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LECTURE NOTES - CEMENT TECHNOLOGY – I INTRODUCTION (1

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Introduction - Cement and its Manufacture The dictionary meaning of ‘cement’ is ‘to join’. Cement may be defined as adhesive substances capable of uniting fragments or masses of solid matter to a compact whole. Constructions are the backbone of civilization and development of society. From the time immemorial, constructions have evolved around some type of building blocks, joined together with some binder. Mud blocks, pieces of stone cut and dressed to size, or bricks are examples of ‘building blocks’, which are joined with, may be mud mortar (specially in climates with little or no rain), lime or cement mortar, or even bitumen, and laid one over the other to erect the structure. Seen in this perspective, cement is the essential binder of the present day constructions, and concrete, again made with cement, is the leading building material the world over. The use of cementing materials is very old. The ancient Egyptians used calcined impure gypsum. The Greeks and Romans used calcined limestone and later learned to make lime mortar by adding other substances like sand, crushed stone or brick, and broken tiles, to lime and water. From the chemistry viewpoint, present-day cements bear similarity with lime, which was known as the classical building material for many centuries. The process of lime manufacture and use in lime mortar involves the following steps; Burning of lime – CaCO3 → CaO + CO2 Slaking of lime – CaO + H2O → Ca(OH)2, and Carbonation, hardening – Ca(OH)2 + CO2 → CaCO3 + H2O. Burning of limestone to make quicklime means release of CO2 occupying 44 percent by weight. Such loss of mass makes quicklime porous. In contact with water, it absorbs water quickly, with considerable evolution of heat (280 cal/gm). This is hydration of lime. The resultant volume is 20 percent greater than that of the reactants. It gives rise to expansive forces. Depending upon the amount of water added slacked lime will have powdery appearance or highly dispersed paste, also known as ‘milk of lime’. The particles of hydrated lime are extremely fine and develop cohesive forces. Upon drying, it will harden and develop strength; which is not very high – may be of the order of 30 – 40 kg/cm2. The actual hardening of lime mortar is completed on carbonation with atmospheric CO2. Silica (SiO2), as obtained in natural rocks and stones, occurs mostly in crystalline form – as in quartz. In crystalline form, Silica is very stable and non-reactive. When heated to high temperature, even the ordinary quartz variety of silicon becomes chemically reactive. In a silicacontaining aqueous solution mixed with lime, a precipitate forms rapidly, giving rise to a ‘gel’-like mass of colloidal dimensions having cohesive forces. Around 1756, it was discovered that lime made from limestone containing a considerable proportion of clayey matter gave better results. This was the beginning of most important advances in the knowledge of cements. It was soon recognized that if a mixture of lime and silica, in finely ground form and in required proportions, is heated to sufficiently high temperatures, calcium silicates having hydraulic properties (i.e. capable of hydrating and hardening in contact with water) are formed. This is the basis of cement manufacture. Various Unit Operations in Cement Manufacture Normal Portland cement is defined as a synthetic mixture of calcium silicates formed from a molten matrix from a suitably proportioned and homogeneously prepared mixture of calcareous and argillaceous components. Accordingly, Portland cement is made primarily from a calcareous material, such as limestone or chalk, and from alumina and silica found as clay or shale. The manufacturing process involves the following principal stages;

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Mining of raw materials, size reduction and grinding, Mixing them intimately in the desired proportions, Burning in a large rotary kiln at a temperature up to about 1450oC, when the materials sinter and partially fuse to form balls, known as ‘clinkers’, Cooling of the clinker and storage, Grinding of the clinker along with gypsum to a fine powdery form. This is ‘cement’. Cement is stored in suitable containers like 50 kg bags, one-tonne ‘jumbo’ bags, or tankers, for dispatch by road, rail or sea route to the point of use.

The above description is rather simplistic, and in actual practice, considerable innovations take place. Take for example the raw materials. Clay may not be separately added and SiO2 obtained from the coal ash and what is contained in limestone may be sufficient. Alumina and iron oxides are needed to act as flux in the clinker formation process, and additives like Bauxite and/or iron ore may have to be separately incorporated in the raw mix. Finish grinding of clinker may not be with only mineral gypsum but other forms of calcium sulphate may be used. Supplementary cementitious materials like fly ash, burnt clay or granulated blast furnace slag can be added at the stage of cement grinding to produce ‘blended’ or ‘composite‘ cements. Depending upon the raw materials being mixed and fed to the kiln in dry form or as slurry with water, different ‘processes’ of cement manufacture are adopted. Finally, considerable engineering judgment and input of material science in all stages of various unit operations are required to optimize the energy requirement, meet demands of environmental restrictions and quality of the final product. All these aspects will be covered in the lectures to follow. Size of the Cement Industry in India. India is the second largest cement producer in the world. The installed production capacity at present is nearly 165 million tonnes (MT) annually. This comprises about 155 MT from ‘large’ plants (93 percent of the total) and another 11 MT from small-scale ‘mini’ cement plants. With 85 percent capacity utilization, it is capable of producing nearly 136 MT per year, nearly 95.5 percent of production being contributed by the large plants. Nearly 60 percent of the production is consumed by the housing sector, another 20 percent in infrastructure, and balance 20 percent in ‘industry and others. About 10 MT of cement and clinkers produced in India are exported. The growth of the Indian cement industry, in terms of total capacity and production, number of units of large plants (128) and kilns (164), average kiln capacity ( > 2000 tpd), proportion of efficient and modern dry process kilns (96 percent), have been gradual over the years. The figures given in brackets are for the year 2004/05.The rate of growth (CAGR) has been in excess of 8 percent per year, which is projected to be sustained in the decades to come. The trend is depicted in Figure I below. The global scenario The total production of cement world-wide is of the order of 2000 MT. The data on production by seven leading cement manufacturing countries (2003 data) is given in Table I below. Table I indicates that production in China is at the top position and India occupies the second position, as already mentioned. One measure of economic development in any country is the ‘per capita cement consumption’. Starting with a value of 57 kg / head in 1994/5 in India, the current value of per capita cement consumption of about 130 kg will appear impressive, but it is much lower than 723 kg in case of China, or even about 300 kg as the world average. This provides impetus to the continuous growth of Indian Cement Industry, to make available the large quantities of cement needed for the infrastructure sector – housing, roads, railways and ports, power generation and other industrial activities.

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TABLE I Cement Production in MT – 2003 Data Country China India USA Japan Korea Spain Italy Others Total Production 862 121.4 92.8 73.8 59.1 44.8 43.5 656.6 1954 % of Total 44.1 6.2 4.7 3.8 3.0 2.3 2.2 33.6

Reference Books

1. A. M. Neville, Properties of Concrete, Longmans, 2. Robert G. Blezard, The History of Calcareous Cements, in Lea’s Chemistry of Cement
and Concrete, 4th ed., Butterworth. 3. W. Czernin, Cement Chemistry and Physics for Civil Engineers, Chemical Publishing Co., New York. 4. Cement Industry Data book, Cement Manufacturers Assn., New Delhi, 5. World Cement Directory, CEMBUREAU, -------

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VARIOUS PROCESSES OF CEMENT MANUFACTURE (1)
Classification of the process of cement manufacture is made on the basis of the state of the raw materials as they are fed to the kiln for Pyroprocessing. The raw materials of calcareous and argillaceous compositions are to be obtained from the nature, crushed, ground and blended together with any other additives or correcting materials (to be described later) before they are fed to the kiln. The Wet Process – The earlier practice of cement manufacture was based on ‘wet’ process, in which the kiln feed entered the kiln in the form of slurry, with moisture content varying from 30 to 50 percent by mass. Such practice was necessitated if the raw materials had high moisture content. The materials in the slurry form could be blended more uniformly and dust losses were lower. Energy required for grinding was relatively lesser, but more thermal energy was required because of extra heat required to evaporate the water. For each 1% moisture content in the raw mix, additional 33 kcal/kg of fuel is required. With the advent of more efficient ‘dry’ process plants (described later), not many wet process cement plants are in operation at present. Many wet process plants of old vintage in different countries have either been ‘converted’ to dry process or simply shut down. Since most of the discussion in this course will center on dry process, some description of wet process of cement manufacture is given here. The process flow sheet shown in Figure I may please be seen. Limestone, after necessary size reduction, is fed in a ball mill with the clay dispersed in water. Limestone is ground to the fineness of flour and the resultant slurry is pumped to storage tanks. When softer raw materials like chalk and clay are used, they are broken up and dispersed in water in wash mills. The two mixtures are pumped to mix in desired proportions, blended and stored in storage tanks. The resultant slurry would have solid particles of > 90µm (micron) size not exceeding 2 percent, and moisture content between 35 to 50 percent. The sedimentation of suspended solids in the slurry storage tanks is prevented by mechanical stirrers or by compressed air, before it enters the kiln. The wet process kilns were of greater length than the dry process, to accommodate the additional dehydration zone. The Dry Process - As the name implies, in this process the kiln feed enters the kiln in dry powder form. The raw materials are crushed and fed in correct proportions into a grinding mill, where they are dried and reduced in size to a fine powder. The raw meal is blended in a blending silo, before entering the kiln. This is called a long dry process kiln. In most modern plants, the raw meal is passed through a suspension preheater, with or without a precalciner having a secondary firing system (see Figure I). Since drying, decarbonation and calcinations of the raw meal take place outside the kiln, the length of the kiln is considerably reduced, and capacity of production increased. Kilns with preheaters and prcalcinators will be described in greater details later on. The Semi-dry Process - This process is adopted sometimes, when the moisture content of the raw meal is so high that it can not be economically dried by the waste heat from the kiln system. The pulverized kiln feed prepared as in the dry process is first pelletised into small nodules in a granulator, by means of addition of about 10 -15 percent water. The nodules are then fed onto a traveling grate and heated by the exit gases from the rotary kiln. The material gets partially calcined and fed to the rotary kiln down a chute. This is called grate process or Lepol kiln (see Figure 2 above). Instead of granulating the kiln feed, some plants use filter press cakes to feed the kiln. The wet-kiln feed slurry is first pressed through large presses for removal of free water before the filter cakes are fed to the rotary kiln. The fuel consumption in Lepol kilns is of the same order as in preheater and precalciner kilns. The dust content in kiln exit gases is reduced as it passes through the feed bed. The clinkers formed are of uniform size. However, the output rates are lower than preheater/precalciner kilns.

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The changing profile of different types of cement plants over the years in India is indicated in Table I below.

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Classification as per Type of Kilns The discussions so far have been in terms of rotary kilns for cement manufacture, which are more common. For example, nearly 96 percent of total cement production in India is through dry process rotary kilns. However, in areas where only a small production of cement is envisaged may be due to limitations of limestone availability, or the market and local demand for cement being limited, or difficult terrain conditions making movement of heavy plant and machineries difficult - small ‘mini’ cement plants employing vertical shaft kilns (VSK) are adopted. Nodules of raw meal along with fine coal powder are prepared and fed from the top of the vertical kiln. The

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7 50 51265 53. In India. at the turn of the 20th century. 2. Butterworth.1 74 1970 93 38441 69. of Dry kilns Installed capacity (t/d) % of total kilns Total kilns Reference Books 1950 32 9151 97. there are about 365 mini cement plants. rotary kilns of smaller capacities can also be adopted.7 1960 70 25001 94. Properties of Concrete. Lea’s Chemistry of Cement and Concrete. Rotary kilns came later. 4th ed. most being of vertical shaft kiln type. producing about 6 MT annually. Longmans..1 9 5500 5. of Semi-dry kilns Installed capacity (t/d) % of total kilns No. TABLE I Types of Cement Plants in India ↓ Items / Year → No. VSK’s were use in the Victorian era. the number is in thousands. The capacity is required to be less than 600 tpd. The first cement kilns were static vertical kilns.4 3 1200 4.5 8 5000 9 18 11865 21. Because of the colour of the feed..5 119 1983 95 39641 41.5 1 300 1.3 1 250 2. A. it is called black meal process.heating takes place on a grate at the bottom. The total installed production capacity is nearly 11 MT. although in practice. Of course. M. when a kiln with a revolving cylinder lined with firebricks for manufacture of cement was patented in 1877. of wet kilns Installed capacity (t/d) % of total kilns No. although many of these are being abandoned now. they are of much smaller capacity. 6 . In China.2 154 1995 61 25746 12 8 5244 2 97 188435 86 166 2001 32 13910 5 8 5260 2 117 282486 93 157 2004 30 12780 3 8 4135 1 126 359727 96 164 33 1. Neville.

Sodium (Na2O) and Potassium (K2O) oxides. α–quartz. Chromium etc. Cement Chemistry Notations It is customary to abbreviate common oxides to single letters. silicon (SiO2).g.g. The total list is given below. and the compound. Boron (B2O3). e.g.SiO2. Among the main oxides. Silica. C for CaO. being made from calcareous and argillaceous raw materials. CaO occurs as Calcite (CaCO3) in limestone. in the environmental issues. Phosphorous (P2O5). Crystobalite and Tridymite). aluminum (Al2O3) and iron (Fe2O3). Primary among them are ‘alkalis’ . Calcium Sulphate Hydration Products Calcium Silicate Hydrates Notation C S A F M K N T P Ć S H CS C-S-H 7 .CHEMISTRY OF CEMENTS (3) Chemical Composition and Phases in Portland cement Portland cement. SiO2 exists naturally in the pure state as different crystalline polymorphs (e.0 percent) can make profound difference in the manufacturing process. rather than the oxides. reduction in solid volume and the amount of CO2 emitted to the environment. Ca3SiO5 is expressed as 3CaO. Al2O3 and Fe2O3 are not essential for the hydraulic properties. CaCO3 → CaO + CO2 We had taken note of this reaction in connection with lime manufacture. SiO2 occurs as aluminosilicates in clay or shale.SiO2 and then expressed as C3S. which are really present as sulphates. Poorly crystalline or amorphous forms are also found as in Opal and Flint etc. It does not mean that the constituent oxides exist separately within the structure of the phases. Titanium. whose presence even in small amounts (<1. to keep the thermal energy required to manageable economical levels. as to be expected. or the properties of the cement. composed of compounds of oxides of calcium (CaO). It decarbonates at about temperature of 680OC and above. and MgO. It is an important reaction in cement manufacture. originating from impurities in the main raw materials. is. both in terms of thermal energy consumed. but their presence is essential as flux in the hottest zone of the kiln in cement manufacture. One exception is MgO. for example Ca3SiO5 is first written as 3CaO. Minor components are those. It is customary to express the chemical formulae of the compounds in cement as the sum of the oxides e. Cement Chemistry Notations Item Oxide Cement / Clinker CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O TiO2 P2O5 Others CO2 SO3 H2O Gypsum. These will be discussed later in this Course. Others include Chlorides (Cl -) Manganese (MnO2).

