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LECTURE NOTES - CEMENT TECHNOLOGY I INTRODUCTION (1)

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;

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.

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 Leas 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, -------

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 > 90m (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.

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

heating takes place on a grate at the bottom. Because of the colour of the feed, it is called black meal process. Of course, rotary kilns of smaller capacities can also be adopted.

The first cement kilns were static vertical kilns. VSKs were use in the Victorian era. Rotary kilns came later, at the turn of the 20th century, when a kiln with a revolving cylinder lined with firebricks for manufacture of cement was patented in 1877. In India, there are about 365 mini cement plants, most being of vertical shaft kiln type. The capacity is required to be less than 600 tpd, although in practice, they are of much smaller capacity. The total installed production capacity is nearly 11 MT, producing about 6 MT annually. In China, the number is in thousands, although many of these are being abandoned now. TABLE I Types of Cement Plants in India Items / Year No. of wet kilns Installed capacity (t/d) % of total kilns No. of Semi-dry kilns Installed capacity (t/d) % of total kilns No. of Dry kilns Installed capacity (t/d) % of total kilns Total kilns Reference Books 1950 32 9151 97.3 1 250 2.7 1960 70 25001 94.4 3 1200 4.5 1 300 1.1 74 1970 93 38441 69.5 8 5000 9 18 11865 21.5 119 1983 95 39641 41.1 9 5500 5.7 50 51265 53.2 154 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

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1. Neville, A. M., Properties of Concrete, Longmans, 2. Leas Chemistry of Cement and Concrete, 4th ed., Butterworth,

CHEMISTRY OF CEMENTS (3)


Chemical Composition and Phases in Portland cement Portland cement, being made from calcareous and argillaceous raw materials, is, as to be expected, composed of compounds of oxides of calcium (CaO), silicon (SiO2), aluminum (Al2O3) and iron (Fe2O3). It is customary to express the chemical formulae of the compounds in cement as the sum of the oxides e.g. Ca3SiO5 is expressed as 3CaO.SiO2. It does not mean that the constituent oxides exist separately within the structure of the phases. One exception is MgO, originating from impurities in the main raw materials. Among the main oxides, CaO occurs as Calcite (CaCO3) in limestone. It decarbonates at about temperature of 680OC and above. CaCO3 CaO + CO2 We had taken note of this reaction in connection with lime manufacture. It is an important reaction in cement manufacture, both in terms of thermal energy consumed, reduction in solid volume and the amount of CO2 emitted to the environment. SiO2 occurs as aluminosilicates in clay or shale, rather than the oxides. Silica, SiO2 exists naturally in the pure state as different crystalline polymorphs (e.g. quartz, Crystobalite and Tridymite). Poorly crystalline or amorphous forms are also found as in Opal and Flint etc. Al2O3 and Fe2O3 are not essential for the hydraulic properties, but their presence is essential as flux in the hottest zone of the kiln in cement manufacture, to keep the thermal energy required to manageable economical levels. Minor components are those, whose presence even in small amounts (<1.0 percent) can make profound difference in the manufacturing process, in the environmental issues, or the properties of the cement. Primary among them are alkalis - Sodium (Na2O) and Potassium (K2O) oxides, which are really present as sulphates, and MgO. Others include Chlorides (Cl -) Manganese (MnO2), Boron (B2O3), Phosphorous (P2O5), Titanium, Chromium etc. These will be discussed later in this Course. Cement Chemistry Notations It is customary to abbreviate common oxides to single letters, e.g. C for CaO, and the compound, for example Ca3SiO5 is first written as 3CaO.SiO2 and then expressed as C3S. The total list is given below; Cement Chemistry Notations Item Oxide Cement / Clinker CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O TiO2 P2O5 Others CO2 SO3 H2O Gypsum, Calcium Sulphate Hydration Products Calcium Silicate Hydrates Notation C S A F M K N T P S H CS C-S-H

Calcium Hydroxide Typical Chemical Composition The cement clinker has typically a composition of; CaO - 60 to 65 %, SiO2 19 to 22 %, Al2O3 5 to 8 %, and Fe2O3 3 to 5 %.

CH

After addition of gypsum (or other form of calcium sulphate) 5 %, the range of typical chemical composition of ordinary Portland cement (taken from a UK source) is as given in the Table below. Chemical Composition of Cement (Typical) Item CaO SiO2 Al2O3 Fe2O3 K2O Na2O SO3 MgO Free Lime Loss on Ignition (LOI) Insoluble residue (IR) Amount, % 63.2 66.4 19.5 22.2 4.1 6.2 2.1 3.3 0.43 0.80 0.14 0.24 2.5 3.0 0.8 1.4 0.9 2.1 0.7 1.7 0.5 1.7

Two terms in the above composition need explanation. Loss on ignition is the loss of mass when heated to 1000OC, which could be due to any moisture or CO2 attracted during storage, CO2 in the limestone filler when permitted to be added, any water content in gypsum not driven out during manufacture, or any adulteration. Insoluble residue is what is insoluble in hydrochloric acid; indicate free quartz, impurities from rock gypsum, or insoluble in adulterants. When industrial wastes like fly ash, which are mostly acid-insoluble, are permitted to be added in composite cements, the values of IR are higher. In Indian cements, the values for CaO content could be somewhat lower, depending upon the quality of limestone. Proportion of MgO in some cases can be higher, the upper limit being 5%. The Phases in Portland cement Before the phases present in cements are identified, let us consider how the oxides interact at different compositions and different temperature, as binary, ternary and quaternary systems. These are best studied in terms of phase diagrams. What is described here is a simple explanation. The System CaO SiO2 The equilibrium phase diagram for the system CaO SiO2 is shown below. It contains four binary compounds CS, C3S2, C2S and C3S. The melting point of pure CaO is about 2750OC, and that of SiO2 is about 1698OC. However, presence of each other lowers the liquidus temperature. Out of the four phases, CS and C3S2 are not hydraulic, nor are they formed during cement manufacture. C2S has a number of polymorphs. On cooling from higher temperatures, - C2S ultimately transforms to form at 630OC. At still lower temperature transformation to - C2S, which is not hydraulic, takes place. Fortunately, C2S can be stabilized to low temperatures by quenching, or by forming solid solutions with a large number of oxide impurities like boric oxide (B2O3) or Phosphorous pentaoxide (P2O5) and MgO.

C3S is the most abundant phase. Although a lower limit of solubility exists for C3S at about 1250OC, its decomposition to C2S and CaO does not occur on cooling; C3S exhibits a range of metastable modifications between room temperature and 1100OC, which are; Rhombohedra ( R ) Monoclinic ( M ) Triclinic ( T ) forms.

CaO Al2O3 System The relevant phase diagram is reproduced below. 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, CA, C12A7, CA2 and CA6. Except CA6, all other phases are hydraulic.

For compositions common in ordinary Portland cement manufacture, C3A is formed, which is responsible for early hydration and setting. Gypsum is used to control the rapid hydration of C3A phase and initial set. CA and C12A7 are predominant phases in aluminous cements. CA2 and CA6 phases may be present in those with high alumina content. Ternary System CaO SiO2 Al2O3 Lime rich binary phases comprise nearly 90 % of cement composition. The equilibrium phase assemblage at the burning temperature for the cement manufacture consists of C3S, C2S and a liquid phase of composition Lc shown in the figure below. This liquid phase is containing the aluminous components. The final phase assemblage obtained on cooling is more complex. It will consist of C3S, C2S, C3A and a melt. The melt, on cooling would crystallize to give C2S, C3A and C12A7. In practice, all the four phases - C3S, C2S, C3A and C12A7 are obtained.

The System CaO Al2O3 Fe2O3 The most significant phase in this system has a composition Ca2 (Alx Fe1-x)2O5, where x is between 0.48 and 0.7.If CaO is also present x is fixed at 0.48, giving a composition close to C4AF called the Ferrite phase. This phase contains a number of other ions in solid solution. Fe3+ also dissolves in C3A, C12A7 and CA, up to about 4.5% at 1325oC. The Quaternary System CaO SiO2 - Al2O3 Fe2O3 We can now take a look at the phases present in Portland cement, which is a quaternary system in the four oxides, besides minor components. More than 95% of the composition of Portland (and aluminous) cements comprise compounds containing CaO, SiO2, Al2O3 and iron oxides. There are no quaternary phases and at equilibrium, any mix composition will crystallize the following four phases; Alite It is tricalcium silicate - Ca3SiO5, which is written as 3CaO.SiO2 or expressed as C3S. Pure C3S consists of 73.7% CaO and 26.3% SiO2. In industrial clinkers, the composition is modified by incorporation of Mg2+, Al3+ and Fe3+ ions in solid solutions, the total of impurity oxides is of the order of 3 to 4 percent. The crystal structure of cement minerals have been studied in details, which is not discussed here. In Indian cements, C3S content typically varies from 30 to 48 percent. Belite It is dicalcium silicate Ca2SiO4, which is written as 2 CaO.SiO2 or expressed as C2S. Pure C2S consists of 65.1% CaO and 34.9 % SiO2. In industrial clinkers, the composition of Belite is modified by incorporation of foreign ions, usually Al2O3 and Fe2O3, the total impurity oxides

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being 4 to 6 percent. Limit of K2O substitution is 1.2 percent. In Indian cements, C2S content typically varies from 27 to 45 percent. It is to be noted that in Portland cements, the total of C3S + C2S content is between 70 to 80 percent, perhaps closer to 75 percent. Aluminate phase It is tricalcium aluminate Ca3Al2O6, which is written as 3 CaO.Al2O3 or expressed as C3A. Pure C3A contains 62.3% CaO and 37.7% Al2O3. The composition is modified by incorporation of foreign ions like Si4+, Fe3+, Na+ and K+. The substitution is substantial it could be 13 percent for cubic and 20 percent for orthorhombic modification of the crystal structure. In Indian cements, C3A content typically varies from 4 to 10 percent. Ferrite phase It is tetra calcium alumino ferrite Ca2AlFeO5, also written as 4 CaO.Al2O3.Fe2O3, or abbreviated as C4AF. Ferrite phase can be prepared with any composition in the solid solution series Ca2 (Alx Fe1-x)2O5, where x is between 0 and 0.7. C4AF is a particular form for x = 0.5. Pure C4AF contains 46.1 percent CaO, 21 percent Al2O3 and 32.9 percent Fe2O3.The composition is substantially modified by variation in A/F ratio and incorporation of foreign ions like Mg2+, Si4+ and Ti4+. Mn3+ can replace all the Fe3+ ions or up to 60 percent of Al3+ ions. The ferrite phase makes up about 5 to 15 percent of ordinary Portland cement clinkers. Calculation of Amount of Different Phases Chemical analysis of cement or clinker is obtained in terms of oxides, as shown in the example given above. Estimation of the relative proportions of the phases is accomplished by the procedure known as Bogue calculation. It is based on the following steps;

Assume that the compositions of the four major phases are C3S, C2S, C3A and C4AF. Assume that Fe2O3 occurs in C4AF. Assume balance of Al2O3 occurs in C3A. Deduct from the CaO content, the amounts attributable to C3A and C4AF and solve two simultaneous equations to calculate the amounts of C3S and C2S.

