Calcium aluminate phases

As noted in Section 3.3.1, the decarbonation of calcite is greatly favoured by intimate mixing with quartz or clay minerals. Under these conditions, much CO2 is lost before any free lime can be detected. The formation of C2S as an early product is well established, but the situation with the calcium aluminate phases is more complex, no one phase being dominant as an initial product (W11). The aluminate or aluminosilicate phases most often reported as early or intermediate products in laboratory experiments with pure chemicals or raw meals have been CA, CjjA, and, less frequently, gehlenite (W12,D6-D8,W13,L8,L9,I6,C9,C10,R10). CjA can form by 850°C (L9,C10) but seems usually to be a later product. Ferrite phase forms readily, and is initially of low Al/Fe ratio (D7,R10). 

The role of the ferrite phase, generally identified as brownmillerite, should be mentioned too. In the case of sulphate attack this phase can be the source of almninate ions [237] moreover the ferrite ions can form the analogue of ettringite or to substitute the aluminate ions in all calcium aluminate phases [222]. The latter case is undoubtedly the most common one in the Portland cement paste. However, the reaction of sulphate ions with ferrites is slower. There is a view that the F/Al ratio in the hydrated phases is lower than in brownmillerite hence, some amount of iron(in) hydroxide is always present [222] (see also Sect. 4.1.1.). This hydroxide occurs in the gel-like form and therefore the diffusion of ions through the gel layer is slowed down. Therefore, the corrosion process is hindered. The other phases containing the Fe ions can be produced too, it is discussed in Chap. 3. 

Alkali metals are present in clinker preferentially in the form of sulfates. The rest are incorporated into the crystalline lattices of clinker minerals. Sodium tends to be preferentially taken up by the calcium aluminate phase, whereas potassium is mainly incorporated into the crystalline lattice of dicalcium silicate, which becomes stabilized in its form. In either case, in the cotrrse of hydration Na and iorts enter the liquid phase together with the balancing aniorts, which eventrrally become incorporated into the hydration products, being replaced with eqirivalent quantities of OH ions ... 

The calcium aluminate phases CA and Cj2A2 may be present in sulfobelitic clinkers if the SO3 content in the raw meal is insufficient to convert the whole amount of AI2O3 into C4A3S. Both phases exhibit a fast hydratioa... 

There are a number of calcium aluminate phases. Most of them exhibit hydraulic properties, and are important for cement chemistry. 

Belite-aluminate cement or aluminate-belite cement, also called porsal cement, contains -C2S (belite) and the calcium aluminate phases CA and its main constituents. It... 

Strontium and barium ions can partially or completely replace calcium ions in the calcium silicate and calcium aluminate phases. 

Skibsted, J., E. Henderson and H. J. Jakobsen. 1993. Characterisation of calcium aluminate phases in cements by Al MAS NMR spectroscopy. Inorg. Chem. 32,1013-1027. 

The reactions in the regulated-set cements containing Cjj A3CF2 (note mixed notation) as a principal phase resemble those in ordinary Portiand cements. Initial reaction rates are controlled by ettringite formation. Setting occurs with formation of the monosulfate, along with some transitory lower-limed calcium aluminate hydrates that convert to the monosulfate within a few hours. 

Special purpose and blended Portland cements are manufactured essentially by the same processes as ordinary Portland cements but have specific compositional and process differences. White cements are made from raw materials of very low iron content. This type is often difficult to bum because almost the entire Hquid phase must be furnished by calcium aluminates. As a consequence of the generally lower total Hquid-phase content, high burning-zone temperatures may be necessary. Past cooling and occasionally oil sprays are needed to maintain both quaHty and color. 

CaO reacting with AI2O3 to form calcium aluminate, CaAl204. Phase changes, on the other hand, are reversible, but may be endothermic or exothermic. 

U.S. imports for consumption, 4 528t Calcium(II), concentration formation constant of chelates, 5 717t 12-Calcium-7-aluminate, phase in Portland cement clinker, 5 472t Calcium absorption, 26 292 Calcium addition, in silicon production, 22 505-506... 