The melting point of pure CaO is about 2750OC. Insoluble residue is what is insoluble in hydrochloric acid. These are best studied in terms of phase diagrams. C2S and C3S. CO2 in the limestone filler when permitted to be added. C3S2. or any adulteration. Al2O3 – 5 to 8 %.1 0.0 0.60 to 65 %. are permitted to be added in composite cements.C2S ultimately transforms to β – form at 630OC. C2S has a number of polymorphs. At still lower temperature transformation to γ .4 19.24 2. the values for CaO content could be somewhat lower. On cooling from higher temperatures. which are mostly acid-insoluble. α .9 – 2. Proportion of MgO in some cases can be higher. When industrial wastes like fly ash. any water content in gypsum not driven out during manufacture. The System CaO – SiO2 The equilibrium phase diagram for the system CaO – SiO2 is shown below. indicate free quartz.5 – 1.43 – 0. which could be due to any moisture or CO2 attracted during storage. and that of SiO2 is about 1698OC.7 – 1.80 0.1 – 3.7 0. β – C2S can be stabilized to low temperatures by quenching. which is not hydraulic. The Phases in Portland cement Before the phases present in cements are identified. depending upon the quality of limestone. or by forming solid solutions with a large number of oxide impurities like boric oxide (B2O3) or Phosphorous pentaoxide (P2O5) and MgO. It contains four binary compounds – CS. the values of IR are higher. Fortunately.2 2.14 – 0. Chemical Composition of Cement (Typical) Item CaO SiO2 Al2O3 Fe2O3 K2O Na2O SO3 MgO Free Lime Loss on Ignition (LOI) Insoluble residue (IR) Amount. nor are they formed during cement manufacture. 8 .2 – 66. In Indian cements.8 – 1.2 4.5 – 3. ternary and quaternary systems.1 – 6. takes place. the range of typical chemical composition of ordinary Portland cement (taken from a UK source) is as given in the Table below. % 63. presence of each other lowers the liquidus temperature.7 Two terms in the above composition need explanation. CS and C3S2 are not hydraulic. SiO2 – 19 to 22 %. CH After addition of gypsum (or other form of calcium sulphate) ≈ 5 %. What is described here is a simple explanation. impurities from rock gypsum. or insoluble in adulterants. CaO . as binary.5 – 22.C2S. Out of the four phases. However.4 0.Calcium Hydroxide Typical Chemical Composition – The cement clinker has typically a composition of. the upper limit being 5%. let us consider how the oxides interact at different compositions and different temperature.3 0. Loss on ignition is the loss of mass when heated to 1000OC. and Fe2O3 – 3 to 5 %.

all other phases are hydraulic. which are. 9 . CaO – Al2O3 System The relevant phase diagram is reproduced below. its decomposition to C2S and CaO does not occur on cooling. C3S exhibits a range of metastable modifications between room temperature and 1100OC. CA. Presence of Al2O3 (and Fe2O3) lowers the liquidus temperature of CaO and helps in reducing the burning temperature for cement manufacture. This system contains stable phases C3A.C3S is the most abundant phase. CA2 and CA6. Rhombohedra ( R ) → Monoclinic ( M ) → Triclinic ( T ) forms. Although a lower limit of solubility exists for C3S at about 1250OC. C12A7. Except CA6.

This liquid phase is containing the aluminous components.SiO2 or expressed as C2S.Al2O3 – Fe2O3 We can now take a look at the phases present in Portland cement.C3S. the total impurity oxides 10 . C2S and a liquid phase of composition Lc shown in the figure below.If CaO is also present x is fixed at 0. the composition of Belite is modified by incorporation of foreign ions. C3S content typically varies from 30 to 48 percent. C3A and C12A7. Gypsum is used to control the rapid hydration of C3A – phase and initial set. Al3+ and Fe3+ ions in solid solutions. The final phase assemblage obtained on cooling is more complex.48 and 0. Belite – It is dicalcium silicate – Ca2SiO4.3% SiO2. CA2 and CA6 – phases may be present in those with high alumina content. In industrial clinkers. C3A is formed. More than 95% of the composition of Portland (and aluminous) cements comprise compounds containing CaO. C2S. Al2O3 and iron oxides.1% CaO and 34. Pure C2S consists of 65.7% CaO and 26.9 % SiO2.Ca3SiO5. SiO2.SiO2 or expressed as C3S. which is a quaternary system in the four oxides. Alite – It is tricalcium silicate .48. The System CaO – Al2O3 – Fe2O3 The most significant phase in this system has a composition Ca2 (Alx Fe1-x)2O5. C2S. There are no quaternary phases and at equilibrium. The melt. up to about 4. all the four phases . C12A7 and CA. giving a composition close to C4AF – called the ‘Ferrite’ phase. which is written as 3CaO. Ternary System CaO – SiO2 – Al2O3 Lime – rich binary phases comprise nearly 90 % of cement composition. In industrial clinkers. C3A and C12A7 are obtained. In Indian cements. Pure C3S consists of 73. besides minor components. The equilibrium phase assemblage at the burning temperature for the cement manufacture consists of C3S. In practice. on cooling would crystallize to give C2S. the total of impurity oxides is of the order of 3 to 4 percent. CA and C12A7 are predominant phases in aluminous cements. usually Al2O3 and Fe2O3. the composition is modified by incorporation of Mg2+. which is written as 2 CaO. The Quaternary System CaO – SiO2 . This phase contains a number of other ions in solid solution. It will consist of C3S. Fe3+ also dissolves in C3A. C3A and a melt.7. which is responsible for early hydration and setting. any mix composition will crystallize the following four phases. where x is between 0.5% at 1325oC.For compositions common in ordinary Portland cement manufacture. The crystal structure of cement minerals have been studied in details. which is not discussed here.

where x is between 0 and 0.Al2O3. It is based on the following steps.7544 C3S. It is to be noted that in Portland cements.7. 11 . Calculation of Amount of Different Phases Chemical analysis of cement or clinker is obtained in terms of oxides. The substitution is substantial – it could be 13 percent for cubic and 20 percent for orthorhombic modification of the crystal structure.0785 Fe2O3.0710 CaO – 7.0683 Al2O3 + 1. 21 percent Al2O3 and 32.6504 Al2O3 – 1. Ferrite phase – It is tetra calcium alumino ferrite – Ca2AlFeO5. Assume balance of Al2O3 occurs in C3A. Fe3+.   Equilibrium may not be maintained during cooling. the total of C3S + C2S content is between 70 to 80 percent. H.3% CaO and 37. New York. 4th ed. It is implied that all the MgO occurs as periclase.1 percent CaO. For cements. Reference Books 1. Na+ and K+. because minor oxide components are ignored.7 SO3) in place of CaO.being 4 to 6 percent. Reinhold.  C4AF = 3. The ferrite phase makes up about 5 to 15 percent of ordinary Portland cement clinkers.7% Al2O3. Aluminate phase – It is tricalcium aluminate – Ca3Al2O6. Chemistry of Portland Cement. Lea’s Chemistry of Cement and Concrete. and Composition of clinker phases differ from the pure compounds. as shown in the example given above. The formulae for clinkers are. Bogue.6920 Fe2O3. as explained before.. or abbreviated as C4AF. Mn3+ can replace all the Fe3+ ions or up to 60 percent of Al3+ ions.3. C2S. 2. • • • • Assume that the compositions of the four major phases are C3S.2 percent. Pure C4AF contains 46.6024 SiO2 – 6.0432 Fe2O3. C2S = . Ferrite phase can be prepared with any composition in the solid solution series Ca2 (Alx Fe1-x)2O5. C2S content typically varies from 27 to 45 percent. The total of four phases calculated plus free lime will not add up to 100 percent. Pure C3A contains 62. also written as 4 CaO. which is written as 3 CaO. Estimation of the relative proportions of the phases is accomplished by the procedure known as ‘Bogue calculation’.The composition is substantially modified by variation in A/F ratio and incorporation of foreign ions like Mg2+.Fe2O3. Deduct from the CaO content.6024 SiO2 + 5.7187 Al2O3 – 1. Limit of K2O substitution is ≈ 1. = 2. The composition is modified by incorporation of foreign ions like Si4+. In Indian cements.5.9 percent Fe2O3.  C3A = 2. Si4+ and Ti4+. C3A and C4AF. C3A content typically varies from 4 to 10 percent. Assume that Fe2O3 occurs in C4AF. perhaps closer to 75 percent.4297 Fe2O3. C4AF is a particular form for x = 0.8675 SiO2 – 0. R. Butterworth. the amounts attributable to C3A and C4AF and solve two simultaneous equations to calculate the amounts of C3S and C2S.0710 CaO + 8. In Indian cements. The above gives the potential phase composition and differs from the true phase composition because.   C3S = 4. put (CaO – 0.Al2O3 or expressed as C3A.

Cement Chemistry. (Liquid)–K2SO4 → (vapour)-K2SO4. The reactions occurring during the burning of the raw meal and clinker formation are summarized in the Table and the Figure below indicates the respective temperatures.e. W. α -C2S → β and/or γ . precipitation of alite from melt. I. Both are taken from Lea’s ‘Chemistry of Cement and Concrete’. Examples and comment CaCO3 → CaO + CO2. polymorphic changes occurring during cooling. H. Taylor. F. C2S. 3 CaO + SiO2 → Ca3SiO5. and the features of the kiln – cooler system are important. Summary of Reactions Occurring during Clinker Formation Reaction type Decomposition Diffusion Melting Liquid phase sintering Polymorphic transformation Evaporation / condensation In summary. The mineralogical state of the clinker obtained at the peak firing temperature becomes thermodynamically unstable during the cooling stage. evaporation and condensation of alkali sulphates. 12 . It is essential to approach phase equilibrium at clinkering temperatures. fineness and homogeneity. solid-state reaction between components Formation of C-A-F-S eutectic at 1338OC between C3S. London. in which the reactants are dissolved. Academic Press. --------- CLINKER FORMATION (1) For satisfactory clinker formation. the physical state i.3. we may note. C3A and C4AF. The chemical composition of the raw materials and their proportions. Below 1300OC – The reactions that take place are.C2S. Rate of cooling and quenching are important. one or more volatile substances form in the course of reaction 2 CaO +SiO2 → Ca2SiO4. the states of both heating (to a high temperature) and subsequent cooling should be accomplished in a satisfactory manner.

0 x % Al2O3+ 2. Role of Mineralisers and Flux – It has been discussed how the presence of Al2O3 and Fe2O3 in the raw mix. e.8SiO2 + 1.95 x % Al2O3+ 2.0 to 4. constitute a cheap source of fluxes lowering the thermal energy required in cement manufacture. it is typically in the range of 0.7SO3) in place of CaO. At 1338oC. Silica ratio (SR) = SiO2 / (Al2O3 + Fe2O3). SR is typically in the range of 2. Na2O and K2O also act as flux. in which much of the belite (C2S) and nearly all the CaO react. When the ratio of A/F is > 1.0. In Portland cements.98.65Fe2O3.2 x% Fe2O3 + % MgO + % Na2O + % K2O. the CaO content is given by. Moduli Values – In the manufacture of Portland cement.0. structure at up to 700OC. Some other useful limits are.38.0. d.900OC.is called ‘lime saturation factor’ (LSF).66 to 1. b. AR determines the quantity of liquid formed at low temperature.02.38 and the amount of MgO present is < 2 percent.8SiO2 + 1. Alumina ratio (AR) = Al2O3 / Fe2O3.38. the quantity of liquid is theoretically maximum at AR of 1.1 x% Fe2O3 + % MgO + % Na2O + % K2O. it is desirable that C3S content is optimized and the free (uncombined) lime content is minimized. For such a situation. the amount of flux present at different temperatures is given by the formulae. Decomposition of calcite at 680OC and above. For LSF> 1.0 to 3. During cooling – The liquid crystallizes giving mainly aluminate and ferrite. Between 1300 – 1450OC – Clinkering. The material nodulises to form clinker.92 to 0. Please note that the above formula is for clinkers. CaO The ratio -------------------------------------------. some 20 to 30 percent of the mix is liquid.  Flux at 1450OC = 3. II.18Al2O3 + 0.  Flux at 1338OC = 6. The value of AR can vary between 1.18Al2O3 + 0. 13 . By 1450OC. although specifications allow a range of 0. Al2O3 and Fe2O3 form a liquid melt. to form alite (C3S). although not essential to the constitution of Portland cement.  Flux at 1400OC = 2. Much of belite and nearly all the lime react in the presence of the melt to form alite. Initial combination of calcite or lime from it with activated quartz and Al2O3 and Fe2O3 ≈ 700 . use (CaO – 0. Decomposition of clay minerals ≈ 900OC.65Fe2O3 LSF largely shows the proportion of alite and belite in the clinker. Increase in SR means proportion of liquid is lower and the clinker becomes difficult to burn. A melt is formed mainly from aluminate and ferrite phases. Where the ratio A/F is < 1. III. Belite forms at 900 – 1200 OC.25 x% Fe2O3 + % MgO + % Na2O + % K2O. Activation of silicates through removal of water and changes in the crystal c. for cement. 2. free lime will be present.a. Other volatiles like MgO. Polymorphic transformations of the alite and belite occur. CaO = 2.