The formulae for clinkers are;

C3S = 4.0710 CaO 7.6024 SiO2 6.7187 Al2O3 1.4297 Fe2O3. C2S = - 3.0710 CaO + 8.6024 SiO2 + 5.0683 Al2O3 + 1.0785 Fe2O3. = 2.8675 SiO2 0.7544 C3S. C3A = 2.6504 Al2O3 1.6920 Fe2O3. C4AF = 3.0432 Fe2O3. For cements, put (CaO 0.7 SO3) in place of CaO. The above gives the potential phase composition and differs from the true phase composition because; Equilibrium may not be maintained during cooling, and Composition of clinker phases differ from the pure compounds, as explained before.

The total of four phases calculated plus free lime will not add up to 100 percent, because minor oxide components are ignored. It is implied that all the MgO occurs as periclase. Reference Books

1. Leas Chemistry of Cement and Concrete, 4th ed., Butterworth.


2. R. H. Bogue, Chemistry of Portland Cement, Reinhold, New York.

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3. H. F. W. Taylor, Cement Chemistry, Academic Press, London. ---------

CLINKER FORMATION (1)


For satisfactory clinker formation, the states of both heating (to a high temperature) and subsequent cooling should be accomplished in a satisfactory manner, The chemical composition of the raw materials and their proportions, the physical state i.e. fineness and homogeneity, and the features of the kiln cooler system are important. It is essential to approach phase equilibrium at clinkering temperatures. The mineralogical state of the clinker obtained at the peak firing temperature becomes thermodynamically unstable during the cooling stage. Rate of cooling and quenching are important. 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. Both are taken from Leas Chemistry of Cement and Concrete.

Summary of Reactions Occurring during Clinker Formation Reaction type Decomposition Diffusion Melting Liquid phase sintering Polymorphic transformation Evaporation / condensation In summary, we may note; Examples and comment CaCO3 CaO + CO2; one or more volatile substances form in the course of reaction 2 CaO +SiO2 Ca2SiO4; solid-state reaction between components Formation of C-A-F-S eutectic at 1338OC between C3S, C2S, C3A and C4AF. 3 CaO + SiO2 Ca3SiO5; precipitation of alite from melt, in which the reactants are dissolved. -C2S and/or - C2S; polymorphic changes occurring during cooling. (Liquid)K2SO4 (vapour)-K2SO4; evaporation and condensation of alkali sulphates.

I. Below 1300OC The reactions that take place are;

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a. Decomposition of calcite at 680OC and above, b. Activation of silicates through removal of water and changes in the crystal c. d. e.
structure at up to 700OC, Decomposition of clay minerals 900OC, Initial combination of calcite or lime from it with activated quartz and Al2O3 and Fe2O3 700 - 900OC, Belite forms at 900 1200 OC.

II. Between 1300 1450OC Clinkering.


A melt is formed mainly from aluminate and ferrite phases. By 1450OC, some 20 to 30 percent of the mix is liquid. Much of belite and nearly all the lime react in the presence of the melt to form alite. The material nodulises to form clinker. III. During cooling The liquid crystallizes giving mainly aluminate and ferrite. Polymorphic transformations of the alite and belite occur. Moduli Values In the manufacture of Portland cement, it is desirable that C3S content is optimized and the free (uncombined) lime content is minimized. For such a situation, the CaO content is given by; CaO = 2.8SiO2 + 1.18Al2O3 + 0.65Fe2O3. CaO The ratio -------------------------------------------- is called lime saturation factor (LSF). 2.8SiO2 + 1.18Al2O3 + 0.65Fe2O3 LSF largely shows the proportion of alite and belite in the clinker. In Portland cements, it is typically in the range of 0.92 to 0.98, although specifications allow a range of 0.66 to 1.02. For LSF> 1.0, free lime will be present. Please note that the above formula is for clinkers; for cement, use (CaO 0.7SO3) in place of CaO. Some other useful limits are; Silica ratio (SR) = SiO2 / (Al2O3 + Fe2O3). SR is typically in the range of 2.0 to 3.0. Increase in SR means proportion of liquid is lower and the clinker becomes difficult to burn. Alumina ratio (AR) = Al2O3 / Fe2O3. The value of AR can vary between 1.0 to 4.0. AR determines the quantity of liquid formed at low temperature. At 1338oC, the quantity of liquid is theoretically maximum at AR of 1.38. Role of Mineralisers and Flux It has been discussed how the presence of Al2O3 and Fe2O3 in the raw mix, although not essential to the constitution of Portland cement, constitute a cheap source of fluxes lowering the thermal energy required in cement manufacture. Al2O3 and Fe2O3 form a liquid melt, in which much of the belite (C2S) and nearly all the CaO react, to form alite (C3S). Other volatiles like MgO, Na2O and K2O also act as flux. When the ratio of A/F is > 1.38 and the amount of MgO present is < 2 percent, the amount of flux present at different temperatures is given by the formulae; Flux at 1338OC = 6.1 x% Fe2O3 + % MgO + % Na2O + % K2O. Flux at 1400OC = 2.95 x % Al2O3+ 2.2 x% Fe2O3 + % MgO + % Na2O + % K2O. Flux at 1450OC = 3.0 x % Al2O3+ 2.25 x% Fe2O3 + % MgO + % Na2O + % K2O. Where the ratio A/F is < 1.38,

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Flux at 1338OC = 8.5 x % Al2O3 5.22 x% Fe2O3 + % MgO + % Na2O + % K2O.


If the level of flux is less than 19 percent, the coating formation is inadequate and refractories are likely to be damaged. Excessive high flux levels at 1338OC will lead to ring formation at the point where the kiln feed enters the burning zone. It is, therefore, necessary to ensure the optimum level of flux by careful design of the raw mix. The desirable range could be about 19 to 26 percent. Somewhat higher level may be required in case of difficult raw materials, but not exceeding 28 29 percent. Mineralisers These are minor components or additives in the raw mix in small amounts, which increase the activity of the clinker phases, facilitate formation of clinker having adequate properties with lower grade limestone or at lower temperatures. From material science, it is known that the activity of a single crystal may be enhanced by introducing defects in the crystal structure. Extrinsic defects can be induced in the clinker phases by crystallochemical substitution forming solid solution, which contribute to the reactivity of the phases. 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; Fluxing action Temperature of first formation of liquid are reduced; the viscosity and surface tension of the liquid are modified; and crystal morphology is modified. Phase relations The relative thermodynamic stabilities of the clinker minerals are changed due to solid solution effects; Hydraulic activity The reactivity of clinker minerals (alite, and more particularly, belite) are modified by solid solution and/or crystal symmetry effects (defects). In cement manufacture, liquid formation is assisted by traces of halides like Cl- and F-. Presence of chlorine (Cl-) in the cement invites opposition from the users, because of risk of corrosion of reinforcing steel. Fluoride addition has the unique combination of acting as a flux, lowering the temperature of melt formation, reducing the viscosity and surface tension of the liquid and enhancing the thermodynamic stability of C3S, enabling its formation at temperature < 1250OC. Formation of liquid may take place at lower temperatures also due to presence of sulphates and carbonates, which have low melting point eutectics ( 800 - 900OC). Among transition metal oxides, the effectiveness to aid C3S formation at 1350OC, at 0.5%addition was found to be as follows; CuO > ZnO > MnO2 > SnO2 > PbO. Fluorspar, Fluorogypsum, Basalt and Barite are among the mineralisers used in the Indian cement industry. Use of fluorspar has been reported to reduce the amount of free lime, increase in C3S content or lower the clinkering temperature. Barium increases the reactivity of C2S phase by substitution in the crystal structure. Chromium and Titanium Oxide can increase the sizes of alite and belite crystals. However, in all such cases, the amount has to be controlled very carefully, to prevent other adverse effects. Reference Books

1. Leas Chemistry of Cement and Concrete, 4th ed., Butterworth.


2. R. H. Bogue, Chemistry of Portland Cement, Reinhold, New York. 3. H. F. W. Taylor, Cement Chemistry, Academic Press, London. -------

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TYPES AND PERFORMANCE CHARACTERISTICS OF CEMENTS (4)


Cement is defined as a hydraulic binder, which, when mixed with water, forms a paste which sets and hardens by means of hydration reactions and processes and which, after hardening, retains its strength and stability even under water. 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. 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 products of hydration of cement gradually fill the space between aggregate particles to give a continuous matrix. Relatively impermeable composite results, which is strong in compression. The solubility of hydration products in water being rather limited, the composite becomes stable and durable. The cement paste sets and hardens as the hydration proceeds after contact with water. The term setting denotes a rather sudden loss of plasticity of the paste and conversion to a solid material. The strength at this stage may not be much. The term hardening denotes the development of hardness and strength following the setting of cement paste. The products of hydration of cement are chemically the same as the products of hydration of the individual phases. The physical behavior of hydrating cement is similar to those of the two calcium silicates. The rates of hydration of the phases are, however, different, as is apparent from the figure below. C3A and C4AF phases have the highest rates of reaction, followed by C3S, and C2S is the slowest to react.

The hydration product of calcium silicate phases, C3S and C2S, are calcium silicate hydrate with a probable composition of C3S2H3 (abbreviated as CSH), and calcium hydroxide Ca(OH)2. The reactions are of the types; For C3S C3S + 6H C3S2H3 + 3 Ca(OH)2,

The corresponding masses involved are: 100 + 24 75 + 49.

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For C2S

C2S + 4H C3S2H3 + Ca(OH)2,

The corresponding masses involved are: 100 + 21 99 + 22. The above equations indicate that both C3S and C2S require about the same amount of water for reaction, but C3S produces more than double the amount of Ca(OH)2. C-S-H has the strength giving properties, whereas Ca(OH)2 has no significant contribution towards strength, except through pozzolanic reaction (see later). The composition of C-S-H indicated as C3S2H3 is, at best, approximate. It indicates the molar ratio of C/S to be 3, whereas, in hardened cement paste, it is much lower between 1.4 to 2, 1.7 being more probable. From the structural viewpoint, C-S-H is known to exist in variety of forms and composition, and a more general description (CaO)x.SiO2. y.(H2O), with x and y having a range of possible values, is more apt. For C3A C3A + 6H C3AH6.

