PHYSICAL PROPERTIES OF PORTLAND CEMENT

Portland cements are commonly characterized by their physical properties for quality control purposes. Their physical properties can be used to classify and compare portland cements. The challenge in physical property characterization is to develop physical tests that can satisfactorily characterize key parameters. This section, taken largely from the PCA (1988), describes the more common U.S. portland cement physical tests. Specification values, where given, are taken from ASTM C 150, Standard Specification for Portland Cement. Keep in mind that these tests are, in general, performed on "neat" cement pastes - that is, they only include portland cement and water. Neat cement pastes are typically difficult to handle and test and thus they introduce more variability into the results. Cements may also perform differently when used in a "mortar" (cement + water + sand). Over time, mortar tests have been found to provide a better indication of cement quality and thus, tests on neat cement pastes are typically used only for research purposes (Mindess and Young, 1981). However, if the sand is not carefully specified in a mortar test, the results may not be transferable. Fineness Fineness, or particle size of portland cement affects hydration rate and thus the rate of strength gain. The smaller the particle size, the greater the surface area-to-volume ratio, and thus, the more area available for water-cement interaction per unit volume. The effects of greater fineness on strength are generally seen during the first seven days (PCA, 1988). Fineness can be measured by several methods: AASHTO T 98 and ASTM C 115: Fineness of Portland Cement by the Turbidimeter. AASHTO T 128 and ASTM C 184: Fineness of Hydraulic Cement by the 150-mm (No. 100) and 75-mm (No. 200) Sieves AASHTO T 153 and ASTM C 204: Fineness of Hydraulic Cement by Air Permeability Apparatus AASHTO T 192 and ASTM C 430: Fineness of Hydraulic Cement by the 45-mm (No. 325) Sieve Soundness When referring to portland cement, "soundness" refers to the ability of a hardened cement paste to retain its volume after setting without delayed destructive expansion (PCA, 1988). This destructive expansion is caused by excessive amounts of free lime (CaO) or magnesia (MgO). Most portland cement specifications limit magnesia content and expansion. The typical expansion test places a small sample of cement paste into an autoclave (a high pressure steam vessel). The autoclave is slowly brought to 2.03 MPa (295 psi) then kept at that pressure for 3 hours. The autoclave is then slowly brought back to

room temperature and atmospheric pressure. The change in specimen length due to its time in the autoclave is measured and reported as a percentage. ASTM C 150,Standard Specification for Portland Cement specifies a maximum autoclave expansion of 0.80 percent for all portland cement types. The standard autoclave expansion test is: AASHTO T 107 and ASTM C 151: Autoclave Expansion of Portland Cement Setting Time Cement paste setting time is affected by a number of items including: cement fineness, water-cement ratio, chemical content (especially gypsum content) and admixtures. Setting tests are used to characterize how a particular cement paste sets. For construction purposes, the initial set must not be too soon and the final set must not be too late. Additionally, setting times can give some indication of whether or not a cement is undergoing normal hydration (PCA, 1988). Normally, two setting times are defined (Mindess and Young, 1981): 1. Initial set. Occurs when the paste begins to stiffen considerably. 2. Final set. Occurs when the cement has hardened to the point at which it can sustain some load. These particular times are just arbitrary points used to characterize cement, they do not have any fundamental chemical significance. Both common setting time tests, the Vicat needle and the Gillmore needle, define initial set and final set based on the time at which a needle of particular size and weight either penetrates a cement paste sample to a given depth or fails to penetrate a cement paste sample. The Vicat needle test is more common and tends to give shorter times than the Gillmore needle test. Table 3.14 shows ASTM C 150 specified set times. Table 3.14: ASTM C 150 Specified Set Times by Test Method Test Method Set Type Time Specification Vicat Initial 45 minutes Final 375 minutes Gillmore Initial 60 minutes Final 600 minutes The standard setting time tests are: AASHTO T 131 and ASTM C 191: Time of Setting of Hydraulic Cement by Vicat Needle AASHTO T 154: Time of Setting of Hydraulic Cement by Gillmore Needles ASTM C 266: Time of Setting of Hydraulic-Cement Paste by Gillmore Needles Strength