Presence of chlorine (Cl-) in the cement invites opposition from the users.5 x % Al2O3 – 5. the coating formation is inadequate and refractories are likely to be damaged. Such levels of impurity-induced defects can take place in the C3S and C2S phases in industrial clinkers The role of mineralisers can be summarized under the following headings. Cement Chemistry. which increase the activity of the clinker phases. the viscosity and surface tension of the liquid are modified. New York. Lea’s Chemistry of Cement and Concrete. Formation of liquid may take place at lower temperatures also due to presence of sulphates and carbonates. H.and F-. H.5%addition was found to be as follows. ------- 14 . therefore. it is known that the activity of a single crystal may be enhanced by introducing ‘defects’ in the crystal structure. enabling its formation at temperature < 1250OC. facilitate formation of clinker having adequate properties with lower grade limestone or at lower temperatures. 2. Mineralisers – These are minor components or additives in the raw mix in small amounts. the effectiveness to aid C3S formation at 1350OC. Taylor. Hydraulic activity – The reactivity of clinker minerals (alite. Barium increases the reactivity of C2S phase by substitution in the crystal structure. Reference Books 1. Somewhat higher level may be required in case of difficult raw materials. The desirable range could be about 19 to 26 percent. Chromium and Titanium Oxide can increase the sizes of alite and belite crystals. in all such cases. Flux at 1338OC = 8. 4th ed. to prevent other adverse effects. W. but not exceeding 28 – 29 percent. R. which have low melting point eutectics (≈ 800 . increase in C3S content or lower the clinkering temperature. Basalt and Barite are among the mineralisers used in the Indian cement industry. which contribute to the reactivity of the phases. liquid formation is assisted by traces of halides like Cl.900OC). Fluoride addition has the unique combination of acting as a flux. However. Fluorspar. In cement manufacture. belite) are modified by solid solution and/or crystal symmetry effects (defects). Butterworth.. 3. Academic Press. London. Fluxing action – Temperature of first formation of liquid are reduced. Chemistry of Portland Cement. Extrinsic defects can be induced in the clinker phases by crystallochemical substitution forming solid solution. and crystal morphology is modified. Fluorogypsum. Excessive high flux levels at 1338OC will lead to ring formation at the point where the kiln feed enters the burning zone. Bogue. CuO > ZnO > MnO2 > SnO2 > PbO. the amount has to be controlled very carefully. Among transition metal oxides. If the level of flux is less than 19 percent. From material science. Use of fluorspar has been reported to reduce the amount of free lime. reducing the viscosity and surface tension of the liquid and enhancing the thermodynamic stability of C3S. because of risk of corrosion of reinforcing steel. It is.22 x% Fe2O3 + % MgO + % Na2O + % K2O. Reinhold. necessary to ensure the optimum level of flux by careful design of the raw mix. lowering the temperature of melt formation. F. and more particularly. Phase relations – The relative thermodynamic stabilities of the clinker minerals are changed due to solid solution effects. at 0.

which is strong in compression. are calcium silicate hydrate with a probable composition of C3S2H3 (abbreviated as C–S–H). C3S and C2S. as is apparent from the figure below. however. 15 . The physical behavior of hydrating cement is similar to those of the two calcium silicates. Much of performance of cement is in terms of setting. hardening and strength development as well as durability under the service condition. The various types of cement are either in terms of levels of performance. or based on its chemical composition. after hardening. The corresponding masses involved are: 100 + 24 → 75 + 49. when mixed with water. The rates of hydration of the phases are. For C3S – C3S + 6H → C3S2H3 + 3 Ca(OH)2. Relatively impermeable composite results. The term setting denotes a rather sudden loss of plasticity of the paste and conversion to a solid material. Hydration Reactions – Hydraulic hardening of Portland cements is primarily due to the hydration of calcium silicates but other phases like aluminates also participate in the process. The cement paste sets and hardens as the hydration proceeds after contact with water. and C2S is the slowest to react. different. The solubility of hydration products in water being rather limited. C3A and C4AF phases have the highest rates of reaction. followed by C3S. the composite becomes stable and durable. The products of hydration of cement gradually fill the space between aggregate particles to give a continuous matrix. The products of hydration of cement are chemically the same as the products of hydration of the individual phases.TYPES AND PERFORMANCE CHARACTERISTICS OF CEMENTS (4) Cement is defined as ‘a hydraulic binder. and calcium hydroxide Ca(OH)2. which. The strength at this stage may not be much. forms a paste which sets and hardens by means of hydration reactions and processes and which. The term hardening denotes the development of hardness and strength following the setting of cement paste. The hydration product of calcium silicate phases. retains its strength and stability even under water’. The reactions are of the types.

For C4AF – Under comparable conditions the products of hydration of the ferrite phase are. y. whereas. In order to prevent this. C-S-H has the strength giving properties. and a more general description (CaO)x.For C2S – C2S + 4H → C3S2H3 + Ca(OH)2. with x and y having a range of possible values. The rate of strength development of cement depends upon the relative proportion of different phases present. but it is possible that a hexagonal C4AH12 crystallises out first and later changes to the cubic form. From the structural viewpoint.4 to 2. but C3S produces more than double the amount of Ca(OH)2. higher C3S content results in greater strength at early ages than when the C2S content is more. except through pozzolanic reaction (see later). The above equations indicate that both C3S and C2S require about the same amount of water for reaction. It indicates the molar ratio of C/S to be 3. Other factors like fineness of grinding are also important.(H2O). C-S-H is known to exist in variety of forms and composition. or some other form of calcium sulphate is added during grinding of cement clinker.7 being more probable. The corresponding masses involved are: 100 + 21 → 99 + 22. 1. The corresponding masses involved are: 100 + 40 → 140.SiO2. whereas Ca(OH)2 has no significant contribution towards strength. Role of calcium sulphate addition in cement The final form of calcium aluminate hydrate existing in hydrated cement is probably the cubic crystal C3AH6. In the presence of calcium sulphate. it is much lower – between 1. similar to those of C3A. approximate. 16 . gypsum. The relative rates of gain of strength for hydrates of different phases are shown in the figure below. which is called flash set. The composition of C-S-H indicated as C3S2H3 is. is more apt. more or less. at best. The reaction of C3A with water proceeds very fast and leads to immediate stiffening. For C3A C3A + 6H → C3AH6. For example. in hardened cement paste. although the rates differ.

S3.the amount of C3A directly hydrating to C3AH6 is considerably arrested. ½ H2O or calcium sulphate anhydrite. but the chloride content may exceed the value permitted in cement specifications. This is shown in the figure below. 2H2O). trisulphate ettringite formed initially reacts with the excess of C3A to form calcium -aluminate monosulphate hydrate (monosulphate) . The quantity mined is not enough for the entire cement production in the country and the distances involved are large in many cases. These may require washing to remove impurities. Chemical gypsum. In India. The rate of heat generated helps in monitoring different stages of hydration of cement and the setting process. (calcium sulphate dihydrate. which impedes further hydration. CaSO4. Following this peak. and calcium sulphoaluminate hydrate (ettringite) – C6A.H32 + 2C3A + 4H → 3 C4ASH12. till the third peak is reached. C6A. Marine gypsum from sea bed has high purity.. a dormant (induction) period follows. C3A + 3CSH2 + 26H → C6A. CaSO4. giving rise to the initial endothermic peak. which is responsible for the first peak.S3. Use of industrial wastes - 17 . mineral gypsum is mostly obtained from the mines in Rajasthan. which may be present as separate crystals or in solid solution with monosulphate. A hexagonal calcium aluminate hydrate. CaSO4. Alkali sulphate – mainly K2SO4 dissolves in water within seconds. due to reaction of C3A with ettringite. This is because of initial rapid release of Ca(OH)2 formed due to hydration of silicates leaves an outer layer of C-S-H. which indicates three peaks in the rate of hydration within first three days or so. The surface layer is broken down and the rate of hydration increase slowly till it reaches a second peak after some time – anything between four to ten hours. during which the cement paste is workable. C4AH19 also forms. During this period. The hydration of C3A before SO3 comes into reaction is accompanied by evolution of much heat. depending upon the cement characteristics. like phospho-gypsum and fluoro-gypsum obtained as waste products from chemical industries is used. Its purity (in terms of SO3 content) is limited. This stage lasts for about one to two hours. once SO3 is depleted. the rate of hydration again slows down. during which the rate of reaction is slow.H32. Immediately after contact with water. Other forms are calcium sulphate hemihydrate.H32 is formed first. formation of hydrate phases gets underway. The calcium sulphate added is usually in the form of mineral gypsum. Rate of heat evolution during hydration Hydration of cement is an exothermic reaction.S3. Ettringite is also called trisulphate. As hydration proceeds and the available calcium sulphate gets consumed. As sulphates control the hydration of C3A.C4ASH12 as the product of reaction. the products of hydration of individual cement grains come in contact with each other forming a network and setting takes place.

Loss on Ignition – 1. Blaine’s. to result in ‘blended’ or ‘composite’ cements. The glass content of Indian Fly ashes (20 – 35 percent) are lower than in other countries (70 – 90 percent) and. to give cementitious products. much of the Ca(OH)2 remains unreacted in pozzolanic reaction. Portland Pozzolana cement (Fly ash based) is specified in IS:1489 – Part I. Addition of 20 – 25 percent is common practice. is not hydraulic. With Indian fly ashes. to that extent. silica fume containing 85 to 90 percent silica in glassy form) can combine with equal mass of lime liberated by cement hydration. These are. 18 .Various industrial wastes are used in cement. • Unburnt carbon. Formation of C-S-H due to pozzolanic reaction manifest after the initial hydration of Portland cement . to form calcium silicate hydrates (C-S-H).may be 3 to 14 days after mixing with water. the reactivity are power. obtained from one source. CaO – 2 – 10 percent. Some of the industrial wastes used in cement are discussed below. SO3. And small amounts of MgO. Use of chemical gypsum for set control was mentioned above. TABLE I TYPICAL COMPOSITION OF INDIAN FLY ASH SiO2 – 52 – 60 percent. In addition. commonly measured as Loss on Ignition (LOI). Al2O3 . can be summed up in terms of five key parameters. and are comparable to other international specifications (Table 2). with the Ca(OH)2 liberated during hydration of silicate phases of Portland cement.5 – 14 percent. in presence of water. although C-S-H following hydration of C3S phase is visible after 24 hours. • Specific surface area. Siliceous pozzolanicity of fly ashes require that the SiO2 phase be in glassy form. unless collected dry. a pozzolana rich in content of active silica (for example. Na2O and K2O. It permits addition of 15 to 35 percent fly ash. Fly ash is obtained as fine particles in the exhaust flue gases in coal-fired thermal power stations. Such C-S-H differs in composition from that resulting due to hydration of the silicate phases in Portland cements. Reactivity goes up with fineness and can be improved by further grinding. which govern the performance of fly ash in cement and concrete. These are collected in the electrostatic precipitators and disposed of. Fe2O3 – 2 – 7 percent. Hydration reaction of fly ash in cement. CaO + SiO2 + H2O → C-S-H. in other words. The main requirements. Nearly equal masses of silica and lime combine. • Residue on 45µ sieve (325 mesh). and • Glass content. which are blended or interground with cement clinker and calcium sulphate.. but can combine with lime in the presence of water. • Moisture content. Fly ash Fly ash is a pozzolana. ettringite is formed rapidly and is observed from 5 hours up to 28 days. which in itself. either in dry or wet state.The pozzolanic reaction involves the active SiO2 component in fly ash combining. Typical chemical composition of Indian fly ashes is given in Table I.20 – 33 percent. The quality requirements are specified in IS: 3812 – Part I – 2003. primarily as additions. Others can be used as raw materials in the manufacture of cement clinker.

TABLE 2 SPECIFICATIONS FOR FLY ASH IN CEMENT AND CONCRETE (Values are %. Cement activity. max Blaine’s m /kg min.95% in BS 3892. % 2 2 ASTM C-618 European Specifications India. LOI (1 hour) max. max. max Free CaO. therefore. 45 micron. The requirements of composition are covered in IS: 12089. Subsequent reference to slag will mean granulated blast furnace slag. Lechatelier. min. S + A + F.8 80@ 4 80** 10 Soundness.8 0. suitable for use in cement. < 0. Water content . N/mm Autoclave. Fineness. 1 35 35 20 70 5 70 5 5 1. MgO. IS: 3812 –Pt. Reactive / soluble SiO2.75 34 320 320 80@ 4. max. Molten slag when allowed to cool in air. #Permitted variation +/. The chemical composition varies over a wide range (Table 3).0 En-450 En-197-1 BS 3892-I Earlier -1981 Current – 2003 25 25 70 6 1. 19 . for use in cement and concrete.5 5 3 1 10 40 *** 75* 10 10 34# 75* 1 10 10 12 2 5–7 5-7 7 12 1.5 3. loses its glassy form. SO3. Requirement of colour consistency in BS 3892 For use in the manufacture of Portland slag cement. It consists essentially of silicates and aluminates of calcium. Drying Shrinkage in IS 3892. min. This is called granulation and what is used in cement and concrete. max Total/ reactive CaO. *** Permitted variation + 10% of average ii. unless other units are indicated) Item SiO2. min. 28 days Lime reactivity.5 2.8 Notes I.Granulated Blast Furnace Slag Blast furnace slag is obtained from blast furnace used in manufacture of pig iron as a molten stream at a temperature of 1400 – 1500OC.5 10 0. mm 0. max. It should. be water quenched to retain the glassy form and its reactivity. the chemical composition of slag should satisfy the following ratios.5% of average iii.15% vi. * 25% fly ash ** 30% fly ash @ 20% fly ash iv. Total Alkalis. which lay down minimum glass content of 85 percent. 105 % max in ASTM v.

