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654
CEMENT

substances occurring abundantly in nature which can thus be used. They are mostly of volcanic origin, and include pumice, tufa, santorin earth, trass and pozzuolana itself. The following analyses show their general composition:—

  Neapolitan
Pozzuo-
lana
(per cent)
Roman
Pozzuo-
lana
(per cent)
Trass
(per cent)
Soluble silica (SiO2) 27.80 32.64 19.32
Insoluble silicious residue 35.38 25.94 50.40
Alumina (Al2O3) 19.80 22.74 13.86
Ferric oxide (Fe2O3) 3.10
Lime (CaO) 5.68 4.06 · ·
Magnesia (MgO) 0.35 1.37 0.13
Sulphuric anhydride (SO3) Trace Trace · ·
Combined water (H2O) 4.27 8.92 7.57
Carbonic anhydride (CO2) · ·
Moisture · · · · 5.04
Alkalis and loss 6.72 4.33 0.58
  100.00 100.00 100.0

An artificial product which serves perfectly as a pozzuolana is granulated blast-furnace slag. The slag, which must contain a high percentage of lime, is granulated by being run while fused into abundance of water. This granulated slag differs from the same slag allowed to cool slowly, in that a portion of the energy which it possesses while fused is retained after it has solidified. It bears to ordinary slowly-cooled slag a similar relation to that borne by plastic sulphur to ordinary crystalline sulphur. This potential energy becomes kinetic when the slag is brought into contact with lime in the presence of water, and causes the formation of a true hydraulic silicate of lime. The following analysis shows the composition of a typical slag:—

  Per Cent.
Insoluble residue 1.04
Silica (SiO2) 31.50
Alumina (Al2O3) 18.56
Manganous oxide (MnO) 0.44
Lime (CaO) 42.22
Magnesia (MgO) 3.18
Soda (Na2O) 0.70
Sulphuric anhydride (SO3) 0.45
Sulphur (S) 2.21
  ———
  100.30
Deduct oxygen equivalent to sulphur 1.10
  ———
  99.20

Granulated slag of this character is ground with slaked lime until both materials are in a state of fine division and intimately mixed. The usual proportions are three of slag to one of slaked lime by weight. The product termed slag cement sets slowly, but ultimately attains a strength scarcely inferior to that of Portland cement. Although it is cheap and suitable for many purposes, its use is not large and tends to decrease. Pozzuolanic cements are little used in England. Generally speaking, they are only of local importance, their cheapness depending largely on the nearness and abundance of some suitable volcanic deposit of the trass or tufa class. They are not usually manufactured by the careful grinding together of the pozzuolana and the lime, but are mixed roughly, a great excess of pozzuolana being employed. This excess does no harm, for that part which fails to unite with the lime serves as a diluent, much as does sand in mortar. In fact, ordinary pozzuolanic cement made on the spot where it is to be used may be regarded as a better kind of common mortar having hydraulic qualities. Good hydraulic mortars may be made from lime mixed with furnace ashes or burnt clay as the pozzuolanic constituent.

Cements of the Portland type differ in kind from those of the pozzuolanic class; they are not mechanical mixtures of lime and active silica ready to unite under suitable conditions, but consist of definite chemical compounds of lime andPortland Cement. silica and lime and alumina, which, when mixed with water, combine therewith, forming crystalline substances of great mechanical strength, and capable of adhering firmly to clean inert material, such as stone and sand. They are made by heating to a high temperature an intimate mixture of a calcareous substance and an argillaceous substance. The commonest of such substances in England are chalk and clay, but where local conditions demand it, limestone, marl, shale, slag or any similar material may be used, provided that the correct proportions of lime, silica and alumina are maintained. The earliest forms of cements of the Portland class were the hydraulic limes. These are still largely used, and are prepared by burning limestones containing clayey matter. Some of these naturally possess a composition differing but little from that of the mixture of raw materials artificially prepared for the manufacture of Portland cement itself. Although hydraulic limes have been in use from the most ancient times, their true nature and the reason of their resistance to water have only become known since 1791. Next in antiquity to hydraulic lime is Roman cement, prepared by heating an indurated marl occurring naturally in nodules. Its name must not be taken to imply that it was used by the ancients; in point of fact the manufacture of this substance dates back only to 1796.

With the growth of engineering in the early part of the 19th century arose a great demand for hydraulic cement. The supply of materials containing naturally suitable proportions of calcium carbonate and clay being limited, attempts were made to produce artificial mixtures which would serve a similar end. Among those who experimented in this direction was Joseph Aspdin, of Leeds, who added clay to finely ground limestone, calcined the mixture, and ground the product, which he called Portland cement. The only connexion between Portland cement and the place Portland is that the cement when set somewhat resembles Portland stone in colour. True, it is possible to manufacture Portland cement from Portland stone (after adding a suitable quantity of clay), but this is merely because Portland stone is substantially carbonate of lime; any other limestone would serve equally well. Although Portland cement is later in date than either Roman cement or hydraulic lime, yet on account of its greater industrial importance, and of the fact that, being an artificial product, it is of approximately uniform composition and properties, it may conveniently be treated of first. The greater part of the Portland cement made in England is manufactured on the Thames and Medway. The materials are chalk and Medway mud; in a few works the latter is replaced by gault.

The composition of typical samples of chalk and clay is shown in the following analyses:—

The composition of typical samples of chalk and clay is shown in the following analyses:—

Chalk.

  Per cent.
Silica (SiO2) 0.92
Alumina + ferric oxide (Al2O2 + Fe2O3) 0.24
Lime (CaO) 55.00
Magnesia (MgO) 0.36
Carbonic anhydride (CO2) 43.40
  ———
  99.92

Clay.

  Per cent.      
Insoluble silicious matter 26.67  Consisting of    
Silica (SiO2) 31.24  Quartz (SiO2) 19.33  
Alumina (Al2O3) 16.60  Silica (SiO2) 5.19  Feldspar 
7.34%
Ferric Oxide (Fe2O3) 8.66  Alumina (Al2O3) 1.47
Lime (CaO) 0.25  Magnesia (MgO) 0.03
Magnesia (MgO) 1.91  Soda (Na20) 0.65
Soda (Na2O) 1.00   ———  
Potash (K2O) 0.45    26.67  
Sodium Chloride (NaCl) 1.86      
Combined water, organic matter, and loss 11.36      
  ———    
  100.00