Cement paste strength is typically defined in three ways, compressive, tensile and flexural. These strengths can be affected by a number of items including: water-cement ratio, cement-fine aggregate ratio, type and grading of fine aggregate, manner of mixing and molding specimens, curing conditions, size and shape of specimen, moisture content at time of test, loading conditions and age (Mindess and Young, 1981). Since cement gains strength over time, the time at which a strength test is to be conducted must be specified. Typically times are 1 day (for high early strength cement), 3 days, 7 days, 28 days and 90 days (for low heat of hydration cement). When considering cement paste strength tests, there are two items to consider: Cement mortar strength is not directly related to concrete strength. Cement paste strength is typically used as a quality control measure. Strength tests are done on cement mortars (cement + water + sand) and not on cement pastes. a.Compressive Strength The most common strength test, compressive strength, is carried out on a 50 mm (2inch) cement mortar test specimen. The test specimen is subjected to a compressive load (usually from a hydraulic machine) until failure. This loading sequence must take no less than 20 seconds and no more than 80 seconds. Table 3.15 shows ASTM C 150 compressive strength specifications. Table 3.15: ASTM C 150 Portland Cement Mortar Compressive Strength Specifications in MPa (psi) Curing Portland Cement Type Time I IA II IIA III IIIA IV V 1 day 12.4 10.0 (1800) (1450) 3 days 12.4 10.0 10.3 8.3 24.1 19.3 8.3 (1800) (1450) (1500) (1200) (3500) (2800) (1200) 7 days 19.3 15.5 17.2 13.8 -6.9 15.2 (2800) (2250) (2500) (2000) (1000) (2200) 28 days 17.2 20.7 (2500) (3000) Note: Type II and IIA requirements can be lowered if either an optional heat of hydration or chemical limit on the sum of C3S and C3A is specified The standard cement mortar compressive strength test is: AASHTO T 106 and ASTM C 109: Compressive Strength of Hydraulic Cement Mortars (Using 50-mm or 2-in. Cube Specimens)

ASTM C 349: Compressive Strength of Hydraulic Cement Mortars (Using Portions of Prisms Broken in Flexure)

b.Tensile Strength `Although still specified by ASTM, the direct tension test does not provide any useful insight into the concrete-making properties of cements. It persists as a specified test because in the early years of cement manufacture, it used to be the most common test since it was difficult to find machines that could compress a cement sample to failure. c.Flexural Strength Flexural strength (actually a measure of tensile strength in bending) is carried out on a 40 x 40 x 160 mm (1.57-inch x 1.57-inch x 6.30-inch) cement mortar beam. The beam is then loaded at its center point until failure. The standard cement mortar flexural strength test is: ASTM C 348: Flexural Strength of Hydraulic Cement Mortars Specific Gravity Test Specific gravity is normally used in mixture proportioning calculations. The specific gravity of portland cement is generally around 3.15 while the specific gravity of portlandblast-furnace-slag and portland-pozzolan cements may have specific gravities near 2.90 (PCA, 1988). The standard specific gravity test is: AASHTO T 133 and ASTM C 188: Density of Hydraulic Cement Heat of Hydration The heat of hydration is the heat generated when water and portland cement react. Heat of hydration is most influenced by the proportion of C3S and C3A in the cement, but is also influenced bywater-cement ratio, fineness and curing temperature. As each one of these factors is increased, heat of hydration increases. In large mass concrete structures such as gravity dams, hydration heat is produced significantly faster than it can be dissipated (especially in the center of large concrete masses), which can create high temperatures in the center of these large concrete masses that, in turn, may cause undesirable stresses as the concrete cools to ambient temperature. Conversely, the heat of hydration can help maintain favorable curing temperatures during winter (PCA, 1988). The standard heat of hydration test is: ASTM C 186: Heat of Hydration of Hydraulic Cement

Loss on Ignition Loss on ignition is calculated by heating up a cement sample to 900 - 1000C (1650 1830F) until a constant weight is obtained. The weight loss of the sample due to heating is then determined. A high loss on ignition can indicate prehydration and carbonation, which may be caused by improper and prolonged storage or adulteration during transport or transfer (PCA, 1988). The standard loss on ignition test is contained in: AASHTO T 105 and ASTM C 114: Chemical Analysis of Hydraulic Cement Cosistency Test Consistency of a cement paste refers to its ability to flow. Normal consistency pastes are required to be prepared for testing cement specimens. A paste is said to have a normal consistency when the plunger of the Vicat Apparatus penetrates it by 101 mm. the corresponding water-cement ratio is reported.