5. which are of importance to concrete making. slag. Other products of hydration of slag in cement are Ettringite. phosphogypsum. Silica Fume – Silica fume is a by-product resulting from the reduction of high purity quartz with coal in electric arc furnaces at temperature of 2000oC in the production of Ferro-silicon alloys or Silicon metal. The slag surface is first covered by Portland cement hydrates.5 – 1. Ca(OH)2 liberated by hydration of Portland cement activates the hydration of the slag component in Portland slag cement.CaO + MgO + 1/3 Al2O3 ----------------------------------SiO2 + 2/3 Al2O3 CaO + MgO + Al2O3 ----------------------------------SiO2 ≥ 1. calcium sulphate. No hydration products can be observed when slag is placed in water.95 IS: 455 permits addition of granulated slag in the range of 25 to 70 percent in the manufacture of Portland Slag cement. ASTM C1240 or ACI Committee Report 226 also offer ample guidance. In the process. there is evidence that the surface of the slag is modified as soon as it comes in contact with water.5 80 . The pH value is not reduced to any appreciable extent.0. Because of relative hardness of slag. C-S-H formed by slag hydration has a lower C/S ratio. the common level is 40 to 50 percent. ≥ 1. CaO + CaS + ½ MgO + Al2O3 ----------------------------------≥ 1. monosulphate aluminate and calcium aluminum hydrates. Known activators are sodium hydroxide. Dissolution of Ca2+ and Al3+ ions from slag also leads to formation of the hydrate. by inter-grinding or separate grinding and blending. However. then reacts with Ca2+ ions from the supersaturated solution forming C-S-H. sodium silicate. lime. Hydration of slag in cement The difference between fly ash and slag is that the latter is hydraulic. 20 . SiO-vapours are produced.4 – 5. sodium carbonate. Apart from IS: 15388 . on its own can hydrate in contact with water.0. Ground granulated slag can also be added to OPC and other ingredients of concrete in a concrete mixer.4.5 0. The essential features of silica fume. however. are the very fine particles and high content of amorphous silica. which oxidise and condense in the form of very tiny spheres of non-crystalline silica. SiO2 + MnO TABLE 3 TYPICAL CHEMICAL COMPOSITION OF SLAGS Characteristics SiO2 Fe2O3 Al2O3 CaO MgO IR S (Sulphide sulphur) Glass content Range.2003. The hydration of slag can be activated. and of course.5 to 1. the reaction is very slow. of the order of 0. percent 29 – 36 0–2 16 – 30 31 – 34 7 – 12 0.

which are wastes from various chemical industries disposed off in liquid form. Barium-bearing waste obtained in the manufacture of white mineral pigments. Types of Cement – Classification of cements in different types are done either on the basis of performance characteristics like strength. The major difficulty is that the sludges are in wet form. Fluoro phosphorous slag. F-. Cl-. Another aspect is the presence of impurities like P2O5. paper. These are obtained from fertilizer. A summary of typical chemical composition of various lime sludges is shown in Table 4. Much wider scope exists for use of sludges. the following industrial wastes have mineralizing properties. • • • • Phosphorous slag and phospho-gypsum. cement 43 Grade 53 Grade Rapid Hardening Sulphate Resisting Low Heat Hydrophobic Cement White Cement Blended and Portland Slag Cement 455 Composite cements Portland Pozzolana Cement . in various amounts. No. or on the basis of chemical composition and resistance to chemical attack. In absence of wet process cement plants. setting and hardening. these sludges must be dried before use in dry process cement plants.Silica fume should contain 85 . which may limit the amount of sludges to be added.Calcined Clay based 1489-II Masonry Cement 3466 Supersulphated Cement 6909 Special Cements Oil Well Cement High Alumina Cement for Structural Use 8229 6452 21 . chromium and soda ash industries and have the potential to form part substitute of limestone.90 percent SiO2. and Zinc-containing wastes. In addition. acetylene. Industrial wastes as raw mix component – Fly ash and slag can be used in limited amounts in the raw mix composition. sugar. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Generic Type Description IS 269 8112 12269 8041 12330 12600 8043 8042 Ordinary Portland 33 Grade. most of which should be in glassy form. It is common practice to add silica fume as a replacement of OPC in concrete mixer. The various types of cements covered in Indian (IS) specifications are listed in Table 5 below. alkalis and Cr2O3 etc.Fly ash based 1489-I . TABLE 5 Types of Cement Covered in IS Specifications S. colour and heat evolution.

In addition. ASTM and EN Cement Standards. Longmans 3.. 2. A. Reference Books 1. Properties of Concrete. Mumbai. S. International Symposium on Cement Industry Solutions to Waste Management. The features and comparison of the specification requirements in all the three are given in a publication listed below...ASTM C150 classifies Portland cement into five ‘types’. Mullick. (Cement Business). Utilisation of Wastes in Indian Cement Industry. European specification EN 197-1 has adopted an elaborate scheme of specifying different types of cements. • • • • • Type I – ordinary Portland Type II – moderate sulphate resisting / moderate low heat Portland Type III – rapid-hardening Portland Type IV – low heat Portland Type V – sulphate-resisting Portland. Canada.. K. Publication no. ASTM C595 and ASTM C150 classify blended hydraulic cements as. and Ahluwalia. A. Calgary. Neville.. 4th ed. Butterworth. Type IS – Portland blast furnace Type I (PM). M. Comparison of BIS. Type IP – Portland-pozzolana Type S – Slag cement. C. 4. 5. 1992. Lea’s Chemistry of Cement and Concrete. K. Mullick. Oct. A. Grasim Industries Ltd. -------- 22 . • • • Type I (SM).

to yield a satisfactory raw mix. as well as silica as quartz. The following classification in terms of CaCO3 content is applicable. If MgO is present (as MgCO3). Such a limestone is more favourable. with the proviso that MgO content does not exceed 6% as per IS requirements. Limestones consist predominantly of CaCO3. it has been possible to have a limestone of composition with LSF = 1. it is called ‘marginal’ grade limestone. in order to correct its chemical composition in terms of moduli values discussed earlier. This is particularly important for limestone deposits. In few instances. degree of crystallinity. the composition deviates from such ‘ideal’. the ‘Total Carbonates’ (TC) should be about 90%. most of the time. they often contain Mg.e. limestone with CaO >48 % can be called ‘high’ grade and used as a ‘sweetener’ with limestone of lower CaO content. certain materials are incorporated in the raw mix in smaller quantities. These are called ‘additives’ and comprise materials providing iron and alumina in the required proportions. because the components are naturally present in a well blended form and can be used singly in cement manufacture. Al and Fe combined as carbonates and silicates. influence the mineral form. In addition. For cement manufacture. There are a number of parameters which determine the suitability of the raw materials for use in cement manufacture. conventionally have 46 – 47 % CaO. High Silica. Clay Component – 23 . The reactions in the cement burning process takes place between the individual phases present in the kiln feed. For intermediate compositions i. comprise more than 90 percent of the mass of the raw mix. i. intensity of compaction etc. as Calcite. grain size. Both occur in the nature as rocks (mostly sedimentary rocks). Limestone containing some admixture of clay minerals is to be preferred. cementing medium. The mode of origin of limestone e.g. It should be noted that mixture of ‘pure’ limestone and ‘pure’ clay will react less favourably. Parameters of Quality of Limestone Deposit – Suitability of limestone is mainly judged on the basis of its chemical composition.e. Pure limestone Marly limestone Lime marl Marl Clay Marl Marly Clay Clay > 95% CaCO3 85 – 95% CaCO3 70 – 85% CaCO3 30 – 70% CaCO3 15 – 30% CaCO3 5 – 15% CaCO3 < 5% CaCO3 For cement manufacture. which. In addition. igneous or metamorphic. CaO > 44 % but < 46 %. whether sedimentary. dissociation characteristics and chemical combinability. or > 82 % CaCO3. On the other hand. low lime limestone with SiO2 > 14% and CaO < 44% is classified as ‘low grade’. fine-grained sedimentary limestone deposits are preferred.RAW MATERIALS AND MINING (4) The raw materials for cement manufacture which are subject of geological exploration are mainly limestone and clay. However. in India. ‘Cement grade’ limestone should. and silica ratio and alumina ratio within desirable range for raw mix composition. Each of these parameters influences the thermo-chemical reactivity.

bedding conditions. Exploration and Reserve Estimation For the manufacture of 1 tonne of cement. 1. With this information as the starting point. assessed and evaluated. Corrective materials – Small amounts of materials other than limestone and clay are needed. surface tests. Estimating and verifying the workable reserves of raw materials. ground water and possibilities of working the deposit are established over extensive areas. Hence. limestone deposit of the order of at least 60 MT are required for a life span of 40 years. known through geological exploration carried out by the nodal governmental agencies (GSI and State Geological Surveys in India). Establishing the range of variation in the quality of raw materials throughout the working life of the deposit. For setting up a one MT cement plant. prima facie. The main purposes of exploration are. Assimilation of coal ash in the clinker provides a source of silica in raw mix composition. Stage I – Field inspection of a number of deposits. Large amount of free quartz is not desirable. Verifying the quality of raw materials.063 mm). more focused and dedicated investigation is required to establish availability of ‘cement grade’ limestone. containing high proportion of oxides which may be deficient in the main raw materials. Suitability of the site for quarrying or open-cast mining are known. Chemical characteristics. With high ash coal used in India. Simple – when the co-efficient of variation is ≤ 4 percent. slate. 2. Laterite or quartz sand is used for increasing SiO2. The main aim is to find out the quality of the deposit. Comprehensive drilling programme enables the deposits to be broadly studied. Availability of limestone in any country is. roasted pyrites or iron ore for Fe2O3. and 24 . The variance of the geochemical data of the deposit enables it to be classified as under. Mineralogical form of silica is important. and much more for longer life and/or larger plant size and future expansion. the deposit of limestone has to be properly explored. Sand (0. The amount of exploration and the number of bore-holes depend upon the variation in the chemical characteristics. Stage II – One or more deposits are selected for detailed investigation. large area mapping and a limited number of exploratory borings. 1. shale and crystalline slates. Depending upon the particle size. Suitability is judged by chemical composition in terms of silica ratio (SR) and alumina ratio (AR). Silt (0. and bauxite for Al2O3.≤ 10 percent. these are classified as Clay (<0.The clay mineral component is generally a soft and loose-textured sedimentary rock deposit of clays. and 3.002 mm). on an average. Stage III – Detailed exploration is carried out with the help of grid of closely spaced bore-holes to determine the chemical composition of limestone and the variation over short distances.063 – 2 mm) or Gravel (> 2mm). Mineralisers are added with marginal or low grade raw materials or when the raw mix has low burnability. Complex .002 – 0.5 tonnes of limestone are required. The exploration is carried out in three stages. often no clay is required to be added separately. more intense exploration being necessary when the variation is large and vice-versa.

bedding. as mining progresses. Indicated – Reserves which have been investigated on the basis of widely spaced bore-holes. Now a large cement plant is being set up in Bangladesh for which limestone from Meghalaya will be transported by a belt conveyor. If ground water is likely to be encountered. ≤ 20 percent. Karnataka. the reserves of cement grade limestone in India are estimated as follows (NCB. such that the features are known only in a general way.334 MT. Inferred – Reserves which are tentatively determined on the basis of limited investigation with few isolated bore-holes. hydrological conditions and legal aspects. western. Proper planning and deployment of mining equipment is necessary. Measured – 16. There is regional imbalance in the availability with deposits being located in the states in southern. 25 . States like Andhra Pradesh. its grade and quality variation and help in proper planning pit design and cost effective mining. provision for pumping out should be made.610 million tonnes (MT). in that order. Various quarry floor or base levels should be connected to each other and the general ground level by ramps. the types of rock. The software developed by NCB enables reliable estimation of limestone reserves. Measured – Reserves which have been subjected to detailed exploration and have been fully investigated with regard to chemical features and range of variation. several benches at several working points are worked upon simultaneously.Intricate . Gujarat. Classification on the basis of extent of exploration – The deposits are classified as under. one above the other. in which the material in the deposit is quarried in several benches or steps. Mining and Quarrying of Limestone – As indicated before. The software is used by Indian cement industry. Madhya Pradesh and Rajasthan account for nearly 75 percent of cement grade limestone deposits and large plants are set up in these states in large numbers. Computer-aided mine planning programme developed for such purposes helps in selecting locations and benches. while states like West Bengal have no deposits and no large plants. forming sufficiently wide roads with gentle slope (1 : 10) for haulage and movement of vehicles. chemical composition. In order to compensate for variation in chemical characteristics of the rocks at different depths and different locations in the deposit. Indicated – 11. The operations are seldom confined to a single bench or single location at a time. a million tonne cement plant producing 3000 T of cement per day (330 working days in a year) will need more than 5000 T of limestone to be quarried every day. northern and eastern zones. tectonics. Similar is the situation in Bangladesh. The usual method is of large scale open-cast mining using benching technique.. Next comes states like Himachal Pradesh. structure and bedding conditions are broadly known. Meghalaya and J&K etc. Total – 89. 1991 data).833 million tonnes. and Inferred – 61.> 10.The mining of limestone involves the following steps.889 MT. On this basis.

3. Ripping – In case of heavily fissured rocks having thin bedding and coarsely crystalline structure. The speed of the ropeway is of the order of 4 m/sec. SP-151985. The entire assemblage comprising the power pack. Berlin 2. W. In case oversize pieces or boulders are obtained. drilling mast. but it is not very common. hydraulic units. Academic Press. haulage and crushing. Rotary drilling or percussive rotary drills are used for forming the blast holes. When the surface is inaccessible for blasting. Comprehensive Appraisal of Cement Grade Limestone Deposits in India. The range varies from 1 to 100 km and capacity is about 500 T/hour. Cement Engineers’ Handbook. National Council for Cement and Building Materials. the rock should be fragmented after blasting to a size. Secondary blasting – In normal course. The teeth can be straight or curved. when the primary crusher is located at the quarry site. The blast holes are charged with explosives and fired with the help of delay-type electric detonators (blasting caps). Drilling – Large-hole blasting with blast holes in single row parallel to the slope of quarry face is common. step bit. so that the limestone after primary crushing is transported for further size reduction. gelignite). The specific explosive consumption can be of the order of 200 to 400 gm per m3 of solid rock to be blasted. Careful planning of blast hole location grid. Mechanical methods with pneumatic or hydraulic breaking hammers are also possible in case of softer rocks and smaller deposits. Ripping teeth are mounted at the rear end of a heavy crawler tractor. The purpose of blasting is to loosen and fragment the rock mass. When the terrain condition is difficult. The holes are more than 12 m in depth – may be 20 to 30 m. The explosives can be powder type (ANC – ammonium nitrate–carbon) or gelatinous (gelatins. Loading and haulage to the site of primary crusher. ‘tunneling’ method can be adopted. tunnels are driven into the face of the deposit and fairly large amount of charge is fired.• • • Drilling. small diameter blast holes are drilled into the boulder and explosive charge @ 60 to 90 kg / m3 fired. As the tractor travels. which can be moved form one bench and location to other. Labahn and Kohlhaas. Cement Chemistry. Another alternative is ‘surface blasting’ with holes distributed over an area instead of single row. noise and other hazards. For this purpose. Another method is to apply gelatin type high explosive on the surface of the rock mass and fire. Blasting / ripping. Bauverlag GMBH. aerial ropeways can be used. It is rather noisy and not preferred. Depending upon the characteristics of the rock and the machine deployed. they have to be broken up further. the teeth penetrate into the rock. roller bit or cross bits are used. this is called ‘mud capping’. Belt conveyors can be used. Reference Books 1. The trucks have payload of 15 to 20 T. depth. F. diameter and the amount of explosive charge is required to break the mass and to minimise the ground vibration. for ease of loading. ripping methods can be used. Loading and haulage – The blasted rock is loaded in cable-operated excavators. Haulage to the primary crushing plant can be on rail-mounted vehicles or rubber-tired heavy trucks or combination thereof. H. which can be taken to the primary crusher for reducing to smaller size. This is called ‘secondary blasting’. Taylor. hydraulic operators or wheel loaders. The drilling machines are with fully hydraulic drive system and have capacities of 30 m/hour or so. 26 . New Delhi. In this method. rod magazine and other accessories are mounted on a traction unit. London. its spacing. as required. and the holes are of 50 to 250 mm diameter.

refractories. The heat for pyroprocessing is supplied by the fuel. 3. Preheat and evolution of CO2 from the carbonates (calcinations) – 805 OC. fuels and the flame characteristics will be described. The heat transfer mechanisms and heat balance involved in cement manufacture will be discussed. Formation of phases and clinkerisation– 800 to 1400 OC. being more common.4. the kiln. The Cement Kiln System – Dry process plants with preheater and precalcinator will be mainly described. the cooler and the refractory. 2. Norms for Exploration of Limestone Deposits. ignited by hot air and gases from the system. There are significant differences in the gas and material temperatures. the following operations take place at the temperatures indicated. These heat transfer functions in cement manufacture take place in the kiln ‘system’ – comprising the preheater and precalcinator. 4. 27 . In this section. and also for a wet process kiln for comparison. the kiln. The heat profile following the sequence of heat transfer operations are shown schematically in the figures given below for a modern dry process kiln with preheater and precalcinator. National Council for Cement and Building Materials. 1. Clinker discharge and cooling.550OC. New Delhi. Slurry preheat and evaporation of free and chemically combined moisture– 100 . PYROPROCESSING AND CLINKER FORMATION (8) During the process of cement manufacture.