The corresponding masses involved are: 100 + 40 140. For C4AF Under comparable conditions the products of hydration of the ferrite phase are, more or less, similar to those of C3A, although the rates differ. The relative rates of gain of strength for hydrates of different phases are shown in the figure below.

The rate of strength development of cement depends upon the relative proportion of different phases present. For example, higher C3S content results in greater strength at early ages than when the C2S content is more. Other factors like fineness of grinding are also important. Role of calcium sulphate addition in cement The final form of calcium aluminate hydrate existing in hydrated cement is probably the cubic crystal C3AH6, but it is possible that a hexagonal C4AH12 crystallises out first and later changes to the cubic form. The reaction of C3A with water proceeds very fast and leads to immediate stiffening, which is called flash set. In order to prevent this, gypsum, or some other form of calcium sulphate is added during grinding of cement clinker. In the presence of calcium sulphate,

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the amount of C3A directly hydrating to C3AH6 is considerably arrested, and calcium sulphoaluminate hydrate (ettringite) C6A.S3.H32 is formed first. Ettringite is also called trisulphate. C3A + 3CSH2 + 26H C6A.S3.H32. As hydration proceeds and the available calcium sulphate gets consumed, trisulphate ettringite formed initially reacts with the excess of C3A to form calcium -aluminate monosulphate hydrate (monosulphate) - C4ASH12 as the product of reaction; C6A.S3.H32 + 2C3A + 4H 3 C4ASH12. A hexagonal calcium aluminate hydrate, C4AH19 also forms, which may be present as separate crystals or in solid solution with monosulphate. The calcium sulphate added is usually in the form of mineral gypsum, (calcium sulphate dihydrate, CaSO4. 2H2O). Other forms are calcium sulphate hemihydrate, CaSO4. H2O or calcium sulphate anhydrite, CaSO4.. In India, mineral gypsum is mostly obtained from the mines in Rajasthan. Its purity (in terms of SO3 content) is limited. The quantity mined is not enough for the entire cement production in the country and the distances involved are large in many cases. Chemical gypsum, like phospho-gypsum and fluoro-gypsum obtained as waste products from chemical industries is used. These may require washing to remove impurities. Marine gypsum from sea bed has high purity, but the chloride content may exceed the value permitted in cement specifications. Rate of heat evolution during hydration Hydration of cement is an exothermic reaction. The rate of heat generated helps in monitoring different stages of hydration of cement and the setting process. This is shown in the figure below, which indicates three peaks in the rate of hydration within first three days or so.

Immediately after contact with water, formation of hydrate phases gets underway. Alkali sulphate mainly K2SO4 dissolves in water within seconds, giving rise to the initial endothermic peak. The hydration of C3A before SO3 comes into reaction is accompanied by evolution of much heat, which is responsible for the first peak. As sulphates control the hydration of C3A, a dormant (induction) period follows, during which the rate of reaction is slow. 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 impedes further hydration. This stage lasts for about one to two hours, during which the cement paste is workable. 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, depending upon the cement characteristics. During this period, the products of hydration of individual cement grains come in contact with each other forming a network and setting takes place. Following this peak, the rate of hydration again slows down, till the third peak is reached, due to reaction of C3A with ettringite, once SO3 is depleted. Use of industrial wastes -

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Various industrial wastes are used in cement, primarily as additions, which are blended or interground with cement clinker and calcium sulphate, to result in blended or composite cements. Others can be used as raw materials in the manufacture of cement clinker. Use of chemical gypsum for set control was mentioned above. Some of the industrial wastes used in cement are discussed below. Fly ash Fly ash is a pozzolana, which in itself, is not hydraulic, but can combine with lime in the presence of water, to give cementitious products. Fly ash is obtained as fine particles in the exhaust flue gases in coal-fired thermal power stations. These are collected in the electrostatic precipitators and disposed of, either in dry or wet state. Typical chemical composition of Indian fly ashes is given in Table I; TABLE I TYPICAL COMPOSITION OF INDIAN FLY ASH SiO2 52 60 percent, Al2O3 - 20 33 percent, Fe2O3 2 7 percent, CaO 2 10 percent, Loss on Ignition 1.5 14 percent, And small amounts of MgO. SO3, Na2O and K2O. The quality requirements are specified in IS: 3812 Part I 2003, and are comparable to other international specifications (Table 2). The main requirements, which govern the performance of fly ash in cement and concrete, obtained from one source, can be summed up in terms of five key parameters. These are; Specific surface area, Blaines, Residue on 45 sieve (325 mesh), Unburnt carbon, commonly measured as Loss on Ignition (LOI), Moisture content, unless collected dry, and Glass content. Siliceous pozzolanicity of fly ashes require that the SiO2 phase be in glassy form. The glass content of Indian Fly ashes (20 35 percent) are lower than in other countries (70 90 percent) and, to that extent, the reactivity are power. Reactivity goes up with fineness and can be improved by further grinding. Portland Pozzolana cement (Fly ash based) is specified in IS:1489 Part I. It permits addition of 15 to 35 percent fly ash. Addition of 20 25 percent is common practice. Hydration reaction of fly ash in cement- The pozzolanic reaction involves the active SiO2 component in fly ash combining, in presence of water, with the Ca(OH)2 liberated during hydration of silicate phases of Portland cement, to form calcium silicate hydrates (C-S-H). CaO + SiO2 + H2O C-S-H. Such C-S-H differs in composition from that resulting due to hydration of the silicate phases in Portland cements. In addition, ettringite is formed rapidly and is observed from 5 hours up to 28 days. Formation of C-S-H due to pozzolanic reaction manifest after the initial hydration of Portland cement - may be 3 to 14 days after mixing with water, although C-S-H following hydration of C3S phase is visible after 24 hours.. Nearly equal masses of silica and lime combine; in other words, a pozzolana rich in content of active silica (for example, silica fume containing 85 to 90 percent silica in glassy form) can combine with equal mass of lime liberated by cement hydration. With Indian fly ashes, much of the Ca(OH)2 remains unreacted in pozzolanic reaction.

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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. It consists essentially of silicates and aluminates of calcium. Molten slag when allowed to cool in air, loses its glassy form. It should, therefore, be water quenched to retain the glassy form and its reactivity. This is called granulation and what is used in cement and concrete. Subsequent reference to slag will mean granulated blast furnace slag, suitable for use in cement. The requirements of composition are covered in IS: 12089, which lay down minimum glass content of 85 percent, for use in cement and concrete. The chemical composition varies over a wide range (Table 3). TABLE 2 SPECIFICATIONS FOR FLY ASH IN CEMENT AND CONCRETE (Values are %, unless other units are indicated) Item SiO2, min. Reactive / soluble SiO2, min. S + A + F, min. MgO, max. LOI (1 hour) max. Total Alkalis, max. SO3, max Free CaO, max Total/ reactive CaO, max. Fineness, 45 micron, max Blaines m /kg min. Cement activity, 28 days Lime reactivity, N/mm Autoclave, %
2 2

ASTM C-618

European Specifications

India, IS: 3812 Pt. 1 35 35 20 70 5 70 5 5 1.5 3.0

En-450 En-197-1 BS 3892-I Earlier -1981 Current 2003 25 25

70 6 1.5 5 3 1 10 40 *** 75* 10 10 34# 75* 1 10 10 12 2 57 5-7 7

12 1.5 2.75

34 320 320 80@ 4.5 10 0.8 0.8 80@ 4

80** 10

Soundness, Lechatelier, mm 0.8

Notes I. *** Permitted variation + 10% of average ii. #Permitted variation +/- 5% of average iii. * 25% fly ash ** 30% fly ash @ 20% fly ash iv. Water content - 95% in BS 3892, 105 % max in ASTM v. Drying Shrinkage in IS 3892, < 0.15% vi. Requirement of colour consistency in BS 3892 For use in the manufacture of Portland slag cement, the chemical composition of slag should satisfy the following ratios;

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CaO + MgO + 1/3 Al2O3 ----------------------------------SiO2 + 2/3 Al2O3 CaO + MgO + Al2O3 ----------------------------------SiO2

1.0,

1.0,

CaO + CaS + MgO + Al2O3 ---------------------------------- 1.5, SiO2 + MnO TABLE 3 TYPICAL CHEMICAL COMPOSITION OF SLAGS Characteristics SiO2 Fe2O3 Al2O3 CaO MgO IR S (Sulphide sulphur) Glass content Range, percent 29 36 02 16 30 31 34 7 12 0.4 5.5 0.5 1.5 80 - 95

IS: 455 permits addition of granulated slag in the range of 25 to 70 percent in the manufacture of Portland Slag cement, by inter-grinding or separate grinding and blending. Because of relative hardness of slag, the common level is 40 to 50 percent. Ground granulated slag can also be added to OPC and other ingredients of concrete in a concrete mixer. Hydration of slag in cement The difference between fly ash and slag is that the latter is hydraulic; slag, on its own can hydrate in contact with water. However, the reaction is very slow. No hydration products can be observed when slag is placed in water; however, there is evidence that the surface of the slag is modified as soon as it comes in contact with water. The hydration of slag can be activated. Known activators are sodium hydroxide, sodium carbonate, sodium silicate, calcium sulphate, phosphogypsum, and of course, lime. Ca(OH)2 liberated by hydration of Portland cement activates the hydration of the slag component in Portland slag cement. The slag surface is first covered by Portland cement hydrates, then reacts with Ca2+ ions from the supersaturated solution forming C-S-H. Dissolution of Ca2+ and Al3+ ions from slag also leads to formation of the hydrate. C-S-H formed by slag hydration has a lower C/S ratio, of the order of 0.5 to 1.4. Other products of hydration of slag in cement are Ettringite, monosulphate aluminate and calcium aluminum hydrates. The pH value is not reduced to any appreciable extent. 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. In the process, SiO-vapours are produced, which oxidise and condense in the form of very tiny spheres of non-crystalline silica. Apart from IS: 15388 - 2003, ASTM C1240 or ACI Committee Report 226 also offer ample guidance. The essential features of silica fume, which are of importance to concrete making, are the very fine particles and high content of amorphous silica.

