REDNER ROSACIA (BSME-5) PORTLAND CEMENT Cement, in the general sense of the word, can be described as a material with

adhesive and cohesive properties which make it capable of bonding mineral fragments into a compact whole. This definition embraces a large variety of cementing materials. For constructional purposes, the meaning of the term cement is restricted to the bonding materials used with stones, sand, bricks, building blocks, etc. The principal constituents of this type of cement are compounds of lime, so that in building and civil engineering we are concerned with calcareous cement. The cements of interest in the making of concrete have the property of setting and hardening under water by virtue of a chemical reaction with it and are, therefore, called hydraulic cements. Hydraulic cements consist mainly of silicates and aluminates of lime, and can be classified broadly as natural cements, Portland cements, and high-alumina cements. The present chapter deals with the manufacture of Portland cement and its structure and properties, both when unhydrated and in a hardened state.

MANUFACTURE OF PORTLANT CEMENT From the definition of Portland cement given above, it can be seen that it is made primarly from a calcareous material, such as limestone or chalk, and from alumina and silica found as clay or shale. Marl, a mixture of calcareous and argillaceous materials, is also used. Raw materials for the manufacture of Portland cement are found in nearly all countries and cement plants operate all over the world. The process of manufacture of cement consists essentially of grinding the raw materials, mixing them intimately in certain proportions and burning in a large rotary kiln at a temperature of up to about 1450 C when the material sinters and partially fuses into balls known as clinker. The clinker is cooled and ground to a fine powder, with some gypsum added, and the resulting product is the commercial Portland cement so widely used throughout the world. Some details of the manufacture of cement will now be given, and these can be best followed with reference to the diagrammatic representation of the process shown in Fig.

Fig. 1.1. Diagrammatic representation of: (a) the wet process and (b) the dry process of manufacture of cement The mixing and grinding of the raw materials can be done either in water or in a dry condition; hence the names wet and dry processes. The actual methodsof manufacture depend also on the hardness of the raw materials used and on their moisture content. Let us consider first the wet process. When chalk is used, it is finely broken up and dispersed in water in a washmill; this is a circular pit with revolving radial arms carrying rakes which break up the lumps of solid matter. The clay is also broken up and mixed with water, usually in a similar washmill. The two mixtures are now pumped so as to mix in predetermined proportions and pass through a series of screens. The resulting cement slurry flows into storage tanks. When limestone is used, it has to be blasted, then crushed, usually in two progressively smaller crushers, and then fed into a ball mill with the clay dispersed in water. There, the comminution of the limestone (to the fineness of flour) is completed, and the resultant slurry is pumped into storage tanks. From here onwards, the process is the same regardless of the original nature of the raw materials. The slurry is a liquid of creamy consistency, with a water content of between 35 and 50 per cent, and only a small fraction of material about 2 per cent larger than a 90 m (No. 170 ASTM) sieve size. There are usually a number of storage tanks in which the slurry is kept, the sedimentation of the suspended solids being prevented by mechanical stirrers or bubbling by compressed air. The lime content of the slurry is governed by the proportioning of the original calcareous and argillaceous materials, as mentioned earlier. Final adjustment in order to achieve the required chemical composition can be made by blending slurries from different storage tanks, sometimes using an elaborate system of blending tanks. Occasionally, for example in the worlds northernmost plant in Norway, the raw material is a rock of such composition that it alone is crushed and no blending is required. Finally, the slurry with the desired lime content passes into the rotary kiln. This is a large, refractory-lined steel cylinder, up to 8 m (or 26 ft) in diameter, sometimes as long as 230 m (or 760 ft), slowly rotating about its axis, which is slightly inclined to the horizontal. The slurry is fed in at the upper end while pulverized coal is blown in by an air blast at the lower end of the kiln, where the temperature reaches about 1450 C. The coal, which must not have too high an ash content, deserves a special mention because typically 220 kg (500 lb) of coal is used to make one tonne of cement. This is worth bearing in mind when considering the price of cement. Oil (of the order of 125 litres (33 US gallons) per tonne of cement) or natural gas were also used, but since the 1980s most oil-fired plants have been converted to coal, which is by far the most common fuel used in most countries. It is worth noting that, because it is burnt in the kiln, coal with a high sulfur content can be used without harmful emissions. The slurry, in its movement down the kiln, encounters a progressively higher temperature. At first, the water is driven off and CO2 is liberated; further on, the dry material undergoes a series of chemical reactions until finally, in the hottest part of the kiln, some 20 to 30 per cent of the material becomes liquid, and lime, silica and alumina recombine. The mass then fuses into balls, 3 to 25 mm (1/8 to 1 in.) in diameter, known as clinker. The clinker drops into coolers, which are of various types and often provide means for an exchange of heat with the air subsequently used for the combustion of the pulverized coal. The kiln has to operate continuously in order to ensure a steady regime, and therefore uniformity of clinker, and also to reduce the deterioration of the refractory lining. It should be noted that the flame temperature reaches 1650 C. The largest existing kiln in a wet-process plant produces 3600 tonnes of clinker a day. Because the manufacture of cement by the wet process is energy intensive, new wet-process plants are no longer built. In the dry and semi-dry processes, the raw materials are crushed and fed in the correct proportions into a grinding mill, where they are dried and reduced in size to a fine powder. The dry powder, called raw meal, is then pumped to a blending silo, and final adjustment is now made in the proportions of the materials required for the manufacture of cement. To obtain a uniform and intimate mixture, the raw meal is blended, usually by means of compressed air inducing an upward movement of the powder and decreasing its apparent density. The air is pumped over one quadrant of the silo at a time, and this permits the apparently heavier material from the non-aerated quadrants to move laterally into the aerated quadrant. Thus the aerated material tends to behave almost like a liquid and,

