CEMENTS & CERAMICS Cement: Cement is a dirty greenish heavy powder which finds its importance as a building material.

It is described as a material which possesses adhesive and cohesive properties to bind rigid masses like stones, bricks, building blocks etc., Cements are hydraulic in nature i.e., it possesses the property of setting and hardening in the presence of water. Further the essential constituents of cement used for constructional purpose are compounds of calcium (calcarious) and argillaceous i.e., (Al + Si) materials. Based on different chemical compositions, cement is classified into four types. They are 1) Natural cement 2) Puzzolana cement 3) Slag cement and 4) Portland cement Natural Cement: This is obtained by calcining and pulverizing natural rocks consiting of clay and limestone. Calcium silicates and aluminates are formed because of the combination of silica and alumina with calcium oxide. Natural cement is usually used for construction of big structures such as dams. Properties: a) It is hydraulic in nature with low strength and b) Its setting time is very less.

Puzzolana Cement: It is one of the ancient cements in the world and was identified by the Romans. It was used by them in making concrete for the construction of walls and domes. This cement was prepared from volcanic ash of Mount Vesuvius around the place called Puzzouli in Italy. The volcanic ash consisting of silicates of calcium, iron and aluminium mixed with lime and on heating result in puzzolanic cement. Properties: a) It is hydraulic in nature and is mixed with Portland cement and is then used for different applications.

Slag Cement: This cement is prepared by mixing hydrated lime and blast furnace slag, which is a mixture of calcium and aluminium silicates in a stream of cold water. It is dried and then pulverized to fine powder. Sometimes, accelerators like clay, or caustic soda are added to hasten the hardening process. Properties: a) It possesses low strength. b) The time required for setting and hardening is more i.e., one week.

Because of these properties it has very few applications and is usually used in making concrete in bulk construction. It is also used as concrete in water logged areas, where the tensile strength is less important. Portland Cement: It is produced by heating a mixture of limestone and clay and crushing the resulting product to a fine powder. Portland cement is most widely used nonmetallic material of construction. It is also known as Magic Powder and is a mixture of calcium silicates and calcium aluminates with small amount of gypsum. The name Portland cement was used because this powder, on mixing with water, sets to give a hard, stone-like mass which resembles the Portland rock. Portland cement is a type of cement and not a brand name. Every cement manufacturer makes Portland cement.

COMPOSITION OF PORTLAND CEMENT: A good sample of Portland cement has the composition of Calcium oxide (or) lime (CaO) = 60-70% Silica (SiO2) = 20-24% Alumina (Al2O3) = 5-7.5% Magnesia (MgO) = 2-3% Ferric oxide (Fe2O3) = 1-2.5% Sulphur trioxide (SO3) = 1-1.5% Sodium oxide (Na2O) = 1% Potassium oxide (K2O) = 1%

RAW MATERIALS: The raw materials used for the manufacturing of Portland cement are: a) Calcareous materials: Those which supply lime eg., limestone, cement rock, chalk and waste calcium carbonate from industrial processes. Limestone high in magnesia (MgO)cannot be used, because it leads to cracking. Similarly chalk freed from flint is to be used. b) Argillaceous materials: Those which supply silica, alumina and iron oxide. Eg: clay, blast furnace, slag ashes, shale and cement rock. Commonly used are clay and shale. c) Gypsum: This is added during the final grinding and it controls the ratio of setting and hardening. METHODS OF MANUFACTURING PROCESS: The manufacture of cement involves the following steps: 1) Mixing of raw materials: A mixture of finely ground limestone and clay (3:1) is made by any one of the following methods. Dry Process: The dry process produces a find ground powder. This process is employed if the limestone and clay are hard. In this process, initially limestone is crushed into pieces and then it is mixed with clay in the proportion of 3:1. This mixture is pulverized to a fine powder and is stored in storage bins and later on it is introduced into the upper end of the rotary kiln. Wet Process: The wet process takes place in the presence of water and usually results in a slurry formation. This process is preferred if limestone and clay are soft. In this process, the clay is washed with water in washmills to remove any foreign material, organic material etc., Powdered limestone is then mixed with the clay paste in a proper proportion (3:1). The mixture is then finely ground and homogenized to form a slurry containing about 40% of water. This is also stored in the storage bins and can be fed into the rotary kiln when necessary. 2) Burning the mixture in a rotary kiln: The rotary kiln is an inclined steel cylinder 150-200 feet long and 10 feet in diameter and it is lined inside with fire bricks. The kiln can be rotated at a desired speed as it is mounted on rollers. As the kiln rotates, the mixture of raw materials stored from the above two process, passes slowly from the upper to the lower end. In other words the slurry of the raw materials enters from the upper end of the rotary kiln while the burning fuel (pulverized coal, oil, or natural gas) and air are induced from the lower end of the kiln. As the mixture or