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Silica fume should contain 85 - 90 percent SiO2, most of which should be in glassy form. It is common practice to add silica fume as a replacement of OPC in concrete mixer. Industrial wastes as raw mix component Fly ash and slag can be used in limited amounts in the raw mix composition. Much wider scope exists for use of sludges, which are wastes from various chemical industries disposed off in liquid form. A summary of typical chemical composition of various lime sludges is shown in Table 4. These are obtained from fertilizer, paper, acetylene, sugar, chromium and soda ash industries and have the potential to form part substitute of limestone. The major difficulty is that the sludges are in wet form. In absence of wet process cement plants, these sludges must be dried before use in dry process cement plants. Another aspect is the presence of impurities like P2O5, F-, Cl-, alkalis and Cr2O3 etc. in various amounts, which may limit the amount of sludges to be added. In addition, the following industrial wastes have mineralizing properties; Phosphorous slag and phospho-gypsum, Fluoro phosphorous slag, Barium-bearing waste obtained in the manufacture of white mineral pigments, and Zinc-containing wastes.

Types of Cement Classification of cements in different types are done either on the basis of performance characteristics like strength, setting and hardening, colour and heat evolution, or on the basis of chemical composition and resistance to chemical attack. The various types of cements covered in Indian (IS) specifications are listed in Table 5 below. TABLE 5

Types of Cement Covered in IS Specifications S. No. 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. 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 - Fly ash based 1489-I - Calcined Clay based 1489-II Masonry Cement 3466 Supersulphated Cement 6909 Special Cements Oil Well Cement High Alumina Cement for Structural Use 8229 6452

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ASTM C150 classifies Portland cement into five types;

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.

In addition, ASTM C595 and ASTM C150 classify blended hydraulic cements as; Type I (SM), Type IS Portland blast furnace Type I (PM), Type IP Portland-pozzolana Type S Slag cement.

European specification EN 197-1 has adopted an elaborate scheme of specifying different types of cements. The features and comparison of the specification requirements in all the three are given in a publication listed below. Reference Books

1. Leas Chemistry of Cement and Concrete, 4th ed., Butterworth. 2. Neville, A. M., Properties of Concrete, Longmans 3. Mullick, A. K., Comparison of BIS, ASTM and EN Cement Standards, Publication no. 5,
Grasim Industries Ltd. (Cement Business), Mumbai. 4. Mullick, A. K., and Ahluwalia, S. C., Utilisation of Wastes in Indian Cement Industry, International Symposium on Cement Industry Solutions to Waste Management, Calgary, Canada, Oct. 1992. --------

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RAW MATERIALS AND MINING (4)


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

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The clay mineral component is generally a soft and loose-textured sedimentary rock deposit of clays, slate, shale and crystalline slates. Depending upon the particle size, these are classified as Clay (<0.002 mm), Silt (0.002 0.063 mm), Sand (0.063 2 mm) or Gravel (> 2mm). Suitability is judged by chemical composition in terms of silica ratio (SR) and alumina ratio (AR). Mineralogical form of silica is important. Large amount of free quartz is not desirable. Assimilation of coal ash in the clinker provides a source of silica in raw mix composition. With high ash coal used in India, often no clay is required to be added separately. Corrective materials Small amounts of materials other than limestone and clay are needed, containing high proportion of oxides which may be deficient in the main raw materials. Laterite or quartz sand is used for increasing SiO2; roasted pyrites or iron ore for Fe2O3; and bauxite for Al2O3. Mineralisers are added with marginal or low grade raw materials or when the raw mix has low burnability. Exploration and Reserve Estimation For the manufacture of 1 tonne of cement, on an average, 1.5 tonnes of limestone are required. For setting up a one MT cement plant, limestone deposit of the order of at least 60 MT are required for a life span of 40 years, and much more for longer life and/or larger plant size and future expansion. Hence, the deposit of limestone has to be properly explored, assessed and evaluated. The main purposes of exploration are; 1. Verifying the quality of raw materials; 2. Establishing the range of variation in the quality of raw materials throughout the working life of the deposit; and 3. Estimating and verifying the workable reserves of raw materials. Availability of limestone in any country is, prima facie, known through geological exploration carried out by the nodal governmental agencies (GSI and State Geological Surveys in India). With this information as the starting point, more focused and dedicated investigation is required to establish availability of cement grade limestone. The exploration is carried out in three stages; Stage I Field inspection of a number of deposits, surface tests, large area mapping and a limited number of exploratory borings. The main aim is to find out the quality of the deposit. Stage II One or more deposits are selected for detailed investigation. Comprehensive drilling programme enables the deposits to be broadly studied. Chemical characteristics, bedding conditions, ground water and possibilities of working the deposit are established over extensive areas. Suitability of the site for quarrying or open-cast mining are known. 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. The amount of exploration and the number of bore-holes depend upon the variation in the chemical characteristics; more intense exploration being necessary when the variation is large and vice-versa. The variance of the geochemical data of the deposit enables it to be classified as under; Simple when the co-efficient of variation is 4 percent, Complex - 10 percent, and

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

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Drilling, Blasting / ripping, Loading and haulage to the site of primary crusher.

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

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4. Norms for Exploration of Limestone Deposits, National Council for Cement and
Building Materials, New Delhi.

PYROPROCESSING AND CLINKER FORMATION (8)


During the process of cement manufacture, the following operations take place at the temperatures indicated;

1. 2. 3. 4.

Slurry preheat and evaporation of free and chemically combined moisture 100 - 550OC, Preheat and evolution of CO2 from the carbonates (calcinations) 805 OC, Formation of phases and clinkerisation 800 to 1400 OC, Clinker discharge and cooling.

These heat transfer functions in cement manufacture take place in the kiln system comprising the preheater and precalcinator, the kiln, the cooler and the refractory. The heat for pyroprocessing is supplied by the fuel, ignited by hot air and gases from the system. In this section, the kiln, refractories, fuels and the flame characteristics will be described. The heat transfer mechanisms and heat balance involved in cement manufacture will be discussed.

The Cement Kiln System


Dry process plants with preheater and precalcinator will be mainly described, being more common. 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, and also for a wet process kiln for comparison. There are significant differences in the gas and material temperatures.

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

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4-stage suspension preheater (top) and suspension flash furnace precalcinator (below). In order to increase the production rates of preheater kilns, they are equipped with facilities of auxiliary firing to pre-calcine the feed outside the kiln. Precalciners are suspension preheaters equipped with a secondary firing system at the bottom-most stage, before the feed enters the kiln. These are called flash furnaces. The degree of calcinations of the feed will be about 90 percent, by burning 30 50 percent of the total thermal energy required. This operation can use fuel of lower calorific value than required for clinkerisation. 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, or it can come from the kiln itself. There are various designs of preheaters and different types of precalcinator, which will be described later on. The dimensions of the kiln i.e. 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, as the loading in a kiln with kiln feed is only about 6 to 10 percent of the cross section. 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; in case of a preheater and precalcinator the l/d ratio could be from 12 to 18 (short rotary kiln). It is supported on two sets of rollers when l/d = 12 to 14 and three supports when l/d = 16 to 18. The kiln is set in an inclination of 3 to 4.5 %, with the feed end being higher and discharge end lower. The speed of rotation is about 1.5 to 2.5 rpm in case of long kilns and 2.5 rpm for shorter precal kilns. Typical dimensions of kiln (length and diameter) adopted for different capacities in India and abroad are given below. Unless otherwise mentioned, each has 5-stage preheater. 10,000 tpd 6 X 96 m, 6,000 tpd 5.25 X 70 m, 3,500 tpd 4.6 X 70 m, 3,300 tpd 4.4 X 52 m, 3,000 tpd - 4.2 X 50 m, 2,000 tpd - 4 X 54 m; to allow for future expansion, 1,000 tpd 3 X 50 m (only SP), Clinker Coolers - These are fitted at the discharge end of the kiln. It performs two functions; To cool the hot clinker discharged from the kiln, and

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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.

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

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Rotary coolers These were used in earlier times and not in use with modern kilns. The temperature of cooled clinker is about 150 OC. Shaft coolers The clinker is discharged into a vertical shaft with cooling air supplied from the bottom. The temperature of cooled clinker is about 300 OC. What are described above are direct coolers. In addition, there are separate after coolers to lower the final temperature to acceptable value. These are particularly adopted in case of large capacity kilns. These after coolers often receive clinkers at 300 to 350 OC and discharge at 80 to 100 OC. One particular type is called G-coolers.

Refractory
In order to protect the steel shell of the kiln from the high temperature encountered during manufacture of cement, a lining of refractory material is provided. The refractory materials are usually bricks of appropriate size and shape so that they can be laid on the round periphery of the kiln. Alternatively, the material is cast in a plastic stage inside the kiln and allowed to harden, much like laying concrete lining. These are called castables. The requirement of refractoriness varies from zone to zone in the kiln, depending upon the temperature. It is the greatest in the burning zone. What helps the matter is the formation of a coating on to the refractory lining. Coating is a mass of clinker and the dust particles that adheres to the lining, having changed from a liquid or semi-liquid to a solid state. A kiln feed with a high liquid content at clinkering temperature is more effective in coating formation. This happens in easy-burning raw mixes with adequate amount of flux i.e. iron, alumina, magnesia and alkalis. Ash in coal also helps in coating formation. The flame characteristics (to be discussed later) also have an influence in coating formation. Requirements of refractory From the above, it is clear that the refractory should possess the following characteristics; 1. Resistance to temperature encountered in the zone, 2. Spalling resistance ability to withstand high temperature changes inside the kiln, caused by start up, shut down or upset operating conditions, 3. Coatability ability to pick up a coating and maintain it, 4. Abrasion resistance, 5. Slag resistance, i.e. resistance against chemical attack from the materials inside the kiln. Choice of refractory material depends upon test results and records of prior use. Tests are routinely conducted for compressive and tensile strength, modulus of elasticity, chemical analysis, thermal conductivity, density, porosity and gas permeability. Specific performance tests are for melting point, deformations under hot load, linear shrinkage etc. 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 results of hot load are expressed as the temperature at which a definite deformation takes place. Types of Refractories In line with different temperature profiles, refractory materials of different chemical composition and properties are used in different zones of the kiln system. The requirements of the burning zone are most demanding. The following types are used in the burning zone; Alumina silica group the main components being alumina and silica. Refractoriness increases with alumina content and high-alumina (Al2O3 > 70 percent) refractory is used in the burning zone. With increasing alumina content, strength, conductivity and spalling resistance also increase. The bricks are manufactured by dry press or a stiff mud brick. Basic group manufactured mainly from periclase (dense crystalline magnesia), dead burned magnesite and chrome ore. For rotary kilns, majority of refractory used are of

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magnesia-chromium classification (Mag-Chrome) with periclase forming the major component (85 % +). In Chrome Mag bricks, chrome ore forms the major component. In these formulations, periclase is responsible for high refractoriness and volume stability and chrome supplies hot strength and spalling resistance. 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. Dolomite bricks - composed mainly of CaO and MgO and have close affinity to the chemical composition of the kiln feed. Once the kiln attains the operating temperature, they form a coating very rapidly. Spinnel bonded bricks these are newer development, having 10 15 % alumina and 80 85 % MgO. They offer much longer service life than mag-chrome liners. However, these cost more than other bricks.

