The major cements: composition and properties

Chemical composition

Portland cement is made up of four main compounds: tricalcium silicate (3CaO · SiO₂), dicalcium silicate (2CaO · SiO₂), tricalcium aluminate (3CaO · Al₂O₃), and a tetra-calcium aluminoferrite (4CaO · Al₂O₃Fe₂O₃). In an abbreviated notation differing from the normal atomic symbols, these compounds are designated as C₃S, C₂S, C₃A, and C₄AF, where C stands for calcium oxide (lime), S for silica, A for alumina, and F for iron oxide. Small amounts of uncombined lime and magnesia also are present, along with alkalies and minor amounts of other elements.

Hydration

The most important hydraulic constituents are the calcium silicates, C₂S and C₃S. Upon mixing with water, the calcium silicates react with water molecules to form calcium silicate hydrate (3CaO · 2SiO₂ · 3H₂O) and calcium hydroxide (Ca[OH]₂). These compounds are given the shorthand notations C–S–H (represented by the average formula C₃S₂H₃) and CH, and the hydration reaction can be crudely represented by the following reactions: 2C₃S + 6H = C₃S₂H₃ + 3CH 2C₂S + 4H = C₃S₂H₃ + CH During the initial stage of hydration, the parent compounds dissolve, and the dissolution of their chemical bonds generates a significant amount of heat. Then, for reasons that are not fully understood, hydration comes to a stop. This quiescent, or dormant, period is extremely important in the placement of concrete. Without a dormant period there would be no cement trucks; pouring would have to be done immediately upon mixing.

Following the dormant period (which can last several hours), the cement begins to harden, as CH and C–S–H are produced. This is the cementitious material that binds cement and concrete together. As hydration proceeds, water and cement are continuously consumed. Fortunately, the C–S–H and CH products occupy almost the same volume as the original cement and water; volume is approximately conserved, and shrinkage is manageable.

Although the formulas above treat C–S–H as a specific stoichiometry, with the formula C₃S₂H₃, it does not at all form an ordered structure of uniform composition. C–S–H is actually an amorphous gel with a highly variable stoichiometry. The ratio of C to S, for example, can range from 1:1 to 2:1, depending on mix design and curing conditions.

Structural properties

The strength developed by portland cement depends on its composition and the fineness to which it is ground. The C₃S is mainly responsible for the strength developed in the first week of hardening and the C₂S for the subsequent increase in strength. The alumina and iron compounds that are present only in lesser amounts make little direct contribution to strength.

Set cement and concrete can suffer deterioration from attack by some natural or artificial chemical agents. The alumina compound is the most vulnerable to chemical attack in soils containing sulfate salts or in seawater, while the iron compound and the two calcium silicates are more resistant. Calcium hydroxide released during the hydration of the calcium silicates is also vulnerable to attack. Because cement liberates heat when it hydrates, concrete placed in large masses, as in dams, can cause the temperature inside the mass to rise as much as 40 °C (70 °F) above the outside temperature. Subsequent cooling can be a cause of cracking. The highest heat of hydration is shown by C₃A, followed in descending order by C₃S, C₄AF, and C₂S.

Types of portland cement

Five types of portland cement are standardized in the United States by the American Society for Testing and Materials (ASTM): ordinary (Type I), modified (Type II), high-early-strength (Type III), low-heat (Type IV), and sulfate-resistant (Type V). In other countries Type II is omitted, and Type III is called rapid-hardening. Type V is known in some European countries as Ferrari cement.

There also are various other special types of portland cement. Coloured cements are made by grinding 5 to 10 percent of suitable pigments with white or ordinary gray portland cement. Air-entraining cements are made by the addition on grinding of a small amount, about 0.05 percent, of an organic agent that causes the entrainment of very fine air bubbles in a concrete. This increases the resistance of the concrete to freeze-thaw damage in cold climates. The air-entraining agent can alternatively be added as a separate ingredient to the mix when making the concrete.

Low-alkali cements are portland cements with a total content of alkalies not above 0.6 percent. These are used in concrete made with certain types of aggregates that contain a form of silica that reacts with alkalies to cause an expansion that can disrupt a concrete.

Masonry cements are used primarily for mortar. They consist of a mixture of portland cement and ground limestone or other filler together with an air-entraining agent or a water-repellent additive. Waterproof cement is the name given to a portland cement to which a water-repellent agent has been added. Hydrophobic cement is obtained by grinding portland cement clinker with a film-forming substance such as oleic acid in order to reduce the rate of deterioration when the cement is stored under unfavourable conditions.

Oil-well cements are used for cementing work in the drilling of oil wells where they are subject to high temperatures and pressures. They usually consist of portland or pozzolanic cement (see below) with special organic retarders to prevent the cement from setting too quickly.