slurry gradually descends, the temperature rises and infact this creates different zones in the rotary kiln, with increasing temperature i.e., a) the drying zone: This is present in the upper part of the kiln, where the temperature is around 4000C. In this zone most of the water in the slurry gets evaporated because of the hot gases. The clay is broken as Al 2O3.SiO2 and Fe2O3 i.e., Al 2 O3 .2 SiO2 .Fe2 O3 .2 H 2 O Al 2 O3 + 2 SiO2 + Fe2 O3 + 2 H 2 O b) calcinations zone or decarbonating zone: This zone is located in the middle portion of the kiln where the temperature is of the order of 1000 0C. In this zone the limestone is completely decomposed into CaO (quick lime) which exists in the form of small lumps, called as nodules. CaCO3 CaO + CO2 c) burning zone or clinkering zone: This zone is at the bottom and is considered to be the hottest portion of the kiln. The temperatures over here ranges around 1400-1500 0C. IN this zone the mixture melts and forms little rounded pasty masses about the size of peas, which are called as clinkers. The clinkers produced are greenish black in color and have a rough texture. In the clinkering zone, lime and clay react with each other forming aluminates and silicates. 2CaO + SiO2 2CaO.SiO2 (C 2 S ) 3CaO + SiO2 3CaO.SiO2 (C 3 S ) 3CaO + Al 2 O3 3CaO. Al 2 O3 (C 3 A) 4CaO + Al 2 O3 + Fe 2 O3 4CaO. Al 2 O3 .Fe2 O3 (C 4 AF ) 3) Grinding or mixing of cement clinkers with gypsum: The clinkers are cooled and then ground to requisite fineness. The finely ground clinkers set quite rapidly, by absorption of moisture from the atmosphere. Therefore in order to reduce the rate of setting it is mixed with 2 to 3% gypsum (CaSO 4.2H2O).

SETTING AND HARDENING OF CEMENT: Portland cement on mixing with water, changes to a plastic mass called cement paste, which slowly loses its plasticity and becomes a stiff and ultimately a rockymass is obtained. This processes is known as setting. After hydration, anhydrated compounds become hydrated, which have less solubility. Hence they are precipitated as insoluble gels or crystals. These have the ability to surround sand, crushed stones, other inert materials and bind them very strongly.

The physical changes occurring in the setting and hardening of cement may be summarized in a flow chart as follows: Cement + Water Metastable gel (colloidal) Crystalline products (hydrated) Hardening Stable gel a) b) Crystalline products (coarser dimensions) Crystalline theory: According to this theory, constitutional compounds after hydration form crystalline products. These crystalline products undergo interlocking which is responsible for hardening of cement. Colloidal theory: According to this theory, during hydration silicate gels are formed which undergo hardening and are responsible for the hardening of cement.

Setting

REACTIONS INVOLVED IN SETTING AND HARDENING OF CEMENT: When cement is mixed with water, the paste becomes quite rigid within a short time which is known as initial set or flash set. This is due to C3A which hydrates rapidly as follows: 3CaO.Al2O3 + 6 H2O 3CaO. Al2O3.6H2O (Crystals) These crystals prevent the hydration reactions of other constitutional compounds forming barrier over them. In order to retard the flash set, gypsum is added during the pulverization of cement clinkers. Gypsum retards the dissolution of C3A by interacting with it forming insoluble complex of sulfoaluminate which does not have quick hydrating property. 3CaO.Al2O3 + x H2O +y CaSO4.2H2O 3CaO. Al2O3. y CaSO4.zH2O The tetracalcium alumino ferrite (C4AF) then reacts with water forming both gels and crystalline compounds as follows: 4CaO.Al2O3.Fe2O3 + 7H2O 3CaO.Al2O3.6H2O + CaO.Fe2O3.H2O Crystals Gels These gels shrink with passage of time and leave some capillaries for the water to come in contact with C3S and C2S to undergo further hydration and hydrolysis reactions enabling the development of greater strength over a length of time. Final setting and hardening of cement paste is due to the formation of tobermonite gel plus crystallization of calcium hydroxide. 2CaO. SiO2 + x H2O 2CaO.SiO2. x H2O Gels 2 (3CaO.SiO2) + 6H2O 3CaO.2SiO2. 3H2O + 3Ca(OH)2 Tobermonite gel Crystalline