For other places, refractory materials of different compositions are used. Details are given in the Table below. Service life and reasons of failure For a kiln operator, kiln shutdown due to refractory failure is the main concern. This manifests as a red spot in the kiln shell, where shell temperature becomes excessive due to lack of protection by the refractory lining. This can lead to warping of the kiln shell and replacement may be called for. The ideal refractory life should coincide with the planned annual shutdown. Thus, service life of 11 or 23 months is ideal. While in the cooler regions in the kiln system, refractory materials last for up to 5 years, in the burning zone, the life could be as short as a few days or extend up to two years. The reasons of unsatisfactory service life of refractory are as follows; Frequency of kiln shutdowns, Too rapid heating of the refractory, Overheating the kiln, improper kiln operation, Quality of the refractory material, improper installations, Chemical composition and uniformity of the kiln feed, Mechanical condition of the tire and the kiln shell, and Poor location and poorly directed flame pattern, as discussed later. 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; magchrome bricks (MgO > 65%) Fireclay brick with Al2O3 content decreasing towards feed end; lightweight bricks Acid fireclay brick RUL, OC 1500 1600 1700 1600 1350 1300

Fuels, Combustion and Flame Characteristics For cement manufacture in India, solid fuels in the form of coal are traditionally used; elsewhere liquid (heavy oil) or gaseous fuels (natural gas, LPG) are also used. In addition, the recent trend is to use waste materials having heat value as alternative fuels in cement manufacture. The origin of coal is from decomposition of vegetation with anaerobic bacteria and subjected to thermal and mechanical loads for centuries. The main constituents in coal as fuel are carbon, hydrogen, oxygen and sulphur, besides moisture and ash. The combustible part of coal is

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composed of complex organic molecules. The volatile matter, which is the matter released on heating to 800 OC, should be of the order of 18 to 22 percent, and ash content low. A classification system for coal is on the basis of combustion behavior. It includes four main coal ranks, starting from most difficult to ignite to the easiest; anthracites, bituminous, sub-bituminous and lignite in that order. These are also according to their ages; anthracite being the oldest and lignite the youngest. With age and residence time at high temperature and pressure, older coal formations have less volatiles and more fixed carbon, thereby the difficulty in ignition. Some details of different types of coals and other fuels used in abroad are given below; Details of coal types and other Fuels Group Anthracite Bituminous, Sub-bituminous Lignite Heavy fuel oil Natural gas Moisture ,% 2 3 12 16 - 25 35 0.1 0.2 Volatile matter, % 3 12 18 40 28 34 28 50 Fixed Carbon, % 88 67 74 39 39 30.8 86 # 58 # Ash, % 7 18 49 8 12 6 Calorific value, kcal/kg 7525 6800 8000 - 6380 5400 4800 4000 9500 7500

# - Total carbon content. Indian coals are mostly sub-bituminous, while imported coals e.g. from Australia are bituminous. The ash content in Indian coals is high and calorific value low. Although, 20 to 25 % ash content is considered satisfactory, often ash content in excess of 30 35 percent and calorific value 3,500 kcal/kg are encountered. The coal ash gets incorporated in the clinker structure during sintering and should be taken into account in working out the raw mix proportions. Chemical composition of ash is similar to that of fly ash discussed before, with SiO2 content in excess of 55 percent. If the weight of coal used is about 20 percent of the weight of clinker, and the coal contains 25 percent ash with 55% silica, about 2 - 3 percent SiO2 of clinker weight is contributed by coal alone. Coal should be dried and pulverized to a fine powder before firing. The fineness of coal is expressed as residue in 90 sieve (R90). For coal with ash content up to 20 25 percent, it should be of the order of about 10 percent. The residue on 200 sieve should 1 to 2 percent and nil on 500 sieve. A rule of thumb for such coal (ash 20%) is R90 = half of volatile matter. Lignite coals have high volatile matter (> 50%) and may pose explosion and fire hazard during grinding and storage. Often, it may have to be flooded with inert gases. Depending on its chemical composition (percent C, H, S, O and water, W), the net calorific value of coal can be calculated as; Hu = 33,900 * C + 1, 21,400 *(H 1/8 * O) + 10,500 * S 2,500 * W, in KJ / kg units, or Hu = 8,096 * C + 28,994 *(H 1/8 * O) + 2,508 * S 597 * W, in Kcal / kg units. For proper combustion of fuel, supply of sufficient amount of oxygen (through air) and the required temperature to ignite the fuel-oxygen mixture are necessary. As the fuel is injected in the system, it remains in suspension in the kiln atmosphere. Sufficient time must be available to accomplish complete combustion while the fuel is in suspension in the kiln. The requirement of oxygen for combustion is worked out as follows;

(i)

C + O2 = CO2; 12 units of C combine with 32 units of O, i.e. C kg of carbon requires 8/3 * C kg of oxygen.

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(ii) (iii)

2 * H2 + O2 = 2 * H2O; 2 units of H combine with 16 units of O, i.e. H kg of hydrogen requires 8 * H kg of oxygen. S + O2 = SO2; 1 unit of S combines with 1 unit of O, i.e. S kg of hydrogen requires S kg of oxygen.

Taking into account the amount of oxygen already present in the coal, combustion of 1 kg coal requires (8/3 * C + 8 *H O + S) kg of oxygen. I kg of air contains 0.23 kg of oxygen and 0.77 kg of nitrogen. Hence air requirement for combustion of 1 kg coal is (8/3 * C + 8 *H O + S) / 0.23 kg; i.e. (11.6 * C + 34.78 * H 4.35 * O + 4.35 * S) kg of air. In other countries having good quality fuel, on an average, 1 kg of fuel requires 10.5 kg of air. The coal required for cement manufacture depends on the moisture content and heat value. It was mentioned that in India, the weight of coal consumed in dry process precalcinator plants is about 20 % of the weight of clinker produced. This will give some idea about the volume of air to be supplied for combustion of coal. The ignition temperatures of different types of fuels are; Coal 250 OC, Fuel oil 200 OC, Natural gas 550 OC, Petroleum coke 595 620 OC. Incomplete combustion of coal due to inadequate supply of oxygen results in formation of carbon mono-oxide (CO) rather than CO2, and only 31 percent of potential heat following complete conversion of C to CO2, is generated. For satisfactory operations, it is essential that incomplete combustion must be avoided and there should be no trace of CO in the kiln exit gases. If, in order to ensure complete combustion, the amount of air supplied is more than what is required, presence of oxygen will be noticed in the exit gases. 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, lower flame temperature and greater heat loss. Ideally, there should be neither any trace of CO nor of oxygen in the kiln exit gases. In practice, this is difficult to achieve. The burning conditions in the kiln not being the ideal, often traces of CO and free oxygen are found together in the exit gas. A practical solution is to work on a range of free oxygen in the exit gas being not less than 0.7 percent, or more than 3.5 percent under stable operating conditions, as shown in the figure below. The most desirable range of oxygen in the kiln exit gas is between 1 to 1.5 percent.

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Use of alternate and secondary fuels Driven by the concern for reducing fuel cost, as well as need for environmental improvement, alternate fuels derived from waste materials, which have some heat value, are being increasingly used in the cement industry. These include rubber, rubber tires, paper, paper waste, waste oils, waste wood, paper sludge, even animal meals and animal remains have been tried. Some cement plants in India have used rice husk as part fuel, in combination with coal. Homogeneity of the waste materials should be ensured. In this sense, burning in the cement kiln is not incineration, but valorisation. The process ensures high level of efficiency in energy recovery from the waste. The thermal energy recovered is used in the kiln itself, and the non-combustible portions become raw materials. Attention has been focused on use of petroleum coke (Pet Coke), which is a solid by-product from oil refineries. Global tendency is to use low or very low sulphur content in liquid fuel oils, and the residue with high sulphur and less volatiles result. Pet Coke has 8 to 12 percent volatiles, residual moisture about 1 percent and can be considered to be similar to imported low volatile bituminous coals. What is distinct is high sulphur content of the order of 5 to 8 percent. Presence of sulphur in the fuel causes operational difficulties. Burning of high sulphur fuel requires appropriate burner design and higher primary air consumption, in order to ensure high flame intensity. As mentioned before, the ignition temperature is 595 620 OC. It has to be pulverized to R90 = 5 percent, corresponding to 8 to 12 percent volatiles. Life of refractory may be affected. The SO3 content in the clinker is of the order of 1 to 1.5 percent, which does not contribute to control of setting time in the way externally added gypsum does. Consequently, the total SO3 content in cement tends to become higher. Flame characteristics To an experienced kiln operator, the flame is characterized by many parameters length, shape, point of ignition, direction and colour. A typical flame is sketched below, which shows that on leaving the nozzle of the burner pipe, the flame first has a plume, followed by the point of ignition and then, finally the flame. 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.

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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, with the fuel getting ignited soon after it leaves the burner. Ignition takes place in the burning zone and the flame extends to the calcining zone. Lack of combustion air makes the flame long, as it searches for oxygen further back in the kiln. A high tip velocity of about 70 80 m/s gives exceptionally good flame pattern, as it happens in indirect firing. If the velocity is about 45 66 m/s, as it happens in case of direct firing, a lazy swirling flame results. In any case, 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. The quantity of total air primary air, secondary air and any parasite air due to leakages, is controlled by the speed of ID fan; the greater the speed, more is the air. The primary air velocity should be twice that of flame propagation speed, so as to prevent a flashback of the flame. Generally, under stable operating condition, there is no change in the flame length, as long as the air-fuel ratio is maintained constant. 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. During the initial start of the kiln, when the kiln temperature is too low to ignite the fuel, a pilot burner (auxiliary torch) is placed at the mouth of the burner pipe to obtain good ignition. The temperature of the flame is given by the relation; Hv T = -------------------, 1.11 * A *s Where, T = Flame temperature, OC, Hv = Heat value of the fuel, kcal/kg, A = amount of air required for combustion, kg/kg of fuel, s = specific heat of combustion gas, adopt 0.29. The values obtained by this calculation are of the order of 2000 to 2650 OC. In practice, lower values are obtained and the colour of the flame changes. The following is a guide; Temperature of flame and colour Flame Temperature, 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

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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, convection and radiation. Some examples are; 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.