CHEMICAL PROPETIES OF PRTLAND CEMENT Silica Fumes is added to Portland cement concrete to improve its properties, in particular its compressive strength, bond strength, and abrasion resistance. Addition of silica fume can yield exceptionally high strengths, and cements containing 520 % silica fume are occasionally produced. However, its setting time is prolonged. Slag-lime cements. Ground granulated blast furnace slag is not hydraulic on its own, but is "activated" by addition of alkalis. Large quantity of alkalis (sodium and

potassium oxides) is carried away by flue gases during clinkering. However, a small quantity is left behind, excess of which causes efflorescence.
Cement may sometimes contain free lime, which may cause expansion. Specifically, high alumina cement is chemical resistant and can withstand frigid temperatures. Also, alumina quickens setting but weakens the cement. MgO (Magnesia) is one of the raw materials for making Portland cement in dry process plants. If too much MgO is added, the cement may become expansive. Production of MgO-based cement using serpentinite and waste CO2 (as opposed to conventional CaO-

based cement using fossil fuels) may reduce anthropogenic emissions of CO2. Also imparts strength to the cement when mixed in small quantity. Excess magnesia makes the cement unsound. Iron oxide/Ferric Oxide is mainly responsible to impart colour to the cement. It also helps in adding strength and hardness to the cement to a certain extent. Sulfur trioxide. Excess quantity of sulfur trioxide also makes cement unsound.

CEMENT MANUFACTURING
Bricklayer Joseph Aspdin of Leeds, England first made portland cement early in the 19th century by burning powdered limestone and clay in his kitchen stove. By this crude method he laid the foundation for an industry which annually processes literally mountains of limestone, clay, cement rock, and other materials into a powder so fine it will pass through a sieve capable of holding water. Cement is so fine that one pound of cement contains 150 billion grains. Portland cement, the basic ingredient of concrete, is a closely controlled chemical combination of calcium, silicon, aluminum, iron and small amounts of other ingredients to which gypsum is added in the final grinding process to regulate the setting time of the concrete. Lime and silica make up about 85% of the mass. Common among the materials used in its manufacture are limestone, shells, and chalk or marl combined with shale, clay, slate or blast furnace slag, silica sand, and iron ore. Each step in manufacture of portland cement is checked by frequent chemical and physical tests in plant laboratories. The finished product is also analyzed and tested to ensure that it complies with all specifications. Two Manufacturing Processes Two different processes, "dry" and "wet," are used in the manufacture of portland cement. When rock is the principal raw material, the first step after quarrying in both processes is the primary crushing. Mountains of rock are fed through crushers capable of handling pieces as large as an oil drum. The first crushing reduces the rock to a maximum size of about 6 inches. The rock then goes to secondary crushers

or hammer mills for reduction to about 3 inches or smaller. In the wet process, the raw materials, properly proportioned, are then ground with water, thoroughly mixed and fed into the kiln in the form of a "slurry" (containing enough water to make it fluid). In the dry process, raw materials are ground, mixed, and fed to the kiln in a dry state. In other respects, the two processes are essentially alike. The raw material is heated to about 2,700 degrees Farenheit in huge cylindrical steel rotary kilns lined with special firebrick. Kilns are frequently as much as 12 feet in diameter large enough to accommodate an automobile and longer in many instances than the height of a 40-story building. Kilns are mounted with the axis inclined slightly from the horizontal. The finely ground raw material or the slurry is fed into the higher end. At the lower end is a roaring blast of flame, produced by precisely controlled burning of powdered coal, oil or gas under forced draft. As the material moves through the kiln, certain elements are driven off in the form of gases. The remaining elements unite to form a new substance with new physical and chemical characteristics. The new substance, called clinker, is formed in pieces about the size of marbles. Clinker is discharged red-hot from the lower end of the kiln CLINKER and generally is brought down to handling temperature in various types of coolers. The heated air from the coolers is returned to the kilns, a process that saves fuel and increases burning efficiency.