176° F. attain approximately the same strength as similar briquettes attain at seven days in water at the ordinary temperature. In like manner briquettes kept at 176° F. for seven days are approximately equal in strength to those kept at the ordinary temperature for twenty-eight days. A cement not perfectly sound will give low results in the hot test, and a cement of indifferent soundness will crack and go to pieces. The test is admittedly severe, but can be passed without difficulty by cement made with proper care and skill. There are many modifications and elaborations of all the tests which have been mentioned. Cement for all important work is submitted to a rigorous system of testing and analysis before it is accepted and used.
Hydraulic Lime is a cement of the Portland as distinct from the pozzuolanic class. The most typical hydraulic lime is that known as Chaux du Theil, made from a limestone found at Ardèche in France. This limestone consists of calcium carbonate most intimately intermixed with very finely divided silica. It contains but little alumina and oxide of iron, which are the constituents generally necessary to bring about the union of silica and lime to form a cement, but in spite of this the silica is so finely divided and so well distributed that it unites readily with the lime when the limestone is burned at a sufficiently high temperature. English hydraulic limes are of a different class; they contain a good deal of alumina and ferric oxide, and in composition resemble somewhat irregular Portland cement.
Analyses of the two classes of hydraulic lime are as follows:—
| Chaux de Theil. Per cent. | Blue Lias. Per cent | |
| Insoluble silicious matter | 0·3 | 2·39 |
| Silica (SiO2) | 21·7 | 14·17 |
| Alumina (Al2O3) | 1·8 | 6·79 |
| Ferric oxide (Fe2O3) | 0·6 | 2·34 |
| Lime (CaO) | 74·0 | 63·43 |
| Magnesia (MgO) | 0·7 | 1·54 |
| Sulphuric anhydride (SO3) | 0·3 | 1·63 |
| Carbonic anhydride (CO2) | 0·6 | 3·64 |
| Water (H20) | 2·69 | |
| Alkalis and loss | · · | 1·38 |
| ——— | ——— | |
| 100·0 | 100·00 |
Hydraulic lime contains a good deal of uncombined lime, and has to be slaked before it is used as a cement. In France this slaking is conducted systematically by the makers, the freshly burned lime being sprinkled with water and stored in large bins where slaking proceeds slowly and regularly until the whole of the surplus uncombined lime is slaked and rendered harmless, while the cementitious compounds, notably tricalcium silicate, remain untouched. In English practice hydraulic lime is slaked by the user. Seeing that regular and perfect slaking is more easily attained when working systematically on a large scale and by storing the material for a long period, the French method is the better and more rational. The product may then be regarded as a cement of the Portland class mixed with slaked lime. When gauged with water and made into a mortar it sets slowly, but ultimately becomes almost as strong as Portland cement. Its slow setting is an advantage for some purposes, e.g. for foundations and abutments where settlements may occur. The structure is free to take its permanent position before the lime sets, and cracks are thus avoided. A case in point is the employment of hydraulic lime in place of Portland cement as grouting outside the cast-iron tubes used for lining tunnels made by the shield system.
Roman Cement is another cement of the Portland class which came into use shortly before the manufacture of artificial Portland cement was attempted. It is still in use, though only for special purposes where a quick-setting material is required. It is made from septaria nodules which are dredged up on the Kent and Essex coasts and consist of about 60% of calcium carbonate mixed with clay, the mass being sufficiently indurated to remain coherent under water. The nodules are not prepared in any way, but simply burned at a moderate red heat.
The resulting cement varies somewhat in composition, but approximates to the following figures:—
| Per cent. | |
| Insoluble silicious matter | 5·86 |
| Silica (SiO2) | 19·62 |
| Alumina (Al203) | 10·30 |
| Ferric oxide (Fe2O3) | 7·44 |
| Manganese dioxide (MnO2) | 1·57 |
| Lime (CaO) | 44·54 |
| Magnesia (MgO) | 2·92 |
| Sulphuric anhydride (SO3) | 2·61 |
| Carbonic anhydride (CO2) | 3·43 |
| Water (H2O) | 0·25 |
| Alkalis and loss | 1·46 |
| ——— | |
| 100·00 |
The most characteristic constituent is the oxide of iron, which gives the cement a reddish colour, and the presence of manganese also differentiates Roman from Portland cement, which rarely contains appreciable quantities of that element. The high percentage of alumina causes the cement to be quick-setting, and it becomes hard in about five minutes. It resists the action of water, salt or fresh, very well, and is therefore useful in situations where the work is likely to be submerged immediately after it has been put in place.
The term Natural Cements is applied to cements made by burning mixtures of clay and carbonate of lime naturally occurring in approximately suitable proportions. They may be regarded as badly-mixed Portland cements, and need no special description. American “natural” cements are of a somewhat different class. They are usually made from a silicious limestone containing magnesia, and are comparatively lightly burned.
The following analysis is typical of a cement of this kind:—
| Per cent. | |
| Silica (SiO2) | 24·30 |
| Alumina (Al203) | 7·22 |
| Ferric oxide (Fe2O3) | 5·06 |
| Lime (CaO) | 33·70 |
| Magnesia (MgO) | 20·94 |
| Water, carbonic anhydride, and loss | 8·78 |
| ——— | |
| 100·00 |
These irregular cements of the Portland class are good building materials for ordinary purposes, but are not so suitable as good artificial Portland cement for heavy and important undertakings.
Passow Cement is a recent product which is in a class by itself. It is made by granulating blast furnace slag of suitable composition and finely grinding the product, either alone or with an admixture of about 10% of Portland cement clinker. It differs from ordinary slag cement (see above) in that it is not a pozzuolanic cement depending on the interaction of granulated slag and lime. The particular method of granulating slag for Passow cement produces a material which sets per se and attains a strength comparable with that of Portland cement. Passow cement has been successfully made from slag of different compositions in Germany, England and America.