Heating the feed bed inside the kiln is primarily by radiation. In the burning zone, the kiln feed in a sticky condition is in a constant state of agitation. Aided by the rough and uneven surface of the coating, it rises along the upward-moving side of the kiln and then tumbles back. The hot particles coming in contact with colder parts, transfers heat by conduction. Meanwhile, new particles are exposed to heat transfer by radiation. The coating receives heat from hot gases by radiation. 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. As a result, 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).

Heat exchangers in the form of chains were common in wet process plants and sometimes used in dry process plants also. The chains get heated by the gases and transfer heat to the feed by conduction, as they come in contact. A similar action takes place when heat is transferred from the kiln wall to the feed. The flame radiates heat to the coating. Part of the heat is radiated to the feed bed and part is transferred by conduction, when the feed comes in contact with the wall. The heat transfer in preheater tower is more efficient, as the time taken is small. The difference between the material and gas temperastures is small. Heat Balance In an ideal situation, 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. In practice, this is not the case. The theoretical heat required for clinker formation is estimated to be

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of the order of 400 440 kcal/kg, yet the thermal energy consumed varies from about 1396 kcal/kg in wet process plants (31% efficiency), 1194 kcal/kg in dry process (37% efficiency) to about 750 850 kcal/kg in preheater-precalcinator kilns (about 57 % efficiency).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. Such an exercise helps in conservation of thermal energy by better house-keeping and operational practices. These will be discussed in greater detail later, in lecture on energy conservation. The theoretical heat required for clinker formation depends on the chemical composition of the raw mix and kiln feed. This can be calculated by the empirical formula; Q = 2.2*Al2O3 + 6.48*MgO + 7.646*CaO 5.1165*SiO2 0.59*Fe2O3; where the oxides are expressed as percentages in the kiln feed (loss free basis) and Q is the heat required, in 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- 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

# - All heat values are in kcal/kg. @ - Unaccounted losses are calculated by difference to balance input and output. Take, for example, the following composition of kiln feed on loss free basis; Al2O3 = 4.84, CaO = 67.43, SiO2 = 20.71, Fe2O3 = 2.78, MgO = 2.58, and Loss on ignition = 0.00. Then, using the above formula; Q = 10.648 + 16.718 + 515.57 105.963 1.642 = 435.33 kcal/kg. The Table above gives typical heat balance computation for a wet process kiln and a dry process pre-heater kiln. The above are by way of example only. Many modern dry process preheater plants in India have reported thermal energy requirements of the order of 670 to 700 kcal/kg, and the average consumption figures for the industry are comparable to the best in the world. The computations given above should generate possible ideas for reducing the requirement of heat in cement manufacture. You are encouraged to think of possibilities.

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Reference Books

1. Labahn and Kohlhaas, Cement Engineers Handbook, Bauverlag GMBH, Berlin.


2. K. Perey, The Rotary Cement Kiln, Edward Arnold. 3. W. H. Duda, Cement Data Book, All volumes, Verlag GmBH, Berlin. 4. Report of VDZ Congress, 2002.

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OTHER UNIT OPERATIONS (7) Contents Size reduction crushing, grinding; homogenization and blending; cement grinding; process control and instrumentation; optimization of operations.

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PLANT AND MACHINERIES (7) Contents Different types of preheaters and precalcinator; grinding mills; packing; lay out; plant maintenance; safety in operations.

Reference Books 1. Labahn and Kohlhaas, Cement Engineers Handbook, Bauverlag GMBH, Berlin. 2. K. Perey, The Rotary Cement Kiln, Edward Arnold. 3. W. H. Duda, Cement Data Book, All volumes, Verlag GmBH, Berlin. 4. Report of VDZ Congress, 2002.

CONCRETE TECHNOLOGY (6) Basic Concepts Concrete is the most widely used man-made construction material the world over. 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, long-span bridges, large dams, nuclear power projects, thermal power plants, expressways, industrial structures etc. There are many reasons for such versatility of concrete. It is made of constituents, which are available from natural resources (e.g. aggregates and water), manufactured from naturally

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occurring raw materials (e.g. cement), or industrial wastes and by-products (e.g. fly ash, slag, silica fume). When the ingredients are mixed with water, concrete in its plastic stage can be moulded to any desired shape, and upon hardening, attain the desired mechanical strength, loadbearing capacity and durability for the service environment. Concrete technology is the technology of the constituent materials; their proportioning; workmanship in mixing, placing, compaction, finishing and curing; and its properties in the fresh and hardened states. An important consideration of cement manufacturing is the properties of cement which are critical for its end use in the concrete constructions. Concrete making materials The basic constituents of concrete are cement, aggregate, and water. Cement and water comprise the binder matrix, within which particles of mineral filler - the aggregate are embedded to form the composite. With the progress of knowledge, at least two more components are recognized various industrial wastes as part substitute of cement, and chemical admixtures to be dosed at the time of mixing the ingredients. Small discrete fibers of steel or polypropylene are sometimes added to impart special properties to concrete. All these are being used, in various degrees, in the concrete being made in the country at the present time. Cement Various types and grades of cement, which result from variations in chemical composition and physical properties were discussed under the topic Types and Performance Characteristics of Cements. Chemical composition and physical characteristics of cements influence a number of properties of the concrete made with it, most notably the strength and durability of concrete. The general trend of rate of strength development of different types of cement (ASTM classification) is shown in the figure below. Although the initial strength development is different, the long-term strength at say five years time tends to be similar in all the cases. If at all, the cements with lower strengths at initial ages types II and IV have the as high strength as type III in the long term.

The strength of concrete depends upon a large number of factors, which is described later on. One of the factors is the strength of cement, when tested in standard mortar cubes as per the specification. As per IS specifications, strength of cement is tested in 1:3 cement mortar made with standard sand and at water-cement ratio of about 0.4, at temperature 27OC and relative humidity 95 %+. It has been shown that for identical mix proportion of concrete, its compressive strength depends upon the strength of cement the higher the cement strength, greater is the strength of concrete (see figure below). In India, OPC is graded into three strength grades 33 grade, 43 grade and 53 grade, the grade designation indicating the minimum strength at 28 days. It is customary to use cement of higher strength characteristics for high strength concrete.

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The influence of cement characteristics on the durability of concrete against chemical attack is discussed later on.

Industrial by-products use of fly ash, granulated blast furnace slag and silica fume has been discussed under the topic Types and Performance Characteristics of Cements. Aggregates aggregates are important because they occupy nearly 75 percent volume of concrete. They can be viewed as fillers in the matrix of cement paste (cement + water), or as building blocks jointed together by the cement paste just like stone masonry is jointed by cement mortar. In any case, the aggregates can not be considered to be inert, as they influence the properties of concrete through the rock type, size, shape and texture, and chemical and micro-structural characteristics. The properties of concrete that are influenced by aggregates are; workability, strength, abrasion and wear resistance and durability etc. Aggregates are arbitrarily classified as fine and coarse on the basis of size. Fine aggregate, also called sand, is of size 4.75 mm and below; while coarse aggregate, also called stone chips or gravel, are of higher sizes. Coarse aggregate of 20 or 40mm sizes are used for structural concrete and 80 mm or 150 mm for mass concrete as in dams. For thin sections with high concentration of reinforcement steel, 10 mm MSA coarse aggregate are used. Aggregates obtained from natural sources are commonly used, while artificial aggregates can also be used. Other classifications are in terms of shape rounded or angular; texture smooth or granular; or the way the size is reduced natural weathering as in river sand, gravel or boulders, or crushed rock. Classification in terms of unit weight can be normal weight, as is mostly used, lightweight as are most artificial aggregates, or heavy weight as are used for nuclear reactors and radiation shielding. Indian standard specification IS: 383 lays down the requirements of concrete aggregates from natural sources. It is not proposed to consider all of them in this lecture; however, the

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requirements of size distribution are described. The principle of densest possible packing of materials, requires that the group should consist of particles of different sizes, each being smaller than the previous one. This principle will be clear from the following example. If we try to fill a container with spheres of the same diameter, there will be void left, occupying 36 percent of the total volume. These voids can be filled up to some extent with spheres of size smaller than the size of voids, and the residual void filled up with next smaller size, and so on. The same principle applies to concrete aggregate, which should comprise of particles of successive smaller sizes. The size distribution is determined by the proportion passing standard sieve sizes. The sizes as per IS specification are; 150, 80, 40, 20, 10, 4.75, 2.36 and 1.18 mm, 600 micron, 300 micron and 150 micron sizes. The desirable grading for each nominal maximum size (MSA) of say, 20 mm or 40 mm, as well as the sand fractions are given in IS: 383. These lots are to be judiciously combined to result in satisfactory grading of the combined aggregate. The importance of grading of aggregate is in the way it facilitates densest possible packing. Ideal grading as given in the specifications is not always available, so whatever materials are available are to be judiciously combined to achieve the goal of dense packing. Another effect is the total surface area, to be covered by cement paste. For the same total volume, the smaller the size of particles, larger is the surface area. This determines the water requirement. In particular, fine aggregate is graded as per the sieve analysis in different zones in IS: 383. The details are as under; Grading of Fine Aggregate as per IS: 383 Sieve Size 10 mm 4.75 mm 2.36 mm 1.18 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 - 10 0 - 10 Zone III 100 90 100 75 100 75 100 60 79 12 40 0 - 10 Zone IV 100 95 100 95 100 90 100 80 100 15 50 0 - 15

These limits are shown graphically in the Figure below. From the above, it is clear that sand belonging to zone I is the coarsest and zone IV the finest. Sands falling in zone II or zone III are very suitable for concrete. Zone IV sand will increase the water demand in concrete enormously; it is used for plastering. Water The usual amount of mixing water in concrete varies from 140 litres to about 200 litres per cubic meter of concrete. Thus, water occupies nearly 15 20 percent by volume and about 6 9 percent by weight of concrete. Compared to other ingredients of concrete, the quality of water usually receives less attention. However, there are many instances of distress to concrete because of mixing and curing water not being of appropriate quality. 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. The permissible limits for solids in water, tested as per IS: 3025, is given below. In addition, there are additional tests for alkalinity (as carbonates and bicarbonates) and acidity in water prescribed in IS: 456.

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

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Item Organic Inorganic Sulphate (as SO3) Chloride (as Cl -) Suspended matter

Limit, mg/l, max 200 3000 400 2000 for plain concrete, 500 for RCC 2000

Chemical admixtures and superplasticisers admixtures are materials, usually organic chemicals, which are added to the concrete (usually in small amounts) before or during its mixing, with a view to modifying one or more properties of concrete in the fresh or hardened state. Although intended to modify one property of concrete, many admixtures are capable of modifying more than one property. The classification in IS: 9103 is based on the intended use, as will be clear from the nomenclature given below;

Set-accelerating admixtures, Set-retarding admixtures, Water-reducing admixtures, Air-entraining admixtures, and Superplasticisers.