Material and Gas temperatures in a wet process (above) and dry process precalcinator kiln (below) From the figures given above.e. although five stages are more common and even six-stage preheaters are used. no part of the kiln is required for driving the moisture off the kiln feed in a slurry form (as in wet process). 28 . These operations are done outside the kiln in a preheater tower (see figure below) i.stage preheater and lower in five. The exit gas temperature leaving the top stage will be about 340OC in a four . evaporation of moisture from the clay minerals and the preheating of the kiln feed. These exit gases are used to heat the material in the grinding mills. it is obvious that a dry process kiln with preheater/precalcinator will be of smaller length than a wet process kiln. What is shown is a four-stage preheater. The heat exchange between the gas and the material takes place in the cyclones while both are in suspension. This is because.or six-stage. before it enters the kiln.

• To cool the hot clinker discharged from the kiln.e. In order to increase the production rates of preheater kilns. before the feed enters the kiln. 3. each has 5-stage preheater. or it can come from the kiln itself. The dimensions of the kiln i.25 X 70 m. to allow for future expansion. Unless otherwise mentioned. the length and the diameter depend upon the capacity of the kiln. It should be noted that the capacity is not the volume of the kiln. The speed of rotation is about 1.000 tpd – 6 X 96 m. It performs two functions. The degree of calcinations of the feed will be about 90 percent.5 rpm in case of long kilns and 2.5 rpm for shorter precal kilns. 3.4.000 tpd .000 tpd . 6. 10.2 X 50 m. Clinker Coolers .000 tpd – 5.000 tpd – 3 X 50 m (only SP).500 tpd – 4. The length to diameter (l/d) ratio in a wet or dry process kiln without precalcinator (called long dry kiln) is of the order of 30 to 35. 1. The air for firing the fuel comes from an auxiliary duct parallel to the length of the kiln using the excess waste gas from the clinker cooler. These are called ‘flash furnaces’.4 X 54 m. It is supported on two sets of rollers when l/d = 12 to 14 and three supports when l/d = 16 to 18. with the feed end being higher and discharge end lower. This operation can use fuel of lower calorific value than required for clinkerisation.5 to 2. as the loading in a kiln with kiln feed is only about 6 to 10 percent of the cross section. by burning 30 – 50 percent of the total thermal energy required.5 %. There are various designs of preheaters and different types of precalcinator.4 X 52 m.300 tpd – 4. 3. Precalciners are suspension preheaters equipped with a secondary firing system at the bottom-most stage. they are equipped with facilities of auxiliary firing to pre-calcine the feed outside the kiln.4-stage suspension preheater (top) and suspension flash furnace precalcinator (below). 2. Typical dimensions of kiln (length and diameter) adopted for different capacities in India and abroad are given below. and 29 .These are fitted at the discharge end of the kiln. in case of a preheater and precalcinator the l/d ratio could be from 12 to 18 (short rotary kiln). The kiln is set in an inclination of 3 to 4.6 X 70 m. which will be described later on.

supplied by primary air fan. What all types of coolers have in common is that the cooling air flows directly through the clinker and some of the heated air is fed as combustion air to the kiln.in a traveling grate supplied with circulatory air (ambient) from a cold air fan forced upwards through the grate and the bed of clinker. Inclined reciprocating grate coolers –Clinker discharged from the kiln moves to. 30 . Planetary coolers – These are cooling cylinders attached to the circumference of the kiln. There are no moving parts. As the clinker is cooled. Continuous traveling grate coolers – These are similar to reciprocating grate coolers except that a continuous moving grate belt is used.100 OC. the air gets hot and is fed back by means of a hot air fan as secondary air to the kiln system. or as secondary air to fire in precalcinator. Clinker coolers are of different types (see figure below). The exhaust air is also used for drying raw materials and fuel. it is difficult to have planetary coolers in precalcinator with tertiary ducts. The temperature of cooled clinker is about 150 OC.and fro. no fans to control and all the air that passes through these tubes enter the kiln and used for combustion.• To supply the kiln with necessary air for combustion of the fuel. Valuable heat from the clinker is recuperated and enters the kiln as hot secondary air. The temperature of cooled clinker is about 80 . However. The clinker can be cooled to about 80 . The primary air for combustion is fed to the kiln via a burner pipe.100 OC.

Coating is a mass of clinker and the dust particles that adheres to the lining. What are described above are ‘direct’ coolers. Abrasion resistance. • Basic group – manufactured mainly from periclase (dense crystalline magnesia). resistance against chemical attack from the materials inside the kiln. Alternatively. Resistance to temperature encountered in the zone. strength. density.Rotary coolers – These were used in earlier times and not in use with modern kilns. These are called ‘castables’. The temperature of cooled clinker is about 150 OC. The refractory materials are usually ‘bricks’ of appropriate size and shape so that they can be laid on the round periphery of the kiln. 1. modulus of elasticity. Tests are routinely conducted for compressive and tensile strength. i. One important test is called ‘refractoriness under load’ (RUL) which gives value of deformation of the refractory brick when subjected to a specified temperature under a specified load for a specified time. the material is cast in a plastic stage inside the kiln and allowed to harden. a lining of refractory material is provided. One particular type is called ‘G-coolers’. Types of Refractories – In line with different temperature profiles. iron. A kiln feed with a high liquid content at clinkering temperature is more effective in coating formation. chemical analysis. With increasing alumina content. it is clear that the refractory should possess the following characteristics. The flame characteristics (to be discussed later) also have an influence in coating formation. The requirement of refractoriness varies from zone to zone in the kiln. Refractoriness increases with alumina content and high-alumina (Al2O3 > 70 percent) refractory is used in the burning zone. 5. In addition. These after coolers often receive clinkers at 300 to 350 OC and discharge at 80 to 100 OC. For rotary kilns. deformations under hot load.e. What helps the matter is the formation of a ‘coating’ on to the refractory lining. The bricks are manufactured by dry press or a stiff mud brick. Shaft coolers – The clinker is discharged into a vertical shaft with cooling air supplied from the bottom. majority of refractory used are of 31 . These are particularly adopted in case of large capacity kilns. there are separate ‘after’ coolers to lower the final temperature to acceptable value. Choice of refractory material depends upon test results and records of prior use. magnesia and alkalis. Specific performance tests are for melting point. caused by start up. Slag resistance. 2. This happens in easy-burning raw mixes with adequate amount of flux i. having changed from a liquid or semi-liquid to a solid state. The requirements of the burning zone are most demanding. thermal conductivity. conductivity and spalling resistance also increase. alumina. Requirements of refractory – From the above. The following types are used in the burning zone. linear shrinkage etc. The results of hot load are expressed as the temperature at which a definite deformation takes place. dead burned magnesite and chrome ore. porosity and gas permeability. much like laying concrete lining. depending upon the temperature. shut down or upset operating conditions.e. 3. It is the greatest in the burning zone. Refractory – In order to protect the steel shell of the kiln from the high temperature encountered during manufacture of cement. • Alumina – silica group – the main components being alumina and silica. Spalling resistance – ability to withstand high temperature changes inside the kiln. 4. The temperature of cooled clinker is about 300 OC. Ash in coal also helps in coating formation. Coatability – ability to pick up a coating and maintain it. refractory materials of different chemical composition and properties are used in different zones of the kiln system.

For other places. • Frequency of kiln shutdowns. In Chrome – Mag bricks. the recent trend is to use waste materials having heat value as alternative fuels in cement manufacture.• • magnesia-chromium classification (Mag-Chrome) with periclase forming the major component (85 % +). solid fuels in the form of coal are traditionally used. having 10 – 15 % alumina and 80 – 85 % MgO. in the burning zone. lightweight bricks Acid fireclay brick RUL. improper installations. as discussed later. the life could be as short as a few days or extend up to two years. Combustion and Flame Characteristics For cement manufacture in India. refractory materials last for up to 5 years. • Chemical composition and uniformity of the kiln feed. and • Poor location and poorly directed flame pattern. The origin of coal is from decomposition of vegetation with anaerobic bacteria and subjected to thermal and mechanical loads for centuries. Details are given in the Table below. refractory materials of different compositions are used. Dolomite bricks .composed mainly of CaO and MgO and have close affinity to the chemical composition of the kiln feed. • Mechanical condition of the tire and the kiln shell. The ideal refractory life should coincide with the planned annual shutdown. hydrogen. chrome ore forms the major component. The main constituents in coal as fuel are carbon. However. magchrome bricks (MgO > 65%) Fireclay brick with Al2O3 content decreasing towards feed end. these cost more than other bricks. kiln shutdown due to refractory failure is the main concern. improper kiln operation. Service life and reasons of failure – For a kiln operator. oxygen and sulphur. OC 1500 1600 1700 1600 1350 1300 Fuels. Types of refractory material for different locations Location Cooling zone Burning zone Transition zone Preheating zone Clinker cooler Type and composition High alumina (>70%) bricks or magchrome bricks Dolomite bricks (MgO >96%) Alumina or high alumina bricks. The combustible part of coal is 32 . Once the kiln attains the operating temperature. • Too rapid heating of the refractory. they form a coating very rapidly. service life of 11 or 23 months is ideal. • Quality of the refractory material. besides moisture and ‘ash’. In these formulations. They offer much longer service life than mag-chrome liners. Basic refractories take to coating formation in a better manner than high-alumina bricks as the coating fuses with the surface layer of the refractory and are thus preferred for the burning zone. periclase is responsible for high refractoriness and volume stability and chrome supplies hot strength and spalling resistance. While in the cooler regions in the kiln system. This manifests as a ‘red spot’ in the kiln shell. The reasons of unsatisfactory service life of refractory are as follows. This can lead to warping of the kiln shell and replacement may be called for. Spinnel – bonded bricks – these are newer development. where shell temperature becomes excessive due to lack of protection by the refractory lining. elsewhere liquid (heavy oil) or gaseous fuels (natural gas. • Overheating the kiln. LPG) are also used. In addition. Thus.

20 to 25 % ash content is considered satisfactory.500 kcal/kg are encountered.3 percent SiO2 of clinker weight is contributed by coal alone. These are also according to their ages. With age and residence time at high temperature and pressure. O and water. 21. C kg of carbon requires 8/3 * C kg of oxygen. anthracites. H. The coal ash gets incorporated in the clinker structure during sintering and should be taken into account in working out the raw mix proportions.900 * C + 1. The ash content in Indian coals is high and calorific value low. A classification system for coal is on the basis of combustion behavior. (i) C + O2 = CO2. S. 12 units of C combine with 32 units of O.8 86 # 58 # Ash. thereby the difficulty in ignition. Chemical composition of ash is similar to that of fly ash discussed before.1 – 0. Lignite coals have high volatile matter (> 50%) and may pose explosion and fire hazard during grinding and storage. % 3 – 12 18 – 40 28 – 34 28 – 50 Fixed Carbon.Total carbon content. For coal with ash content up to 20 – 25 percent. Indian coals are mostly sub-bituminous. which is the matter released on heating to 800 OC. The volatile matter. the net calorific value of coal can be calculated as.994 *(H – 1/8 * O) + 2. it may have to be flooded with inert gases. Hu = 33. Some details of different types of coals and other fuels used in abroad are given below. or Hu = 8. with SiO2 content in excess of 55 percent. and the coal contains 25 percent ash with 55% silica. it remains in suspension in the kiln atmosphere. sub-bituminous and lignite – in that order.% 2 3 – 12 16 . 33 . Details of coal types and other Fuels Group Anthracite Bituminous. Sufficient time must be available to accomplish complete combustion while the fuel is in suspension in the kiln. Although. It includes four main coal ranks. kcal/kg 7525 – 6800 8000 . from Australia are bituminous.400 *(H – 1/8 * O) + 10. should be of the order of 18 to 22 percent. Sub-bituminous Lignite Heavy fuel oil Natural gas Moisture .096 * C + 28.composed of complex organic molecules. while imported coals e.2 Volatile matter. Often. As the fuel is injected in the system. anthracite being the oldest and lignite the youngest. % 88 – 67 74 – 39 39 30. W). For proper combustion of fuel. The fineness of coal is expressed as residue in 90 µ sieve (R90). A rule of thumb for such coal (ash ≤ 20%) is R90 = half of volatile matter. The residue on 200 µ sieve should 1 to 2 percent and nil on 500 µ sieve. in Kcal / kg units.500 * W. starting from most difficult to ignite to the easiest.g. Coal should be dried and pulverized to a fine powder before firing. often ash content in excess of 30 – 35 percent and calorific value ≈ 3.500 * S – 2.6380 5400 – 4800 4000 9500 7500 # . If the weight of coal used is about 20 percent of the weight of clinker.508 * S –597 * W. about 2 . it should be of the order of about 10 percent. bituminous.e.25 35 0. % 7 – 18 4–9 8 – 12 6 Calorific value. in KJ / kg units. older coal formations have less volatiles and more ‘fixed’ carbon. The requirement of oxygen for combustion is worked out as follows. and ash content low. supply of sufficient amount of oxygen (through air) and the required temperature to ignite the fuel-oxygen mixture are necessary. Depending on its chemical composition (percent C. i.

