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|In Roman and earlier civilizations the term cement was applied only to mixtures of lime, pozzolana, sand, water, etc., used as a mortar to bind larger stones. Today, portland cement, the subject of this section, can be briefly defined as follows: The product obtained by finely grinding clinker produced by calcining to incipient fusion (i.e., sintering) an intimate and properly proportioned mixture of argillaceous and calcareous materials. History The Egyptians were probably the first to join building stones with a mixture of sand and a cementitious material (i.e., having the property of or acting like cement). It is generally accepted that the cement used by the Egyptians on such structures as the Great Pyramid was calcined gypsum, Later the Greeks began to calcine limestone for use as a mortar with sand and water. Still later, broken brick and tile were added to the mortar to make the first concrete. The Greeks and Romans found that some sands produced mortars that were especially resistant to the action of water. Hydraulic (i.e., underwater-hardening) cements formed by combining slaked lime, water, and finely divided siliceous materials (e.g., pozzolana) possess superior strength and are capable of resisting the destructive action of water. They were used on the Pantheon, Colosseum, and other structures, some of which are still standing. In 1756 an English engineer, John Smeaton, found that an argillaceous limestone (i.e., containing an appreciable amount of clay as an impurity) produced a cement with greater resistance to the action of water. Despite Smeaton's findings, the use of the old mixture of lime and pozzolana long retained its popularity. Significant contributions in cement technology from England, Swe¬den, France, and Holland were made in the next 68 years. However, the invention of portland cement is generally credited to Joseph Aspdin, an Englishman, who in 1824 patented "portland cement." The name was selected because, on hardening, it resembled the natural building stone from the Isle of Portland, England. The patent features mixing ground limestone and argillaceous materials in appropriate proportions and calcining (i.e., expelling CO2 by roasting) the mixture. This superseded the existing practice of calcining naturally occurring argillaceous limestone. In about 1845 Isaac Johnson, also English, conducted experiments on proportioning the components and calcining them at higher tem¬peratures. His accomplishments are accepted as the beginning of the present-day portland cement industry. The U.S. cement industry originated with the demand for good hydraulic cement for building structures such as the Erie Canal, which was started in 1817. The first discovery of cement rock (i.e., naturally occurring argillaceous limestone with near-optimum ratios of calcium carbonate, alumina, and silica) near Fayetteville, N.Y., was made by C. White. In 1818, White secured a patent for the manufacture of natural cement from that deposit. Subsequently, several natural cement plants were built in 1830-1840 at Rosendale, N.Y., and in the Lehigh Valley of Pennsylvania. David Saylor, who participated in establishing a natural cement plant at Coplay, Pa., in 1850 discovered that a superior cement could be produced by calcining the rock at higher temperatures than hith¬erto. In 1871, Saylor obtained a patent and commenced the manufac¬ture of portland cement. By 1890, there were 17 portland cement plants in the United States with a combined annual output of 62,300 tons. At the end of 1970, the number of plants producing portland cement in the United States (including Puerto Rico) was 169, down from a maximum of 185 in 1967, with total annual shipments of 73.4 million tons valued at $1,298 million. (Fig. 1). In 1970, annual world production of hydraulic cement (which includes pozzolanic materials, hydraulic limes, natural cement, alumina cement, and portland cement, all of which are in current use in various parts of the world) reached 630 million tons (Table 1). Flowsheets of typical U.S. cement plants are shown in Chapter 13. Chemical Composition and Physical Properties It is generally accepted that portland cement clinker consists of a mixture of compounds or synthetic minerals. The four principal compounds are:|