Among the list above, superplasticisers, both normal and set-retarding types are more prominent. They can significantly reduce the amount of mixing water required in concrete. Use of superplasticisers help in improving the workability of concrete, improve strength by lowering the water-cement ratio, improve durability, or combination thereof. Commonly used superplasticisers are based on Melamine Sulphonates (MSF) or Naphthalene Sulphonates (NSF), Modified Lignosulphonates (MLS), Acrylic Polymer (AP) or Polycaboxylatethers (PCE) etc. The performance of concrete admixtures depends upon both the admixture and the cement and their compatibility, in addition to concrete mix proportions and the environmental conditions in the field. Among the characteristics of the cement, which affect the performance of admixtures are the C3A, SO3 and alkali contents, nature of sulphate, and the fineness of cement. It is necessary to evaluate concrete admixtures for specific use with the concrete-making materials and mix proportions to be used in the work, under the field conditions.

Properties of Concrete
Concrete is required to have necessary characteristics both in the fresh and hardened states. After mixing, fresh concrete should be amenable to placing in the formwork and consolidating it. This is called workability. Strength and durability are important properties in the hardened states. Workability - Workability of concrete is not a single measure, but have four distinct aspects;

The mix should be stable, in that it should not segregate during transportation and placing. The tendency of bleeding should be minimized. 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. The mix should be compactable to achieve proper and through compaction in the situation of placing and with the facilities of compaction, and It should have finishability to obtain a satisfactory surface finish.

The various factors influencing workability are;

Materials and Mix Proportions water content, maximum size of aggregate, shape of aggregate whether rounded or crushed, fineness of sand and coarse : fine aggregate ratio.

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Temperature and Humidity - high temperature causes evaporation and reduces slump, dry weather reduces workability. Delay in placement- workability reduces with time elapsed after mixing.

There are a number of test methods for workability of concrete, each measuring a particular aspect. These test methods are described in IS: 1199 and can be viewed in the laboratory. Slump test, which essentially measures the wetness of concrete, is more popular because it is easy to carry out. Compaction factor (CF) test measures the compaction achieved by a given input of compacting effort, is more suitable for low workability. Vee-bee time test is suitable for very low workability also called zero slump concrete. Flow table test, described in IS: 9103 is suitable for high workability to flowing concrete, as in self compacting concrete (SCC) to be described later on. IS: 456 gives general guidance for the degree of workability, which is reproduced below. Requirement of Workability (IS: 456-2000) Placing conditions Pavements with pavers; shallow sections Mass concrete; lightly reinforced sections in slabs, beams, walls, columns; floors; hand placed pavements; canal lining. Heavily reinforced sections in slabs, beams, walls, columns. Slipform work; pumped concrete Trench fill; In-situ piling Tremie Concrete Degree of workability Very low Low Slump, mm CF 0.75 0.80 # 25 75

Medium Medium High Very high

50 - 100 75 100 100 150 Flow > 600 mm #

# - slump test is not suitable and other tests indicated are more appropriate.
Strength of concrete Concrete is relatively stronger in compression and weak in tension. Hence, compressive strength of concrete is considered to be most important. Many other desirable properties of concrete are held to be related to its compressive strength albeit indirectly, so much so that compressive strength is many times taken synonymous with the overall quality of concrete. As per Indian practice, compressive strength is determined on 150 mm cube specimens. The procedure is detailed in IS: 516. In USA and some other countries, the strength is determined on 6" diameter and 12" high (150 mm x 300 mm) cylindrical specimens. Compressive strength of concrete depends upon a very large number of intrinsic and external parameters. The single most important factor is water cement ratio. As long as the concrete is workable, greater is its strength, the lower the water-cement ratio (see figure below). Next is the importance of cement strength, which has been described before. There is a saying a chain is not stronger than its weakest element. Aggregates occupying nearly 75 percent of the total volume are not, per se, the limiting factor. This is because the mechanical strength of commonly used aggregates is far greater than that of concrete made with it. If the broken piece of a concrete specimen after testing is examined, failure would be noticed to have taken place around the aggregate particles, and sometimes through the mortar phase, but very seldom failure in the aggregate pieces are found. The aggregate-mortar interface is thus the weakest link. The aggregates influence strength of concrete by way of controlling the bond at the aggregate- mortar interface. The shape and size of the test specimen are also important.

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As a general rule, the following observations can be made, each having profound scientific reasons; Strength increase with age of test and duration of moist curing, Crushed rock aggregates give higher strength than river shingles or pebbles, Aggregates with granular texture result in higher strength than with smooth texture. Smaller maximum size of aggregates (MSA) results in higher strength than larger MSA. Concrete tested in 100 mm cube specimen will give higher strength than 150 mm specimens. 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. Higher speed of loading during strength test gives higher strength value.

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). As a general rule tensile strength of brittle materials like concrete are about one-tenth of its compressive strength (see Figure below). Flexural strength is somewhat greater than tensile strength determined on split cylinders and is a design parameter for concrete pavements. Durability - Durability of concrete is its resistance to various deteriorating agencies that may reside inside the concrete itself, or be present in the service environment to which the concrete structure is exposed. For proper performance of a structure, it is important to ensure not only adequate strength and load-carrying capacity but also durability. Concrete under conditions of normal usage is quite durable. However, there are a number of deteriorating agencies which can attack concrete. The causes could be physical, mechanical, thermal or chemical in nature. In this lecture, the action of chemical agencies like chlorides, sulphate, carbon di-oxide, acids etc. present in the service environment and in soils, sub-soil and ground water, which can attack the cement + water (cement paste) system and reinforcement will be discussed. In each case, it is necessary to understand the origin of the problem, so that solutions can be suggested. The basic mechanisms are described below.

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The main products of hydration of cement are C-S-H, C-A-H and C-H. The response of the hydration products to the principal deteriorating agencies like sulphate (SO3--), chlorides (Cl-) and carbon dioxide (CO2) are documented in the text books. While calcium hydroxide (CH) and calcium aluminate hydrates (CAH) are the fast reacting components of the cement paste; CSH is also susceptible to attack by all the three aggressive ions. In many cases, the type and extent of reaction depend upon the cations. The basic chemical reactions, which are widely reported in the literature, are summarised below;

Sulphate Attack: The main reactions of sulphate attack on concrete are as under; Formation of sulphoaluminates (ettringite) by reaction of CS and C-A-H C3A + 3 CS H2 + 26 H C3A(CS)3H32, Results in increase in volume of reaction products, causes expansion and spalling; 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. Magnesium sulphate reacts; in addition, with the C-S-H phase leading to its decalcification i.e. substitution of Mg+ for Ca+ and formation of M-S-H and other expansive salt identified above. Formation of brucite (MH) and gypsum takes place in reaction with CH, especially in seawaters;

MS + CH + 2 H MH + CSH2 Both contributing to deterioration

When alkali sulphate concentration is high and conditions are favourable, formation of alkali sulphate crystals take place; for example

NS + 10 H NS H10 (mirabilite)

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Contributing to surface deterioration by spalling and splitting. Carbonation: Carbon dioxide in air or dissolved in water reacts with hydrated cement systems. CH-phase is most susceptible to carbonation. Other products of cement hydration can also be affected by carbonation, being finally decomposed to form calcium carbonate and hydrated silica, alumina and ferric oxide. For example, total carbonation of CSH gel can lead to decomposition into calcite and amorphous silica;

C3S2H3 + 3 C 3CC + 2S +3H

Formation of thaumasite has also been reported at lower temperatures. In all such reactions, OHis consumed, thus lowering down the pH of pore solution. Chlorides: Besides being the principal cause of reinforcement corrosion as described later, chloride salts react with hydrates phases also. Reaction of chlorides with hydrates of C3A and C4AF, forming Friedels Salt and its ferrite analogue is the primary mechanism of chloride binding. Magnesium chloride leads to ion exchange between Calcium and Magnesium. Calcium chloride reacts with cement hydrates to form expansive compound calcium oxychloride (3CaO, CaCl2, 15H20). 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. Alkali-silica reaction (ASR) involves rocks and minerals containing reactive forms of silica. Amorphous, microcrystalline and poorly crystalline silica, fractured or strained quartz and glassy silica are among the commonly known alkali-reactive forms of silica. Granite, granite gneiss and schist, quartzite and sandstone, containing strained quartz is among the reactive rocks found in India. Expansion and cracking leading to loss of strength, elasticity and durability are among the physical manifestations of ASR. Environmental conditions, notably presence of moisture and temperature are important parameters. Corrosion of Reinforcement: The basic mechanism of corrosion of steel, as an Electrochemical phenomenon, can be summarised in terms of an anode process and a cathode process; Fe 2 e- + Fe2+ (Metallic iron) Cathode: O2 + H2O + 2 e- 2(OH)In addition, the corrosion undergone by steel is due to combination of iron and (OH-) ions; Fe + O2 + H2O Fe2+ + 2(OH) iron hydroxide (rust). Anode: The process is summarised in the Figure below.

For transformation of metallic iron to rust, the requirements are;

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1. Iron must be available in a metallic (Fe) state at the surface of the reinforcing steel; 2. Oxygen and moisture must be available for the cathode process; and 3. The electrical resistivity of concrete must be low to facilitate the electron flow in the metal from anodic to cathodic areas. From engineering stand point; two types of situations are necessary to be considered. The steel reinforcement, being well protected in the alkaline medium in concrete, would take a certain amount of chloride ion to be present so that corrosion can take place. On the other hand, if the passivity is destroyed because of one reason or the other, and the pH of concrete is below a certain threshold value, only oxygen and water are needed for corrosion to take place. Presence of chlorides is not necessary. Concrete constructions, in order to be durable, 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. Practical limits of tolerable chloride ion concentration and limiting pH value are best arrived at by in-service record of concrete. From what is described above, it is seen that most of the deteriorating actions are expansionproducing, which causes cracking. Such cracking allows more of the aggressive ions to permeate inside the concrete, thereby producing more distress. Presence of moisture is necessary for the chemical reactions to take place and proceed. In addition, there could be cracking caused by thermal effects, which would also allow the ingress of the chemical agencies into concrete. A logical approach to prevent deterioration comprises;

Make concrete as dense and impermeable as possible, by adopting low water-cement ratio and thorough compaction. Most specifications suggest water-cement ratio to be 0.45 or less, depending upon the severity of the service environment, because low water-cement ratio ensures low permeability of concrete (see Figure below). Use of right type of cement, including composite cements. Portland Pozzolana cement (PPC) and Portland Slag cement (PSC) are recommended to combat sulphate attack, lower the heat of hydration and reduce the risk of reinforcement corrosion. Adequate cement content to retain passivity of steel and allow proper workability of concrete; use of chemical admixtures and superplasticisers. IS: 456 gives guidance on minimum cement content and maximum water-cement ratio for concrete exposed to aggressive environments of varying degrees. Steps to alleviate thermal cracking in massive sections.