Environmental effects on concrete / cement: Acid attack: Concrete contains free calcium hydroxide, so in acidic water lime dissolves making the concrete weak. pH value decreases and deterioration of concrete increases. Lime is more soluble in softwater than in hardwater. Therefore concrete deteriorate more quickly by interacting with softwater. Concrete should not be in contact with acids. Acid proof polymer modified concrete must be used to resist acid attack. Ca (OH ) 2 + H 2 SO4 CaSO4 + 2 H 2O Sulphate attack: Sulphates are present in soil, ground waters and marine water environment. Sulphates react with C3A to give bulky material causing cracks due to expansion. This is avoided by using sulphate resistant cements, which contain less C 3A (3-8%). Such danger is avoided by eliminating C3A from the cement composition If cement contains C 4AF instead of C3A, it is resistant to sulphate attack. Carbon Dioxide Attack: Diffusion of CO2 into concrete and conversion of Ca (OH) 2 to CaCO3 is called as carbonation, Carbonation depends on the porosity of concrete. Good quality of concrete is less porous and diffusion of concrete is less, in porous and low quality concrete, CO2 diffuses readily and carbonation reaches very early. When alkalinity due to Ca(OH)2 around concrete is lost due to carbonation, reinforcement corrosion starts. In the absence of hydroxide, iron oxide coating becomes porous and nonprotective. Ca (OH ) 2 CaCO3 + H 2O Chloride Attack: Chlorides enter concrete through water used for construction and by diffusion from the environment. Chlorides diffuse through porous and low quality concrete and reach the reinforcement. In presence of chlorides, the protective oxide layer around iron becomes less protective and porous that causes electrochemical corrosion of iron. The rate of electrochemical corrosion 1) decreases with increase in concentration of hydroxide concentration or alkalinity of reinforcement. 2) Increases with increase in concentration of chlorides and 3) increases with increase in the ratio of chlorides and Hydroxides.
Concentartion.of .Chloride.Ions.in.concrete Concentration.of .Hydroxide.Ions.in.Concrete

Chloride / HydroxideRatio =

As the chloride / hydroxide ratio increases above 0.65 electrochemical corrosion of reinforcement starts.

CERAMICS The word ceramic is derived from the Greek Keramos means burnt stuff. In modern usage ceramics are polycrystalline inorganic metallic or non-metallic materials that are processed and used at high temperature. Ceramic materials include a wide range of silicates, metallic oxides and combination of silicates and metallic oxides. Properties of Ceramics: 1) They are usually hard and brittle in nature and generally being in the form of amorphous or glossy solids. 2) The atomic bonding in these materials is of mixed ionic or covalent character. 3) They have high temperature resistance. 4) They have good electrical resistance and act as insulators. 5) They have good resistance to chemical attack and weathering. 6) They have high compressive strength and tensile strength. Ceramics generally consists of the following three major components.

1) 2) 3)

Plastic Portion: This is usually provided by clay, which imparts the necessary plasticity and workability. Non-Plastic Crystalline Portion: This is generally provided by silica, which contributes mechanical strength. Flux (or) Glossy material: This is generally provided by feldspar (K2O.Al2O3.6H2O), which helps in bonding and cementing the ingredients together.

Classification of Ceramic Materials: Ceramic materials are classified in the following way. 1) Functional classification based on industrial application. Eg:- Abrasives, Refractories, Minerals, Rocks, Cementing materials etc., 2) Structural classification based on structural criteria. Eg:- Crystalline ceramics, Non-crystalline ceramics, Glass-bonded ceramics etc., Various types of Ceramic Materials: 1) Structural Clay Products: Structural lay products include bricks, tiles, blocks and glazed and unglazed decorative products. Many of the structural clay products are made from relatively low-grade clays, shales and grog (Calcined fire clays).

The raw materials are ground and then screened. The powdered raw materials are mixed with water to increase plasticity. The sticky and plastic clay is moulded in the desired shapes. The moulded articles are then dried in outdoors and finally fired in kiln at 875 to 11000C for about 7 days. 2) White Wares (or) White Pottery (or) Triaxial wares: The term white ware or white pottery usually refer to glazed or unglazed ceramic materials which have white or cream colour after firing and have fine structure. White wares are usually prepared from suitable proportions of china clay, feldspar and quartz and it is called Triaxial are. The three raw materials are powdered and made into paste by mixing suitable amount of water and subjected to desired shape by moulding process. This is followed by careful drying and then firing at 1350 to 15000C when a partial verification take place. White ware product consisting of a refractory body with a glossy coating is called the glaze. 3) Earthenwares and Stnewares: Clay products, which are hard and strong like stone come under this category. Relatively softer type of clay products which are obtained by burning at lower temperatures are called Earthen wares, while the clay products which are denser and harder but are obtained by firing at high temperatures are called Stonewares. Earthenwares and Stonewares are usually glazed to render them strong, compact and impervious to water. Earthen wares are two types. The Coarse and the fine. Earthen wares are obtained from mixed earths of clays or clay mixed with sands. Stonewares: A typical formulation of producing stoneware is as follows: Clay 50%, Feldspar 20%, Flint (a gray siliceous material) 15%, Kaolin 5% and grog 10%. The shaping is done by casting or moulding. The shapes are dried and fired at 1000 0C followed by suitable glazing. Use of Stonewares: Stonewares are used for the construction of sanitary fixations, pipes, piping vessels, drainage pipes etc., Glazes: Glazes are low melting glasses of different compositions, which form firm and continuous layer on a ceramic surface. A glaze comprises a mixture of glass forming

materials of proper composition such as lead silicate, borosilicate etc., a glaze is applied on a ceramic body to achieve the following objects. 1) To produce decorative effect. 2) To make surface impervious to liquids, water etc., 3) To increase durability 4) To provide a smooth and glossy surface and 5) To protect the surfaces from the environment / atmospheric action.