Portland Cements I.

Definition Portland cement has been defined as the product obtained by pulverizing clinker consisting essentially of hydraulic calcium silicates, usually containing one or more forms of calcium silicates as an interground addition. Hydraulic calcium silicates possess the ability to harden without drying or by reaction with atmospheric carbon dioxide, thus differentiating them from other inorganic binders such as plaster of paris. Historical Cement was used by the Egyptians in constructing the Pyramids The Greeks and Romans used volcanic tuff mixed with lime for cement, and a number of these are still standing In 1824, an Englishman, Joseph Aspdin, patented an aritificial cement made by the calcination of an argillaceous limestone. He called this Portland because concerete made from it resembled a famous building stone obtained from the Isle of Portland Uses and Economics Before 1900, cement was relatively little used in this country because manufacture of Portland cement was an expensive process. With the invention of labor-saving machinery, cement is now low cost and is applied everywhere in the construction. Types of Portland Cement Type I: Regular Portland Cements usual products for general construction Type II: Moderate-Heat-of-Hydration and-Sulfate-Resisting Portland Cements use where moderate heat of hydration is required or for general construction exposed to moderate sulfate action Type III: High-Early Strength (HES) Portland Cement contain a higher proportion of tricalcium silicate (3CaOSiO2) than regular Portland cements Type IV: Low-Heat Portland Cements contain a lower percentage of 3CaOSiO2 and ticalcium aluminate (3CaOAl2O3), thus lowering the heat of evolution. Type V: Sulfate-Resisting Portland Cements those which, by their composition or processing, resist sulfates better than the other four types. Manufacturing Procedures Raw Material Extraction Generally, raw materials consisting of combinations of limestone, shells or chalk, and shale, clay, sand, or iron ore are mined from a quarry near the plant.

II.

III.

IV.

V.

Raw Material Preparation At the quarry, the raw materials are reduced by primary and secondary crushers. Stone is first reduced to 5-inch size (125-mm), then to 3/4-inch(19 mm). Once the raw materials arrive at the cement plant, the materials are proportioned to create a cement with a specific chemical composition. Two methods of manufacture: dry and wet process. a. Dry Process In the dry process, dry raw materials are proportioned, ground to a powder, blended together and fed to the kiln in a dry state. The raw materials are dried, ground and mixed to form a fine, homogenous powder, with moisture content of less than one percent. b. Wet Process In the wet process, about 80% limestone and 20% clay are ground in ball mills with water, producing very fine, thin paste, called slurry. The slurry is stored in large basins ready for use. The slurry is fed into the upper end of rotary kiln, while at the lower kiln, a very intense flame is maintained by blowing finely ground coal. Clinker Production (Burning and Cooling) Inside the kiln, raw materials reach temperatures of 2600oF to 3000oF (1430oC to 1650oC). At 2700oF (1480oC), a series of chemical reactions cause the materials to fuse and create cement clinker-grayish-black pellets, often the size of marbles. Cement Grinding The clinker is ground in a ball mill horizontal steel tube filled with steel balls. As the tube rotates, the steel balls tumble and crush the clinker into a super fine powder. Addition of Gypsum and Packing Gypsum is often added to Portland cement to prevent early hardening or "flash setting", allowing a longer working time. The time it takes for cement to cure varies depending on the mixture and environmental conditions; initial hardening can occur in as little as twenty minutes, while full cure can take over a month.

VI.