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Rational use of cement in concrete


From the discussions above, it should be clear that cement plays a vital role in ensuring the desired properties of concrete for a particular application. Rational use of cement means use of cement of the right quality in right quantity to ensure satisfactory concrete mix. The proportions of ingredients of concrete, e.g. cement, coarse and fine aggregate, and water is chosen on a scientific basis, aided by trials. This is called concrete mix design. Although there are a number of methods of mix design, they are all approximate and only lead to trial mixes. Since there is nothing as an exact method of concrete mix design, there are some cardinal principles that lead to the trials. These are; The workability of concrete depends upon the water content in the mix, for a given set of aggregates (maximum size, grading, coarse to fine ratio), The compressive strength of concrete depends primarily on the water-cement ratio; when cement quality is variable, it also depends on the strength of cement, and The durability of concrete depends upon the water-cement ratio, cement content and the 'type' i.e. chemical composition of cement. Potential for alkali-silica reaction depends upon the potential reactivity of the aggregates and the cement characteristics. At present, there are no reliable, short-term tests for long-term durability of concrete. Hence , design for durability is adherence to guidance given in the specifications, for example, IS: 456.

High Performance Concrete Definitions - Many attempts have been made to define high performance concrete. A quantitative definition is that It should have a maximum water-cement ratio of 0.35, a minimum durability factor of 80 percent in freeze-thaw resistance test as per ASTM C666, a minimum compressive strength of 21 MPa at 4 hours, 34 MPa at 1 day or 69 MPa at 28 days. However, such quantitative definitions may not be satisfactory in all situations. Among more general, qualitative definitions are; Concrete, which meets special performance requirements that cannot be always achieved routinely by using only conventional materials and normal mixing, placing and

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curing practices. The requirements may involve enhancement of characteristics such as strength, toughness, volume stability or service life in severe environments; 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; these properties are usually a high strength or a low permeability.

Since the specification of high performance concrete is derived from its intended use, qualitative definitions are more appropriate. Apart from high compressive strength, such applications may focus on other properties of concrete, like elastic modulus, abrasion - erosion - cavitations resistance, high workability, self-leveling and self-compacting properties etc. Durability of concrete is a common thread and high strength may not be always emphasized. A good example is the tunnel lining concrete for the Channel Tunnel in Europe. Requirements of durability dictated that the co-efficient of permeability should be of the order of 10 13 m/s. The compressive strength of concrete was required to be 45 MPa. By adopting water-cement ratio of 0.35, the requirement of permeability was met. The compressive strength achieved was about 63 MPa, far in excess of the design requirement. High performance concrete is made with the same cements, aggregates, admixtures, additives, and water, as in normal usage, but with proper curing and adequate quality control. 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. Development of high performance concrete follows certain logical steps, as discussed below. The Logical Development - The development of high performance concrete is based on the following well-known relationships of concrete technology; For high strength, water-cement ratio should be low. The strength - w/c ratio rule holds good for concrete strength of about 100 MPa or more. Low water-cement ratio is also required for low permeability of concrete, which is vital for high durability. Impermeability is also aided by pore filling effects of fine pozzolanic additions. 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 0.45 or so. That is why, most concrete specifications limit the water - cement ratio to about 0.45 or so for concrete exposed to severe service environments. Thus, low water-cement ratio ensures both high strength and low permeability, or high durability. 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. However, too high a cement content will cause high heat of hydration and increase cracking tendency. Hence, part of the cement is to be replaced by other cementitious materials like silica fume, fly ash or ground granulated slag, or combinations thereof. Such fine powders also help in pore filling and reduce permeability. Use of low water-cement ratio and other cementitious materials as silica fume etc. makes use of superplasticisers mandatory. Thus, the composition of high performance concrete is automatically chosen - cement, aggregates, water, superplasticisers, silica fume and fly ash or slag. Mechanisms of high performance - High strength and low permeability are logical developments of presence of silica fume and superplasticiser in concrete. 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. As pointed out earlier, this is achieved through reduction in watercement ratio as well as dense packing of fine particles.

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The role of superplasticisers, long chain molecule organic compounds, is to get adsorbed onto cement grains, impart a negative charge to them, which repel each other and get deflocculated and dispersed. 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. Alternately, it enables water content to be reduced by about 20 percent or more and results in high strength, because of low water-cement ratio. The role of silica fume is many-fold. Because of enormous surface area as well as relatively large content of glassy silica, it is a very reactive Pozzolana. When contribution of silica fume to the compressive strength of concrete is compared based on water-cement ratio in the mix, mixes containing silica fume has higher compressive strength at 28 days. It also helps in augmenting early strength of concrete. Since the heat of hydration of both are of the same order, use of silica fume enables the heat rise in concrete to be lowered - a critical advantage for mass concrete. However, incorporation of silica fume in concrete increases the water demand. Hence, superplasticisers are required. Dense packing is another basis of superior performance of concrete containing silica fume and superplasticiser. The cement grains, which in normal circumstances tend to flock together, are dispersed by superplasticiser. The extremely fine silica fume particles are then packed in the space between dispersed cement grains and normally packed fine and coarse aggregate. The overall result is a denser microstructure. A concrete exhibit less porosity with no evidence of capillary pores and only very narrow - less than 0.5 m gel pores is visible under high magnification in electron microscope. C-S-H gel particles in concrete containing silica fume appear not as individual particles, but rather as a massive, dense structure. By residing in the pores in hydrated cement paste, silica fume particles, on hydration, block the pores. Such porerefining action reduces the size of pores. Another important mechanism is improving the transition zone around aggregate particles. In normal strength concrete with only cement, the transition zone around aggregate is 20 m to 100 m wide and richer in calcium hydroxide and ettringite, as against C-S-H phase in the bulk matrix. The porosity is also higher. Thus, the transition zone forms a weak link. In presence of silica fume, dense C-S-H occupies all the space around aggregate and direct bond with aggregate is established. The porosity of the transition zone is eliminated. Result of strengthened transition zone is reduction in micro cracking at the interface between cement paste and aggregate. The stress-strain curve remains linear up to about 85 percent of failure stress or higher. Improvement in Durability Corrosion Resistance - From durability considerations, reduction in air and water permeability is important. Improved corrosion resistance of high performance concrete in terms of impermeability to chloride and oxygen diffusion, improved electrical resistance and chloride-binding capacity are reported. Alkali-Silica Reaction (ASR) - Through the presence of silica fume and low water-cement ratio, high performance concrete helps in alleviating alkali-silica reaction in concrete. 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. The alkalinity in the pore solution is reduced. Consequent to the depletion of calcium hydroxide in pozzolanic reactions, which is the main source of calcium in the system and can exchange with some alkali (Na or K) in the ASR gel, the alkali cycle is broken. Presence of moisture is required for ASR expansion to take place and continue. Reduced permeability of concrete makes ingress of water from the outside difficult and alleviates ASR. Mix design and field practices - Choice of materials, concrete mix design and field practices are quite critical for high performance concrete. There is not much experience to go by and practices with normal grades of concrete are of little help.

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Mix Design - Some points to remember are; Mixes are cohesive, free from segregation, but 'sticky'. May require about 25 mm more slump for comparable level of workability than in normal grades. Quality control will, perforce, be stringent, so standard deviation (SD) is not likely to exceed 5 MPa or Coefficient of variation (COV) not more than 3 to 4 percent. Hence, margin over characteristic strength need not be high. This will save on cement content. MSA of coarse aggregate should be 20 mm. Proportion of coarse aggregate to sand content may be 1.0 - 1.5. Presence of fine powders increases water content. Project specifications in many cases stipulate the maximum water-cement ratio and percent of silica fume to cement by weight.

Steps of mix design are suggested below; 1. Check compatibility of superplasticiser to cement and establish its water reducing efficiency. With viable superplasticisers, reduction in water content of 25 - 30 percent is possible. Establish optimum dosage by trials on cement + water mixes. 2. Make preliminary estimate of water-binder ratio (w/b) for target strength by establishing such relationship. For target 28-days compressive strength in 80 -100 MPa range, start trial mixes with cement + silica fume at steps of 400 - 450 kg/m3 and w/b at 0.25, 0.30 and 0.35. Effort should be made to keep the cement content minimum possible. 3. For each trial, gradually increase the amount of superplasticiser until the desired workability is attained. 4. Adjust the sand and coarse aggregate contents, until optimum result is obtained. Field Practices, Curing - The mix design arrived after laboratory trials should be tested for physical properties. Next, the mix design should be checked under field conditions and necessary adjustments made to allow for placing and transportation methods and required slump retention. A further mock-up or prototype testing should preferably be made to see the effect of reinforcement congestion. Detailing of rebar may have to be altered in critical areas. The optimum sequence of mixing of ingredients should be established by trials and no prior guidance is possible. Mixing time will be longer than in normal mixes. Temperature of fresh concrete at the mixing stage should be kept lower than what is stipulated at the time of placement, to allow for temperature rise during transportation. Cooling of aggregates may be necessary. In addition, ice flakes may replace part of the mix water. Insulation of drums of transit mixers and concrete pipelines is preferable. High performance concrete containing silica fume is cohesive, so there is little bleed water to rise to the top and offset water lost due to evaporation. Plastic shrinkage cracking is likely, if curing is not proper. Initial curing should commence after initial setting of concrete and removal of side forms, with moist covers, opaque colour plastic sheets or curing compound. Final moist curing should commence after final setting and continue for at least 7 to 10 days. Reference Books 1. A.M. Neville, Properties of Concrete, 4th Ed., Longman, (Indian Edition), 2. P. K. Mehta and P. J. M. Monteiro: Concrete: Microstructure, Properties and Materials, Indian Edition, Indian Concrete Institute, Chennai. 3. Handbook of Concrete Mixes, SP 23 (ST), Bureau of Indian Standards, New Delhi. . Indian Standards Specifications 1. IS: 456 -2000, Code of Practice for Plain and Reinforced Concrete,

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2. 3. 4. 5.

IS: 383 Specifications for Aggregates from Natural Sources, IS: 9103 Specification for Chemical Admixtures, IS: 516 and IS: 1199 Methods of testing concrete, IS: 3812 Methods of testing of Aggregates. -----------

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