by aerating all quadrants in turn for a total period of about one hour, a uniform mixture is obtained. In some cement plants, continuous blending is used. In the semi-dry process, the blended meal is now sieved and fed into a rotating dish called a granulator, water weighing about 12 per cent of the meal being added at the same time. In this manner, hard pellets about 15 mm (1/2 in.) in diameter are formed. This is necessary, as cold powder fed direct into a kiln would not permit the air flow and exchange of heat necessary for the chemical reactions of formation of cement clinker. The pellets are baked hard in a pre-heating grate by means of hot gases from the kiln. The pellets then enter the kiln, and subsequent operations are the same as in the wet process of manufacture. Since, however, the moisture content of the pellets is only 12 per cent as compared with the 40 per cent moisture content of the slurry used in the wet process, the semi-dry-process kiln is considerably smaller. The amount of heat required is also very much lower because only some 12 per cent of moisture has to be driven off, but additional heat has already been used in removing the original moisture content of the raw materials (usually 6 to 10 per cent). The process is thus quite economical, but only when the raw materials are comparatively dry. In such a case the total coal consumption can be as little as 100 kg (220 lb) per tonne of cement. In the dry process (see Fig. 1b), the raw meal, which has a moisture content of about 0.2 per cent, is passed through a pre-heater, usually of a suspension type; that means that the raw meal particles are suspended in the rising gases. Here, the raw meal is heated to about 800 C before being fed into the kiln. Because the raw meal contains no moisture to be driven off and because it is already preheated, the kiln can be shorter than in the wet process. The pre-heating uses the hot gas leaving the kiln. Because that gas contains a significant proportion of the rather volatile alkalis) and chlorides, a part of the gas may need to be bled off to ensure that the alkali content of the cement is not too high. The major part of the raw meal can be passed through a fluidized calciner (using a separate heat source) introduced between the pre-heater and the kiln. The temperature in the fluidized calciner is about 820 C. This temperature is stable so that the calcination is uniform and the efficiency of the heat exchange is high. A part of the raw meal is fed direct into the kiln in the usual manner but, overall, the effect of the fluidized calciner is to increase the decarbonation (dissociation of CaCO 3) of the raw meal prior to entry into the kiln and thus greatly to increase the kiln throughput. What is probably the largest dryprocess plant in the world produces 10 000 tonnes of clinker a day using a kiln 6.2 m (20 ft) in diameter and 105 m (345 ft) long. In the U.S. more than 80% of cement production uses the dry process. It should be stressed that all processes require an intimate mixture of the raw materials because a part of the reactions in the kiln must take place by diffusion in solid materials, and a uniform distribution of materials is essential to ensure a uniform product. On exit from the kiln, regardless of the type of process, the clinker is cooled, the heat being used to preheat the combustion air. The cool clinker, which is characteristically black, glistening, and hard, is interground with gypsum in order to prevent flash setting of the cement. The grinding is done in a ball mill consisting of several compartments with progressively smaller steel balls, sometimes preceded by passing through a roll press. In most plants, a closed-circuit grinding system is used: the cement discharged by the mill is passed through a separator, fine particles being removed to the storage silo by an air current, while the coarser particles are passed through the mill once again. Closed-circuit grinding avoids the production of a large amount of excessively fine material or of a small amount of too coarse material, faults often encountered with open-circuit grinding. Small quantities of grinding aids such as ethylene glycol or propylene glycol are used. Information about grinding aids is given by Massazza and Testolin. The performance of a ball mill can be improved by pre-grinding the clinker in a horizontal impact crusher. Once the cement has been satisfactorily ground, when it will have as many as 1.1 10 12 particles per kg (5 1011 per lb), it is ready for transport in bulk. Less commonly, the cement is packed in bags or drums. However, some types of cement, such as white, hydrophobic, expansive, regulatedset, oil-well, and high-alumina, are always packed in bags or drums. A standard bag in the United Kingdom contains 50 kg (110 lb) of cement; a US sack weighs 94 lb (42.6 kg); other bag sizes are also used. Bags of 25 kg are becoming popular.

Except when the raw materials necessitate the use of the wet process, the dry process is used nowadays in order to minimize the energy required for burning. Typically, the burning process represents 40 to 60 per cent of the production cost, while the extraction of raw materials for the manufacture of cement represents only 10 per cent of the total cost of cement. Around 1990, the average energy consumption in the United States for the production of 1 tonne of cement by the dry process was 1.6 MWh. In modern plants, this figure is much reduced, being below 0.8 MWh in Austria.Electricity consumption, which accounts for some 6 to 8 per cent of total energy used, is typically of the order: 10 kWh for crushing the raw materials, 28 kWh in the raw meal preparation, 24 kWh in burning, and 41 kWh in grinding. The capital cost of installation of a cement plant is very high: nearly US$200 per tonne of cement produced per annum. In addition to the main processes, there are also other processes of manufacture of cement, of which one, using gypsum instead of lime, perhaps deserves mention. Gypsum, clay and coke with sand and iron oxide are burnt in a rotary kiln, the end products being Portland cement and sulfur dioxide which is further converted into sulfuric acid. In areas where only a small cement production is required or where investment capital is limited, a vertical kiln of the Gottlieb type can be used. This fires nodules of raw meal and fine coal powder combined, and produces agglomerated clinker which is then broken up. A single kiln, 10 m (33 ft) high, produces up to 300 tonnes of cement a day. China used several thousand of such kilns, but now has a very large modern cement industry, producing 1000 million tonnes per annum.