If.23 kg.(ii) (iii) 2 * H2 + O2 = 2 * H2O. Taking into account the amount of oxygen already present in the coal.35 * O + 4. or more than 3.5 percent. A practical solution is to work on a range of free oxygen in the exit gas being not less than 0. as shown in the figure below.6 * C + 34. S + O2 = SO2. and only 31 percent of potential heat following complete conversion of C to CO2. Coal – 250 OC. The coal required for cement manufacture depends on the moisture content and heat value. In practice. I kg of air contains 0. The ignition temperatures of different types of fuels are. 1 kg of fuel requires 10.5 percent under stable operating conditions. the weight of coal consumed in dry process precalcinator plants is about 20 % of the weight of clinker produced. i.e. Fuel oil – 200 OC. Natural gas – 550 OC. on an average. is generated.e. Petroleum coke – 595 – 620 OC. 2 units of H combine with 16 units of O. in order to ensure complete combustion. often traces of CO and free oxygen are found together in the exit gas. it is essential that incomplete combustion must be avoided and there should be no trace of CO in the kiln exit gases. presence of oxygen will be noticed in the exit gases. lower flame temperature and greater heat loss.e. 1 unit of S combines with 1 unit of O. i.35 * S) kg of air.78 * H – 4. For satisfactory operations.23 kg of oxygen and 0. It was mentioned that in India.77 kg of nitrogen. The burning conditions in the kiln not being the ideal. 34 . The most desirable range of oxygen in the kiln exit gas is between 1 to 1. Incomplete combustion of coal due to inadequate supply of oxygen results in formation of carbon mono-oxide (CO) rather than CO2. This will give some idea about the volume of air to be supplied for combustion of coal. Ideally. there should be neither any trace of CO nor of oxygen in the kiln exit gases. In other countries having good quality fuel. combustion of 1 kg coal requires (8/3 * C + 8 *H – O + S) kg of oxygen. this is difficult to achieve.5 kg of air. H kg of hydrogen requires 8 * H kg of oxygen. (11.7 percent. Such excess air means larger volume of air than required has to be raised to the operating temperature in the kiln. less heat available for actual burning process. Hence air requirement for combustion of 1 kg coal is (8/3 * C + 8 *H – O + S) / 0. S kg of hydrogen requires S kg of oxygen. i. the amount of air supplied is more than what is required.

which have some heat value. the flame first has a plume.5 percent. in combination with coal. Burning of high sulphur fuel requires appropriate burner design and higher primary air consumption. In this sense. even animal meals and animal remains have been tried. rubber tires. and the residue with high sulphur and less volatiles result. Pet Coke has 8 to 12 percent volatiles. Presence of sulphur in the fuel causes operational difficulties. the total SO3 content in cement tends to become higher. corresponding to 8 to 12 percent volatiles. followed by the point of ignition and then. The length could be the total flame length from the tip of the nozzle to the end or the ignited flame length from the point of ignition. The thermal energy recovered is used in the kiln itself. which does not contribute to control of setting time in the way externally added gypsum does. Some cement plants in India have used rice husk as part fuel. waste wood. the ignition temperature is 595 – 620 OC. paper waste. the flame is characterized by many parameters – length. Homogeneity of the waste materials should be ensured. These include rubber. Consequently. A typical flame is sketched below. Global tendency is to use low or very low sulphur content in liquid fuel oils.Use of alternate and secondary fuels Driven by the concern for reducing fuel cost. which is a solid by-product from oil refineries. in order to ensure high flame intensity. Flame characteristics – To an experienced kiln operator. The SO3 content in the clinker is of the order of 1 to 1. alternate fuels derived from waste materials. As mentioned before. What is distinct is high sulphur content of the order of 5 to 8 percent. direction and colour. Attention has been focused on use of petroleum coke (Pet Coke). finally the flame. Life of refractory may be affected. are being increasingly used in the cement industry. burning in the cement kiln is not incineration. as well as need for environmental improvement. residual moisture about 1 percent and can be considered to be similar to imported low volatile bituminous coals. which shows that on leaving the nozzle of the burner pipe. and the non-combustible portions become raw materials. 35 . waste oils. shape. but ‘valorisation’. paper. The process ensures high level of efficiency in energy recovery from the waste. paper sludge. point of ignition. It has to be pulverized to R90 = 5 percent.

as long as the air-fuel ratio is maintained constant. as it happens in indirect firing. under stable operating condition. The temperature of the flame is given by the relation.29. the tip velocity should be more than 35 m/s to keep the coal particles in suspension in the circular burner pipe and not allow them to settle down. Generally. as it searches for oxygen further back in the kiln. OC White to dazzling white Light yellow to white Yellow to light yellow Orange to yellow Bright cherry red to orange Cherry red to bright cherry red Dark red to cherry red Colour of the flame >1540 1320 – 1540 1090 – 1320 900 – 1090 825 – 900 750 – 825 650 – 750 36 . with the fuel getting ignited soon after it leaves the burner. is controlled by the speed of ID fan. During the initial start of the kiln. OC. The following is a guide. In practice. the greater the speed. The initial ignition of the fuel is primarily dependant on sufficient heat to ignite the fuel and on sufficient air to obtain combustion of the fuel. Ignition takes place in the burning zone and the flame extends to the calcining zone. The values obtained by this calculation are of the order of 2000 to 2650 OC. T = Flame temperature.The percentage of combustion air present and the velocity of fuel-air mixture at the tip of the burner are the main factors influencing the length of the flame. It is always preferable to have as short a flame as possible. Hv T = -------------------. adopt 0. 1. A = amount of air required for combustion. The primary air velocity should be twice that of flame propagation speed. If the velocity is about 45 – 66 m/s. Lack of combustion air makes the flame long. kcal/kg. secondary air and any parasite air due to leakages. more is the air. as it happens in case of direct firing. The quantity of total air – primary air. A high tip velocity of about 70 – 80 m/s gives exceptionally good flame pattern.11 * A *s Where. lower values are obtained and the colour of the flame changes. when the kiln temperature is too low to ignite the fuel. there is no change in the flame length. a pilot burner (auxiliary torch) is placed at the mouth of the burner pipe to obtain good ignition. Hv = Heat value of the fuel. s = specific heat of combustion gas. In any case. a lazy swirling flame results. Temperature of flame and colour Flame Temperature. so as to prevent a flashback of the flame. kg/kg of fuel.

Heat exchangers in the form of chains were common in wet process plants and sometimes used in dry process plants also. As a result. The coating receives heat from hot gases by radiation. The difference between the material and gas temperastures is small. convection and radiation. the thermal energy expended during cement manufacture for clinkering the raw mix should match with the thermal energy supplied by the ignition of the fuel. Part of the heat is radiated to the feed bed and part is transferred by conduction. transfers heat by conduction. when the feed comes in contact with the wall.Lowest visible red to dark red Lowest visible red 475 – 650 475 > Heat Transfer and Heat Balance Total heat transfer in the entire kiln system involves all the three modes – conduction. it rises along the upward-moving side of the kiln and then tumbles back. Part of the heat then radiates to the bed of the feed and part of the part is transferred by conduction as the feed comes in contact with the wall tumbling back. the temperature of the wall is lowest when it emerges from the bed and highest immediately before it comes into contact with the feed bed (see figure below). The hot particles coming in contact with colder parts. Heat Balance – In an ideal situation. as the time taken is small. Aided by the rough and uneven surface of the coating. The flame radiates heat to the coating. the kiln feed in a ‘sticky’ condition is in a constant state of agitation. Meanwhile. The heat transfer in preheater tower is more efficient. The theoretical heat required for clinker formation is estimated to be 37 . Radiation: Conduction: Convection: Flame ----------------------- Feed bed Hot kiln wall ---------------- Feed bed Heat from kiln interior --- Kiln shell Kiln chains ----------------- Feed bed Hot kiln exit gases ------- steam in boiler tubes. The chains get heated by the gases and transfer heat to the feed by conduction. In practice. Some examples are. new particles are exposed to heat transfer by radiation. A similar action takes place when heat is transferred from the kiln wall to the feed. as they come in contact. Heating the feed bed inside the kiln is primarily by radiation. In the burning zone. this is not the case.

The computations given above should generate possible ideas for reducing the requirement of heat in cement manufacture. The above are by way of example only.All heat values are in kcal/kg.kiln 858 39 -5 892 396 4 184 5 154 109 40 892 Wet Process kiln 1378 11 -7 1382 389 565 224 3 86 84 31 1382 # .718 + 515. Fe2O3 = 2.2*Al2O3 + 6. The theoretical heat required for clinker formation depends on the chemical composition of the raw mix and kiln feed. Q = 10.963 – 1. yet the thermal energy consumed varies from about 1396 kcal/kg in wet process plants (31% efficiency).43. CaO = 67. and the average consumption figures for the industry are comparable to the best in the world.33 kcal/kg.of the order of 400 – 440 kcal/kg. Typical Heat Balance Calculation # Item Heat Input From fuel From raw materials From cooling air Total Input Heat Expenditure Theoretical heat required for clinker burning Evaporation of water Exit gas losses Dust losses Radiation and convection losses Losses at the cooler Unaccounted for @ Total Expenditure SP.78. the following composition of kiln feed on loss free basis.58. These will be discussed in greater detail later. The Table above gives typical heat balance computation for a wet process kiln and a dry process pre-heater kiln.57 – 105. SiO2 = 20. Take. Al2O3 = 4.48*MgO + 7. Such an exercise helps in conservation of thermal energy by better ‘house-keeping’ and operational practices. Q = 2. using the above formula. Many modern dry process preheater plants in India have reported thermal energy requirements of the order of 670 to 700 kcal/kg.A heat balance consists of compiling all the heat that is given to the kiln and then comparing this total to the total of thermal work done and losses taking place.Unaccounted losses are calculated by difference to balance input and output. You are encouraged to think of possibilities. MgO = 2. in kcal/kg. This can be calculated by the empirical formula.84.642 = 435.59*Fe2O3. @ . where the oxides are expressed as percentages in the kiln feed (loss free basis) and Q is the heat required. and Loss on ignition = 0. 38 .648 + 16.71. Then.646*CaO – 5. in lecture on ‘energy conservation’. for example.00.1165*SiO2 – 0. 1194 kcal/kg in dry process (37% efficiency) to about 750 – 850 kcal/kg in preheater-precalcinator kilns (about 57 % efficiency).

process control and instrumentation. 2. K. optimization of operations. 39 . grinding. Edward Arnold. Berlin. Perey. Duda. 4. cement grinding. Verlag GmBH. Berlin. 2002. Bauverlag GMBH. 3. The Rotary Cement Kiln. H. All volumes. Labahn and Kohlhaas. homogenization and blending.Reference Books 1. Cement Data Book. ------ OTHER UNIT OPERATIONS (7) Contents – Size reduction – crushing. Report of VDZ Congress. W. Cement Engineers’ Handbook.

manufactured from naturally 40 . Labahn and Kohlhaas. It finds wide applications ranging from boundary walls and beams and slabs for simple housing units to exotic applications like tall structures and sky-scrappers. Reference Books – 1. The Rotary Cement Kiln. industrial structures etc. large dams. grinding mills. nuclear power projects. thermal power plants.PLANT AND MACHINERIES (7) Contents Different types of preheaters and precalcinator. plant maintenance. lay out. packing. aggregates and water). Berlin. Report of VDZ Congress. Perey. 4. Edward Arnold. All volumes.g. 3. CONCRETE TECHNOLOGY (6) Basic Concepts Concrete is the most widely used man-made construction material the world over. H. Duda. W. 2002. Berlin. Bauverlag GMBH. which are available from natural resources (e. Cement Engineers’ Handbook. Verlag GmBH. It is made of constituents. long-span bridges. There are many reasons for such versatility of concrete. Cement Data Book. safety in operations. 2. K. expressways.

Although the initial strength development is different. It is customary to use cement of higher strength characteristics for high strength concrete. most notably the strength and durability of concrete. aggregate. An important consideration of cement manufacturing is the properties of cement which are critical for its end use in the concrete constructions. and water. Concrete making materials – The basic constituents of concrete are cement. The strength of concrete depends upon a large number of factors.the aggregate are embedded to form the composite. In India. Small discrete fibers of steel or polypropylene are sometimes added to impart special properties to concrete. and chemical ‘admixtures’ to be dosed at the time of mixing the ingredients. compaction. finishing and curing.occurring raw materials (e. One of the factors is the strength of cement. fly ash. 41 . and upon hardening. at least two more components are recognized – various industrial wastes as part substitute of cement. Cement – Various types and grades of cement. workmanship in mixing. concrete in its plastic stage can be moulded to any desired shape. Cement and water comprise the binder matrix. greater is the strength of concrete (see figure below). in various degrees. When the ingredients are mixed with water. strength of cement is tested in 1:3 cement mortar made with ‘standard’ sand and at water-cement ratio of about 0. slag. silica fume). in the concrete being made in the country at the present time. 43 grade and 53 grade. placing. the long-term strength at say five years’ time tends to be similar in all the cases. The general trend of rate of strength development of different types of cement (ASTM classification) is shown in the figure below. With the progress of knowledge. As per IS specifications. the grade designation indicating the minimum strength at 28 days. or industrial wastes and by-products (e. which result from variations in chemical composition and physical properties were discussed under the topic ‘Types and Performance Characteristics of Cements’. It has been shown that for identical mix proportion of concrete. Chemical composition and physical characteristics of cements influence a number of properties of the concrete made with it. and its properties in the fresh and hardened states. within which particles of mineral filler . the cements with lower strengths at initial ages – types II and IV have the as high strength as type III in the long term. All these are being used. their proportioning.g. Concrete technology is the technology of the constituent materials. If at all. cement). attain the desired mechanical strength.g.4. when tested in standard mortar cubes as per the specification. OPC is graded into three strength grades – 33 grade. loadbearing capacity and durability for the service environment. its compressive strength depends upon the strength of cement – the higher the cement strength. which is described later on. at temperature 27OC and relative humidity 95 %+.