Chemical Admixtures Definition Chemical admixtures are the ingredients in concrete other than portland cement, water, and aggregate that are added to the mix immediately before or during mixing. Producers use admixtures primarily to reduce the cost of concrete construction; to modify the properties of hardened concrete; to ensure

the quality of concrete during mixing, transporting, placing, and curing; and to overcome certain emergencies during concrete operations. Five Distinct Classes of Chemical Admixtures 1. Water-Reducing admixture 2. Retarding Admixture 3. Accelerating Admixture 4. Superplasticizer 5. Corrosion-Inhibiting Admixture Water-reducing admixtures - usually reduce the required water content for a concrete mixture by about 5 to 10 percent. Consequently, concrete containing a water-reducing admixture needs less water to reach a required slump than untreated concrete. Retarding admixtures - which slow the setting rate of concrete, are used to counteract the accelerating effect of hot weather on concrete setting. High temperatures often cause an increased rate of hardening which makes placing and finishing difficult. Accelerating admixtures - increase the rate of early strength development, reduce the time required for proper curing and protection, and speed up the start of finishing operations. Superplasticizers - also known as plasticizers or high-range water reducers (HRWR), reduce water content by 12 to 30 percent and can be added to concrete with a low-tonormal slump and water-cement ratio to make high-slump flowing concrete. Corrosion-inhibiting admixtures - fall into the specialty admixture category and are used to slow corrosion of reinforcing steel in concrete. Corrosion inhibitors can be used as a defensive strategy for concrete structures, such as marine facilities, highway bridges, and parking garages, that will be exposed to high concentrations of chloride.

VII.

Compounds in Cement

Chemical Name Tricalcium Silicate

Chemical Formula 3CaOSiO2

Notation C3S

Percent by Weight 50

Dicalcium Silicate Tricalcium Aluminate Tricalcium Aluminoferrite Gypsum

2CaOSiO2 3CaOAl2SO3 4CaO Al2SO3Fe2SO4 CaSO4H2O

C2S C3A C4AF CSH2

25 8 12 3.5

C3S Hydrates and hardens rapidly and is responsible for initial set and early strength. Portland cements with higher percentages of C3S will exhibit higher early strength. C2S Hydrates and hardens slowly and is largely responsible for increase in strength beyond 7 days C3A Hydrates and hardens the quickest. Liberates a large amoung of heat almost immediately and contributes somwhat to early strength. C4AF Hydrates rapidly but contributes very little to strength. Its use allows lower kiln temperature in Portland cement manufacturing. Most Portland cement effects are due to C4AF CSH2 Without gypsum, C3A hydration would cause Portland cement to set almost immediately after addition of water. Hydration of cement During hydration, cement reacts with water liberating heat and forming products calcium silicate hydrates and calcium hydroxide. The following reactions occur: a. Hydration of Tricalcium Silicate 2 (3CaOSiO2) + 6H2O 3CaO2SiO23H2O + 3Ca(OH)2 2C3S + 6H C3S2H3 + 3Ca(OH)2

2C3S + 6H C-S-H (Cement Gel) + 3Ca(OH)2 100 + 24 75 + 49 (by weight)

b. Hydration of Dicalcium Silicate 2 (2CaOSiO2) + 4H2O 3CaO2SiO23H2O + 3Ca(OH)2 2C2S + 4H C3S2H3 + 3C(OH)2 2C2S + 4H C-S-H (Cement Gel) + 3Ca(OH)2 100 + 21 99 + 22 (by weight) VIII. Other Cements 1. Pozzolans A pozzolan is a siliceous and Aluminous material which, in itself, possess little or no cementitious value but which will, in finely divided form and in the presence of water, react chemically with calcium hydroxide at ordinary temperature to form compounds possessing cementitious properties. 2. High-Alumina Cements High-aluminacement, essentially a calcium aluminate cement, is manufactured by fusing a mixture of limestone and bauxite, the latter usually containing iron oxide, silica, magnesia and other impurities. 3. Silicate Cements Silica-filled, chemically setting silicate cements withstand all concentrations of inorganic acids except hydrofluoric. 4. Sulfur Cements Sulfur cements are resistant to nonoxidizing acids and salts but should not be used in the presence of alkalies, oils, greases or solvents. 5. Polymer Concrete Polymer concretes are really polymer-bonded concretes and usually contain no Portland cement. 6. Magnesium Oxychloride Cements Magnesia cements are produced by the exothermic action of 20% solution of magnesium chloride on a blend of magnesia obtained by calcining magnesite and magnesia obtained from brines.