Calcium aluminate chloride, phase in Portland cement clinker, 5 472t Calcium aluminate fluoride, phase in Portland cement clinker, 5 472t Calcium aluminoferrite, phase in Portland cement clinker, 5 472t Calcium aluminoferrite hydrate, 5 477t Calcium—aluminum alloys, 4 530 Calcium amalgam, 22 773 Calcium ammonium nitrate, 2 724 Calcium analysis, of water, 26 37 Calcium A zeolite, separation of hydrocarbons by, 16 823 Calcium—barium—silicon alloy, 22 519 Calcium-bearing manganese silicon,... 

The relative reactivity of the different mineral phases of cement with water is usually given as C A>C S>C S>C AF. Aluminate phases and their hydration products therefore play an important role in the early hydration process. Because of the high reactivity of calcium aluminate, the aluminate hydration reaction is carried out in the presence of sulfate ions. The latter provide control of the reaction rate through the formation of mixed aluminum sulfate products (ettringite and monosulfoaluminate) Calcium sulfate which is added to the cement clinker hence controls the properties of the aluminate hydration products. Sulfates thus play a crucial role in cement hydration and the influence of chemical admixtures on any process where sulfates are involved may be expected to be significant [127],... 

STAR [STeam Active Reforming] A catalytic reforming process for converting aliphatic hydrocarbons to olefins or aromatic hydrocarbons. Hydrocarbons containing five or fewer carbon atoms are converted to olefins. Those containing six or more are dehydrocyclized to aromatic hydrocarbons. The reactions take place in the vapor phase, in a fixed catalyst bed, in the presence of steam. The catalyst is platinum/tin alloy on zinc calcium aluminate. Developed by Phillips Petroleum Company. The first commercial plant was built for Coastal Chemicals in Cheyenne, WY, in 1992 another was built for Polibutenos Argentinos in 1996. The process is now offered by Uhde. 

Several other anhydrous calcium aluminosilicates are known, including grossular or garnet (C3AS3), which is a high-pressure phase, various dehydration products of zeolites, and various products formed metastably by crystallization from melts or glasses. Most are too acid in composition to be of clear relevance to cement chemistry, but some of the devitrification products, especially those with compositions near to CA and structures similar to those of nepheline (Na3KAl4Si40i6) or kalsilite (KAlSiOj (Y4), are of possible interest in relation to the formation of calcium aluminate cements. 

Portland cement clinkers contain small amounts of alkalis and sulphates derived from the raw materials and fuel. Both alkalis and SO3 can be present in the major clinker phases, but tend to combine preferentially with each other to form alkali or potassium calcium sulphates, and it is necessary to consider these components together. In addition, silicate and aluminate phases containing sulphate can form either as intermediates or in undesirable deposits in eement making, and a calcium aluminate sulphate is a major constituent of some expansive and other speeial cements. 

Table 2.3 lists some phases containing MgO that are in varying degrees relevant to cement chemistry. It is not a complete list of phases with essential MgO in the CaO-MgO-AljOj-SiOj system. As seen in Chapter 1, some MgO is also taken up by all four of the major clinker phases, typical contents being 0.5-2.0% for alite, 0.5% for belite, 1.4% for the aluminate phase, and 3.0% for the ferrite phase. Magnesium oxide (periclase), like calcium oxide, has the sodium chloride structure it is cubic, with a = 0.4213 nm, space group Fm3m, Z = 4, = 3581 kgm (S5) and refrac-... 

CjAHg is the only stable ternary phase in the CaO-AUOj H,0 system at ordinary temperatures, but neither it nor any other hydrogarnet phase is formed as a major hydration product of typical, modern Portland cements under those conditions. Minor quantities are formed from some composite cements and, in a poorly crystalline state, from Portland cements. Larger quantities were given by some older Portland cements, and are also among the normal hydration products of autoclaved cement-based materials. CjAHg is formed in the conversion reaction of hydrated calcium aluminate cements (Section 10.1). 

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