75 mm and below. For thin sections with high concentration of reinforcement steel. Classification in terms of unit weight can be ‘normal weight’. the 42 . and chemical and micro-structural characteristics. ‘lightweight’ as are most artificial aggregates. In any case. Aggregates – aggregates are important because they occupy nearly 75 percent volume of concrete. or the way the size is reduced – natural weathering as in river sand. also called ‘sand’. 10 mm MSA coarse aggregate are used. the aggregates can not be considered to be inert. while artificial aggregates can also be used. Aggregates obtained from natural sources are commonly used. Industrial by-products – use of fly ash. or crushed rock. abrasion and wear resistance and durability etc. or ‘heavy weight’ as are used for nuclear reactors and radiation shielding. texture – smooth or granular. however. Other classifications are in terms of shape – rounded or angular. Aggregates are arbitrarily classified as ‘fine’ and ‘coarse’ on the basis of size. as is mostly used. strength. shape and texture. is of size 4. Fine aggregate. gravel or boulders. Coarse aggregate of 20 or 40mm sizes are used for structural concrete and 80 mm or 150 mm for mass concrete as in dams. The properties of concrete that are influenced by aggregates are. are of higher sizes. as they influence the properties of concrete through the rock type. granulated blast furnace slag and silica fume has been discussed under the topic ‘Types and Performance Characteristics of Cements’. They can be viewed as fillers in the matrix of cement paste (cement + water). Indian standard specification IS: 383 lays down the requirements of concrete aggregates from natural sources.The influence of cement characteristics on the durability of concrete against chemical attack is discussed later on. also called ‘stone chips’ or ‘gravel’. or as building blocks jointed together by the cement paste – just like stone masonry is jointed by cement mortar. size. It is not proposed to consider all of them in this lecture. while coarse aggregate. workability.

Zone IV sand will increase the water demand in concrete enormously. From the above. occupying 36 percent of the total volume. the smaller the size of particles. IS: 456 specifies that water used for mixing and curing shall be clean and free from harmful amounts of substances that can be deleterious to concrete or steel reinforcement. In particular. it is used for plastering. These lots are to be judiciously combined to result in satisfactory grading of the combined aggregate.15 These limits are shown graphically in the Figure below. This determines the water requirement. there will be void left. These voids can be filled up to some extent with spheres of size smaller than the size of voids. so whatever materials are available are to be judiciously combined to achieve the goal of dense packing. it is clear that sand belonging to zone I is the coarsest and zone IV the finest. Another effect is the total surface area. 600 micron. 300 micron and 150 micron sizes. 80. 4. 150. The same principle applies to concrete aggregate. the quality of water usually receives less attention.75 mm 2. 40.10 Zone III 100 90 – 100 75 – 100 75 – 100 60 – 79 12 – 40 0 . Grading of Fine Aggregate as per IS: 383 Sieve Size 10 mm 4.36 and 1. If we try to fill a container with spheres of the same diameter. tested as per IS: 3025. The permissible limits for solids in water.requirements of size distribution are described. there are additional tests for alkalinity (as carbonates and bicarbonates) and acidity in water prescribed in IS: 456. requires that the group should consist of particles of different sizes. In addition. is given below.10 Zone IV 100 95 – 100 95 – 100 90 – 100 80 – 100 15 – 50 0 . 2. and so on. 10. there are many instances of distress to concrete because of mixing and curing water not being of appropriate quality. For the same total volume. Thus. fine aggregate is graded as per the sieve analysis in different ‘zones’ in IS: 383.10 0 . Sands falling in zone II or zone III are very suitable for concrete. Water – The usual amount of mixing water in concrete varies from 140 litres to about 200 litres per cubic meter of concrete. 20 mm or 40 mm. However. The importance of grading of aggregate is in the way it facilitates densest possible packing. Compared to other ingredients of concrete.75. This principle will be clear from the following example.36 mm 1. water occupies nearly 15 – 20 percent by volume and about 6 – 9 percent by weight of concrete. The details are as under. The sizes as per IS specification are.18 mm. which should comprise of particles of successive smaller sizes. larger is the surface area. 43 . The desirable ‘grading’ for each nominal maximum size (MSA) of say. The size distribution is determined by the proportion passing standard sieve sizes. as well as the sand fractions are given in IS: 383. The principle of densest possible packing of materials. and the residual void filled up with next smaller size. to be covered by cement paste. 20.18 mm 600 micron 300 micron 150 micron Percentage passing Zone I Zone II 100 100 90 – 100 90 – 100 60 – 95 75 – 100 30 – 70 55 – 90 15 – 34 35 – 59 5 – 20 8 – 30 0 . Ideal grading as given in the specifications is not always available. each being smaller than the previous one.

IS: 456 44 .Grading limits for sand in different zones. IS: 383 Permissible Limits for Solids in Water.

Among the characteristics of the cement. The tendency of bleeding should be minimized. Acrylic Polymer (AP) or Polycaboxylatethers (PCE) etc.Workability of concrete is not a single measure. Air-entraining admixtures. improve strength by lowering the water-cement ratio. This is called workability. After mixing. 500 for RCC 2000 Chemical admixtures and superplasticisers – admixtures are materials. Water-reducing admixtures. • Materials and Mix Proportions – water content. in that it should not segregate during transportation and placing. both normal and set-retarding types are more prominent.Item Organic Inorganic Sulphate (as SO3) Chloride (as Cl -) Suspended matter Limit. and It should have finishability to obtain a satisfactory surface finish. They can significantly reduce the amount of mixing water required in concrete. The mix should be cohesive and mobile enough to be placed in the form around the reinforcement and should be able to be cast into the required shape. under the field conditions. but have four distinct aspects. 45 . Use of superplasticisers help in improving the workability of concrete. The performance of concrete admixtures depends upon both the admixture and the cement and their compatibility. The mix should be compactable to achieve proper and through compaction in the situation of placing and with the facilities of compaction. in addition to concrete mix proportions and the environmental conditions in the field. Modified Lignosulphonates (MLS). and Superplasticisers. usually organic chemicals. SO3 and alkali contents. maximum size of aggregate. Among the list above. Strength and durability are important properties in the hardened states. Although intended to modify one property of concrete. which affect the performance of admixtures are the C3A. max 200 3000 400 2000 for plain concrete. It is necessary to evaluate concrete admixtures for specific use with the concrete-making materials and mix proportions to be used in the work. Commonly used superplasticisers are based on Melamine Sulphonates (MSF) or Naphthalene Sulphonates (NSF). The classification in IS: 9103 is based on the intended use. which are added to the concrete (usually in small amounts) before or during its mixing. mg/l. The various factors influencing workability are. Properties of Concrete – Concrete is required to have necessary characteristics both in the fresh and hardened states. superplasticisers. fresh concrete should be amenable to placing in the formwork and consolidating it. as will be clear from the nomenclature given below. Workability . Set-retarding admixtures. improve durability. fineness of sand and coarse : fine aggregate ratio. or combination thereof. many admixtures are capable of modifying more than one property. shape of aggregate – whether rounded or crushed. • • • • • Set-accelerating admixtures. and the fineness of cement. • • • • The mix should be stable. nature of sulphate. with a view to modifying one or more properties of concrete in the fresh or hardened state.

workability reduces with time elapsed after mixing. the strength is determined on 6" diameter and 12" high (150 mm x 300 mm) cylindrical specimens. Strength of concrete – Concrete is relatively stronger in compression and weak in tension. The aggregate-mortar interface is thus the weakest link. The shape and size of the test specimen are also important. Next is the importance of cement strength. walls. dry weather reduces workability. Aggregates occupying nearly 75 percent of the total volume are not. which essentially measures the ‘wetness’ of concrete. The procedure is detailed in IS: 516. the lower the water-cement ratio (see figure below). This is because the mechanical strength of commonly used aggregates is far greater than that of concrete made with it. columns. IS: 456 gives general guidance for the degree of workability. floors. shallow sections Mass concrete.high temperature causes evaporation and reduces slump. Heavily reinforced sections in slabs. is more suitable for ‘low’ workability. beams. and sometimes through the mortar phase.slump test is not suitable and other tests indicated are more appropriate. which is reproduced below. There are a number of test methods for workability of concrete. each measuring a particular aspect.• • Temperature and Humidity . per se. canal lining. In-situ piling Tremie Concrete Degree of workability Very low Low Slump. compressive strength is determined on 150 mm cube specimens. Many other desirable properties of concrete are held to be related to its compressive strength – albeit indirectly. Hence. These test methods are described in IS: 1199 and can be viewed in the laboratory.75 – 0. compressive strength of concrete is considered to be most important. There is a saying ‘a chain is not stronger than its weakest element’. 46 . Compaction factor (CF) test measures the compaction achieved by a given input of compacting effort. The aggregates influence strength of concrete by way of controlling the bond at the aggregate. which has been described before. Flow table test. is more popular because it is easy to carry out. lightly reinforced sections in slabs. Delay in placement. but very seldom failure in the aggregate pieces are found. Requirement of Workability (IS: 456-2000) Placing conditions Pavements with pavers. greater is its strength.100 75 – 100 100 – 150 Flow > 600 mm # # .80 # 25 – 75 Medium Medium High Very high 50 . as in ‘self compacting’ concrete (SCC) to be described later on. In USA and some other countries.mortar interface. Compressive strength of concrete depends upon a very large number of intrinsic and external parameters. If the broken piece of a concrete specimen after testing is examined. Vee-bee time test is suitable for ‘very low’ workability – also called ‘zero slump’ concrete. so much so that compressive strength is many times taken synonymous with the overall quality of concrete. pumped concrete Trench fill. described in IS: 9103 is suitable for ‘high’ workability to ‘flowing’ concrete. Slump test. columns. As long as the concrete is workable. beams. hand placed pavements. the limiting factor. The single most important factor is water cement ratio. failure would be noticed to have taken place around the aggregate particles. walls. As per Indian practice. Slipform work. mm CF 0.

acids etc. As a general rule tensile strength of brittle materials like concrete are about one-tenth of its compressive strength (see Figure below). Tensile strength of concrete can be measured by ‘split cylinder’ test (IS: 5816) or flexural test on beam specimens under ‘two-point’ loading (IS: 516). it is necessary to understand the origin of the problem. it is important to ensure not only adequate strength and load-carrying capacity but also durability. • • • • • • • Strength increase with age of test and duration of moist curing. For proper performance of a structure. or be present in the service environment to which the concrete structure is exposed’. Concrete tested in 100 mm cube specimen will give higher strength than 150 mm specimens. sulphate. However. sub-soil and ground water. carbon di-oxide. there are a number of deteriorating agencies which can attack concrete. each having profound scientific reasons. In this lecture. which can attack the cement + water (cement paste) system and reinforcement will be discussed.As a general rule. The causes could be physical. so that solutions can be suggested. The basic mechanisms are described below. Aggregates with granular texture result in higher strength than with smooth texture. present in the service environment and in soils. the following observations can be made. Concrete under conditions of normal usage is quite durable. Higher speed of loading during strength test gives higher strength value. the action of chemical agencies like chlorides. mechanical. Flexural strength is somewhat greater than tensile strength determined on split cylinders and is a design parameter for concrete pavements. Crushed rock aggregates give higher strength than river shingles or pebbles. Durability . The strength of a concrete measured in 150 x 300 mm cylinder specimen is about 80 percent of the strength determined on 150 mm cube specimen.Durability of concrete is ‘its resistance to various deteriorating agencies that may reside inside the concrete itself. 47 . thermal or chemical in nature. Smaller maximum size of aggregates (MSA) results in higher strength than larger MSA. In each case.

While calcium hydroxide (CH) and calcium aluminate hydrates (CAH) are the fast reacting components of the cement paste. In many cases. with the C-S-H phase leading to its decalcification i. formation of alkali sulphate crystals take place. the type and extent of reaction depend upon the cations. C-A-H and C-H. The response of the hydration products to the principal deteriorating agencies like sulphate (SO3--). Formation of brucite (MH) and gypsum takes place in reaction with CH.e. especially in seawaters. Results in increase in volume of reaction products. The basic chemical reactions. Formation of calcium sulphate (gypsum) in reaction with CH NS + CH + 2H  NH + CS H2 • The acidic nature of sulphate attack causes surface deterioration by softening without expansion. • Formation of sulphoaluminates (ettringite) by reaction of CS and C-A-H C3A + 3 CS H2 + 26 H  C3A(CS)3H32. Sulphate Attack: The main reactions of sulphate attack on concrete are as under. chlorides (Cl-) and carbon dioxide (CO2) are documented in the text books. in addition. CSH is also susceptible to attack by all the three aggressive ions. which are widely reported in the literature. causes expansion and spalling. for example • NS + 10 H  NS H10 (mirabilite) 48 . substitution of Mg+ for Ca+ and formation of M-S-H and other expansive salt identified above. • MS + CH + 2 H MH + CSH2 Both contributing to deterioration When alkali sulphate concentration is high and conditions are favourable. are summarised below. Magnesium sulphate reacts.The main products of hydration of cement are C-S-H.

