Raw mix formulation
The characteristic greenish-gray to brown color of ordinary Portland cement derives from a number of transitional elements in its chemical composition. These are, in descending order of coloring effect, chromium, manganese, iron, copper, vanadium, nickel and titanium. The amount of these in white cement is minimized as far as possible. Cr2O3 is kept below 0.003%, Mn2O3 is kept below 0.03%, and Fe2O3 is kept below 0.35% in the clinker. The other elements are usually not a significant problem. Portland cement is usually made from cheap, quarried raw materials, and these usually contain substantial amounts of Cr, Mn and Fe. For example, limestone used in cement manufacture usually contain 0.3-1% Fe2O3, whereas levels below 0.1% are sought in limestone for white manufacture. Typical clays used in gray cement raw mix may contain 5-15% Fe2O3. Levels below 0.5% are desirable, and conventional clays are usually replaced with kaolin. Kaolin is fairly low in SiO2, and so a large amount of sand is usually also included in the mix. Iron and manganese usually occur together in nature, so that selection of low-iron materials usually ensures that manganese content is also low, but chromium can arise from other sources, notably from the wear of chrome steel grinding equipment during the production of raw mix. See raw mill. This wear is exacerbated by the high sand-content of the mix, which makes it extremely abrasive. Furthermore, to make a combinable raw mix, the sand must be ground to below 45 μm particle diameter. Often this is achieved by grinding the sand separately, using ceramic grinding media to reduce contamination.
In general, the rotary kilns used to chemically combine the raw materials are operated at a higher peak temperature (1450-1500°C) than that required for gray clinker manufacture (1400-1450°C). This requires a higher fuel consumption (typically 20-50% more), and results in lower kiln output (typically 20-50% less) for a given sized kiln. The reason for this is the relatively small amount of liquid produced during sintering, because of the low iron-content of the mix. The final reaction in the kiln, conversion of belite to alite, requires the melt liquid as a solvent, and is slower if the amount of melt is low. This can be partially compensated by adding to the raw mix a combination of calcium sulfate and fluoride in the form of calcium fluoride or waste cryolite. This combination reduces the reaction temperature. In cases where the clinker Fe2O3 content is above 0.2% (which is almost always the case), the unique processes of "bleaching" and "quenching" are also employed. "Bleaching" involves directing a second flame (apart from that used to heat the kiln) onto the bed of clinker close to the kiln exit to reduce Fe(III) to Fe(II). This reduction is rigorously avoided in gray cement production, because of the deleterious effect it can have on clinker quality. But in white clinker production, where the iron content is low, this is not an issue. Subsequently, to prevent the re-oxidation of the iron, "quenching" is performed. This consists of rapidly lowering the clinker temperature from 1200°C to below 600°C in a few seconds, as it leaves the kiln. This usually involves dropping it into cold water. This contributes to the relatively poor energy efficiency of the process, since the sensible heat of the clinker is not recycled as in normal clinker manufacturer.
Clinker grinding and handling
The clinker is next ground to cement (perhaps after a drying stage). Here calcium sulfate is added to control set, in the form of a high-purity grade of gypsum or anhydrite. In some specifications (not ASTM), a small amount of titanium dioxide may be added to improve reflectance. At all stages, great care is needed to avoid contamination with colored materials.
White Portland cement differs physically from gray cement only in terms of its color. Its setting behavior and strength development are essentially the same as that expected in gray cement and it meets standard specifications such as ASTM C 150 and EN 197. In practice, because much white cement is used in pre-cast concrete products, it is commonly made to a high-early strength specification such as ASTM C 150 Type III. This aids concrete manufacturers' production rate. Higher potential strength also helps to counteract the strength-diminishing effects of pigment addition. In addition to the usual specifications, manufacturers guarantee the whiteness of the product, typically in terms of a reflectance measurement, such as L*a*b L-value, or tristimulus. In the latter case, because off-color white cement tends to be greenish, the Tri-Y (green) value is used. Because the color so much depends upon the "bleaching" and "quenching" operations, merely specifying a low iron content does not guarantee good whiteness.