CaCl2. 49 . containing strained quartz is among the reactive rocks found in India. can be summarised in terms of an anode process and a cathode process. • Fe + ½ O2 + H2O → Fe2+ + 2(OH) → iron hydroxide (rust). granite gneiss and schist. Other products of cement hydration can also be affected by carbonation. as an Electrochemical phenomenon. Corrosion of Reinforcement: The basic mechanism of corrosion of steel. Magnesium chloride leads to ion exchange between Calcium and Magnesium. Calcium chloride reacts with cement hydrates to form expansive compound calcium oxychloride (3CaO. For transformation of metallic iron to rust. quartzite and sandstone. Reaction of chlorides with hydrates of C3A and C4AF. forming Friedel’s Salt and its ferrite analogue is the primary mechanism of ‘chloride – binding’. • Fe → 2 e. Alkali-silica reaction (ASR) involves rocks and minerals containing reactive forms of silica. CH-phase is most susceptible to carbonation. elasticity and durability are among the physical manifestations of ASR. notably presence of moisture and temperature are important parameters. 15H20). being finally decomposed to form calcium carbonate and hydrated silica. Chlorides: Besides being the principal cause of reinforcement corrosion as described later. fractured or strained quartz and glassy silica are among the commonly known alkali-reactive forms of silica. Carbonation: Carbon dioxide in air or dissolved in water reacts with hydrated cement systems. For example. Alkali-Aggregate Reaction: Chemical reactions between aggregate containing certain reactive constituents and alkalis (sodium and potassium salts) and hydroxyl ions released by the hydration of cement can have deleterious effects on concrete. the requirements are. the corrosion undergone by steel is due to combination of iron and (OH-) ions. Granite.+ Fe2+ (Metallic iron) • Cathode: ½ O2 + H2O + 2 e. alumina and ferric oxide.Contributing to surface deterioration by spalling and splitting. Amorphous. microcrystalline and poorly crystalline silica. In all such reactions. Environmental conditions. Expansion and cracking leading to loss of strength. thus lowering down the pH of pore solution. total carbonation of CSH gel can lead to decomposition into calcite and amorphous silica. Anode: The process is summarised in the Figure below. OHis consumed. • C3S2H3 + 3 C  3CC + 2S +3H Formation of thaumasite has also been reported at lower temperatures.→ 2(OH)In addition. chloride salts react with hydrates phases also.

have to ensure that the limiting amount of chloride ions is not exceeded in concrete and neither the pH value of concrete is lowered below the threshold value. Presence of chlorides is not necessary. which would also allow the ingress of the chemical agencies into concrete. On the other hand. there could be cracking caused by thermal effects. In addition. because low water-cement ratio ensures low permeability of concrete (see Figure below). would take a certain amount of chloride ion to be present so that corrosion can take place. Oxygen and moisture must be available for the cathode process. A logical approach to prevent deterioration comprises. only oxygen and water are needed for corrosion to take place.45 or less. • • • • Make concrete as dense and impermeable as possible. Presence of moisture is necessary for the chemical reactions to take place and proceed. Practical limits of tolerable chloride ion concentration and limiting pH value are best arrived at by in-service record of concrete. The steel reinforcement. and 3. Use of right type of cement. if the passivity is destroyed because of one reason or the other. depending upon the severity of the service environment. Steps to alleviate thermal cracking in massive sections. thereby producing more distress. which causes cracking. Concrete constructions. in order to be durable. Iron must be available in a metallic (Fe) state at the surface of the reinforcing steel. two types of situations are necessary to be considered. by adopting low water-cement ratio and thorough compaction. lower the heat of hydration and reduce the risk of reinforcement corrosion. Most specifications suggest water-cement ratio to be 0.1. From engineering stand point. it is seen that most of the deteriorating actions are expansionproducing. The electrical resistivity of concrete must be low to facilitate the electron flow in the metal from anodic to cathodic areas. IS: 456 gives guidance on minimum cement content and maximum water-cement ratio for concrete exposed to aggressive environments of varying degrees. Portland Pozzolana cement (PPC) and Portland Slag cement (PSC) are recommended to combat sulphate attack. and the pH of concrete is below a certain threshold value. 50 . Adequate cement content to retain passivity of steel and allow proper workability of concrete. Such cracking allows more of the aggressive ions to permeate inside the concrete. use of chemical admixtures and superplasticisers. From what is described above. 2. being well protected in the alkaline medium in concrete. including composite cements.

grading. for a given set of aggregates (maximum size.35. short-term tests for long-term durability of concrete. e. At present.Rational use of cement in concrete – From the discussions above. aided by trials. Potential for alkali-silica reaction depends upon the potential reactivity of the aggregates and the cement characteristics. • • The workability of concrete depends upon the water content in the mix. This is called concrete mix design. which meets special performance requirements that cannot be always achieved routinely by using only conventional materials and normal mixing. for example. they are all approximate and only lead to trial mixes. a minimum compressive strength of 21 MPa at 4 hours. • High Performance Concrete Definitions . cement content and the 'type' i. it also depends on the strength of cement. there are no reliable.Many attempts have been made to define high performance concrete.g. Although there are a number of ‘methods’ of mix design. These are. coarse to fine ratio). there are some cardinal principles that lead to the trials. design for durability is adherence to guidance given in the specifications.’ However. A quantitative definition is that ‘It should have a maximum water-cement ratio of 0. chemical composition of cement. such quantitative definitions may not be satisfactory in all situations. cement. coarse and fine aggregate. Rational use of cement means use of cement of the right quality in right quantity to ensure satisfactory concrete mix. Since there is nothing as an exact method of concrete mix design. • Concrete. and water is chosen on a scientific basis. placing and 51 . Hence . The compressive strength of concrete depends primarily on the water-cement ratio. Among more general. a minimum durability factor of 80 percent in freeze-thaw resistance test as per ASTM C666. and The durability of concrete depends upon the water-cement ratio. when cement quality is variable. The proportions of ingredients of concrete. IS: 456. 34 MPa at 1 day or 69 MPa at 28 days.e. qualitative definitions are. it should be clear that cement plays a vital role in ensuring the desired properties of concrete for a particular application.

Low water-cement ratio is also required for low permeability of concrete. High performance concrete is made with the same cements. which is vital for high durability. For high strength. The compressive strength achieved was about 63 MPa. silica fume and fly ash or slag. such applications may focus on other properties of concrete.45 or so for concrete exposed to severe service environments. these properties are usually a high strength or a low permeability. far in excess of the design requirement.The development of high performance concrete is based on the following well-known relationships of concrete technology. The relationship between coefficient of permeability of cement paste and water-cement ratio is such that the permeability increases asymptotically for water-cement ratio above 0. Impermeability is also aided by pore filling effects of fine pozzolanic additions. fly ash or ground granulated slag. qualitative definitions are more appropriate. abrasion . As pointed out earlier. That is why.cement ratio to about 0. as in normal usage. part of the cement is to be replaced by other cementitious materials like silica fume. water. Durability of concrete is a common thread and high strength may not be always emphasized. Hence. The requirements may involve enhancement of characteristics such as strength. Thus. superplasticisers. The strength . One important consideration is that it should be possible to produce high performance concrete in the field with uniform characteristics between batches and placed in the structure with conventional methods. Apart from high compressive strength. A good example is the tunnel lining concrete for the Channel Tunnel in Europe. Development of high performance concrete follows certain logical steps. the requirement of permeability was met. By adopting water-cement ratio of 0.erosion . Thus.cement. 52 . However. Such fine powders also help in pore filling and reduce permeability. The Logical Development . like elastic modulus.High strength and low permeability are logical developments of presence of silica fume and superplasticiser in concrete.35. Mechanisms of high performance .w/c ratio rule holds good for concrete strength of about 100 MPa or more.45 or so. or • The essential feature of this concrete is that its ingredients and proportions are specifically chosen so as to have particularly appropriate properties for the expected use of the structure. and water. Requirements of durability dictated − that the co-efficient of permeability should be of the order of 10 13 m/s. Since the specification of high performance concrete is derived from its intended use. as discussed below. self-leveling and self-compacting properties etc. water-cement ratio should be low. The dual requirements of high strength and low permeability are linked to each other through the need to reduce the volume of relatively larger capillary pores. aggregates. the composition of high performance concrete is automatically chosen . or high durability. makes use of superplasticisers mandatory. Low water-cement ratio will require high cement content to ensure that the amounts of water and cement paste are adequate for the workability of concrete. The compressive strength of concrete was required to be 45 MPa. high workability. volume stability or service life in severe environments. low water-cement ratio ensures both high strength and low permeability. this is achieved through reduction in watercement ratio as well as dense packing of fine particles. too high a cement content will cause high heat of hydration and increase cracking tendency. but with proper curing and adequate quality control.curing practices. or combinations thereof. Use of low water-cement ratio and other cementitious materials as silica fume etc. additives.cavitations resistance. toughness. admixtures. aggregates. most concrete specifications limit the water .

block the pores. the transition zone forms a weak link. Result of strengthened transition zone is reduction in micro cracking at the interface between cement paste and aggregate. When contribution of silica fume to the compressive strength of concrete is compared based on water-cement ratio in the mix.5µ m gel pores is visible under high magnification in electron microscope. mixes containing silica fume has higher compressive strength at 28 days.less than 0. are dispersed by superplasticiser. the ‘alkali cycle’ is broken.a critical advantage for mass concrete. The porosity of the transition zone is eliminated. The role of silica fume is many-fold. It also helps in augmenting early strength of concrete. impart a negative charge to them. Thus.Through the presence of silica fume and low water-cement ratio. In presence of silica fume. The C-S-H formed due to pozzolanic reactions between silica fume (and / or fly ash) and calcium hydroxide has lower C/S ratio and arrests alkali ions in solid solution. long chain molecule organic compounds. use of silica fume enables the heat rise in concrete to be lowered . Presence of moisture is required for ASR expansion to take place and continue. Another important mechanism is improving the transition zone around aggregate particles. There is not much experience to go by and practices with normal grades of concrete are of little help. The extremely fine silica fume particles are then packed in the space between dispersed cement grains and normally packed fine and coarse aggregate. The alkalinity in the pore solution is reduced.Choice of materials. but rather as a massive. improved electrical resistance and chloride-binding capacity are reported. Dense packing is another basis of superior performance of concrete containing silica fume and superplasticiser. which repel each other and get deflocculated and dispersed. dense C-S-H occupies all the space around aggregate and direct bond with aggregate is established. is to get adsorbed onto cement grains. as against C-S-H phase in the bulk matrix. A concrete exhibit less porosity with no evidence of capillary pores and only very narrow . Mix design and field practices . it enables water content to be reduced by about 20 percent or more and results in high strength. dense structure. Consequent to the depletion of calcium hydroxide in pozzolanic reactions. Hence. concrete mix design and field practices are quite critical for high performance concrete. which is the main source of calcium in the system and can exchange with some alkali (Na or K) in the ASR gel. because of low water-cement ratio. In normal strength concrete with only cement. Because of enormous surface area as well as relatively large content of glassy silica. The porosity is also higher. The stress-strain curve remains linear up to about 85 percent of failure stress or higher. superplasticisers are required. C-S-H gel particles in concrete containing silica fume appear not as individual particles. The cement grains. Improved corrosion resistance of high performance concrete in terms of impermeability to chloride and oxygen diffusion.From durability considerations. Since the heat of hydration of both are of the same order. The overall result is a denser microstructure. Reduced permeability of concrete makes ingress of water from the outside difficult and alleviates ASR. on hydration. Alternately.The role of superplasticisers. high performance concrete helps in alleviating alkali-silica reaction in concrete. By residing in the pores in hydrated cement paste. Alkali-Silica Reaction (ASR) . Improvement in Durability – Corrosion Resistance . Such porerefining action reduces the size of pores. incorporation of silica fume in concrete increases the water demand. it is a very reactive Pozzolana. silica fume particles. 53 . The resulting improvement in workability of concrete could be either to produce flowing concrete for the same cement and water contents as in the control mix. the transition zone around aggregate is 20µ m to 100 µ m wide and richer in calcium hydroxide and ettringite. However. which in normal circumstances tend to flock together. reduction in air and water permeability is important.

Establish optimum dosage by trials on cement + water mixes. Proportion of coarse aggregate to sand content may be 1. May require about 25 mm more slump for comparable level of workability than in normal grades. so standard deviation (SD) is not likely to exceed 5 MPa or Coefficient of variation (COV) not more than 3 to 4 percent. Code of Practice for Plain and Reinforced Concrete. 54 . 2. margin over characteristic strength need not be high. Chennai. Quality control will. Next. Field Practices. to allow for temperature rise during transportation. the mix design should be checked under field conditions and necessary adjustments made to allow for placing and transportation methods and required slump retention. J. For each trial. Detailing of rebar may have to be altered in critical areas. M. With viable superplasticisers. Final moist curing should commence after final setting and continue for at least 7 to 10 days. P. until optimum result is obtained. Hence.1. start trial mixes with cement + silica fume at steps of 400 . Mehta and P. Monteiro: Concrete: Microstructure. Make preliminary estimate of water-binder ratio (w/b) for target strength by establishing such relationship. In addition. 1. Longman. reduction in water content of 25 . 0. Properties of Concrete. A further mock-up or prototype testing should preferably be made to see the effect of reinforcement congestion. ice flakes may replace part of the mix water.30 percent is possible. .The mix design arrived after laboratory trials should be tested for physical properties.M. High performance concrete containing silica fume is cohesive. gradually increase the amount of superplasticiser until the desired workability is attained. MSA of coarse aggregate should be 20 mm. For target 28-days compressive strength in 80 -100 MPa range. Indian Concrete Institute.Some points to remember are. 2. Temperature of fresh concrete at the mixing stage should be kept lower than what is stipulated at the time of placement. but 'sticky'. free from segregation. Handbook of Concrete Mixes. Adjust the sand and coarse aggregate contents. opaque colour plastic sheets or curing compound. Cooling of aggregates may be necessary. Mixing time will be longer than in normal mixes. Indian Edition. perforce.35. Insulation of drums of transit mixers and concrete pipelines is preferable.30 and 0. Plastic shrinkage cracking is likely. if curing is not proper. • • • • Mixes are cohesive. Neville. so there is little bleed water to rise to the top and offset water lost due to evaporation. Steps of mix design are suggested below.0 ..450 kg/m3 and w/b at 0. Presence of fine powders increases water content. Indian Standards Specifications 1. Check compatibility of superplasticiser to cement and establish its water reducing efficiency. Project specifications in many cases stipulate the maximum water-cement ratio and percent of silica fume to cement by weight. 4. Properties and Materials. 4th Ed. The optimum sequence of mixing of ingredients should be established by trials and no prior guidance is possible. Effort should be made to keep the cement content minimum possible. K. with moist covers. be stringent. Initial curing should commence after initial setting of concrete and removal of side forms. 3.Mix Design . New Delhi. A. Curing .25.5. 3. Reference Books – 1. SP – 23 (ST). Bureau of Indian Standards. (Indian Edition). IS: 456 -2000. This will save on cement content.

----------- α β γ ≈ µ "→ 55 . 3. IS: 383 – Specifications for Aggregates from Natural Sources.2. IS: 3812 – Methods of testing of Aggregates. 5. IS: 516 and IS: 1199 – Methods of testing concrete. 4. IS: 9103 – Specification for Chemical Admixtures.