Portland cement hydration products

The low strength of the transition zone is attributed to higher porosity and to the orientation of large CH crystals with weak intercrystalline bonds. Hadley (1972) has shown that hollow grains composed of Portland cement hydration products, which increased porosity, appeared more often in the interface than in bulk cement paste. These are known as Hadley grains, where the pores and voids may appear in the form of clusters, which create critical flaws. 

Concrete is a composite typically composed of aggregate and cement paste. It is the connection between these phases - the interfacial transition zone (ITZ) that is most important.. The ITZ is the weakest link in the composite system with lowest mechanical properties of the three [1-4], The ITZ can affect the overall elastic module and the stress distributions in a concrete material. The ITZ is comparatively more porous than that of bulk cement paste, and often less well bonded to the aggregate [3]. This region can have a low formation of calcium-silicate-hydrate (C-S-H gel), a product of Portland cement hydration responsible for the good mechanical properties and durability [5]. 

In the system comprising Portland cement and polyacrylamide more hydrated material is formed, but again a significant part of the cement remains non-hydrated. The cement hydration products are similar to those formed in the absence of the polymer, but they exhibit a denser packing. 

In a mature hydrated portland cement, the products formed are C-S-H gel, Ca(OH)2, ettringite (AFt phase), monosulfate (AFm phase), hydrogamet phases, and possible amorphous phases high in Al" and SO4 ions. A small amount of cryptocrystalline CH may be intimately mixed with C-S-H phase. 

Calcium Silicates. Cements aie hydiated at elevated tempeiatuies foi the commercial manufacture of concrete products. Using low pressure steam curing or hydrothermal treatment above 100°C at pressures above atmospheric, the products formed from calcium siUcates are often the same as the hydrates formed from their oxide constituents. Hence lime and siUca ate ftequendy used in various proportions with or without Portland cement in the manufacture of calcium siUcate hydrate products. Some of these compounds are Hsted in Table 6. 

As far as the final hydration products of ordinary Portland cement are concerned, there is an indication from isothermal calorimetry [57] that there is very little difference in the presence or absence of a calcium lignosulfonate water-reducing admixture. In this work, the heat evolved per unit of water incorporated into the hydrate has been determined for two cements, with the results shown in Fig. 1.25. It can be seen that the relationship between the amount of heat evolved and the amount of water combined with the cement is maintained whether the admixture is present or not. This work also indicated that the retardation in the early stages is compensated for at later times by an acceleration. 

Addition of dampproofers based on caprylic, capric or stearic acids, stearates or wax emulsions do not have any effect on the setting characteristics of hydration products of Portland cement. However, the unsaturated fatty acid salts, such as oleates, although not affecting the tricalcium silicate hydration, have a marked effect on the ettringite and monosulfate reaction [12] and this is illustrated in the isothermal calorimetry results in Fig. 4.4. It is possible that a calcium oleoaluminate hydrate complex is formed involving the double bond of the oleic acid. 

Table 7.31 Hydration products for mineral components of Portland cement (Jolicoeur et al. [125])...

Upon addition of water, the hydration reactions initiate, and the hydraulic cement begins to gain strength. This process is very complex, but the strengthening effect is due basically to the formation of three types of hydration products colloidal products such as C2S xH20, which have a size of less than 0.1 p.m submicrocrystalline products such as Ca(OH)2, Al +, Fe +, and S04 phases with sizes from 0.1 to 1 tim and microcrystalline products, primarily of Ca(OH)2, with particle sizes greater than 1 p,m. The most common type of hydraulic cement, Portland cement, usually contains mostly colloidal products. 

Many cements used today are composites of Portland cement and industrial waste materials that can enter into the hydration reactions and contribute to the strength of the hardened product. These substances include pulverized fuel ash (PFA) from burning of pulverized coal in thermal power stations, crushed blast-furnace slag (Section 17.7), and natural or artificial pozzolanas—that is, volcanic ash and similar finely particulate siliceous or aluminosilicate materials that can react with the Ca(OH)2 in Portland cement to form hydrated calcium silicates and aluminates. As noted earlier, the solubility of Ca(OH)2 is such that the pH of pore water in Portland cements will be about 12.7, at which the Si-O-Si or Si-O-Al links in the solid pozzolanas will be attacked slowly by OH- to form discrete silicate and aluminate ions and thence hydrated calcium silicate or aluminate gels. 

The most widely used single component, calcium sulfoaluminate admixture, is composed of 30% CAS, 50% CaSO and 20% CaO with small amounts of glassy phase. Particle s3ize is coarser than that of Portland cement. Larger particle size ensures that the potential expansion due to hydration is extended over a period of time. Chemical and physical properties of the most widely used proprietary product, Denka CSA, are given in Table 6.10 [74], Other CSAs include mixtures of C ASH and 2 CS (monosulfate and gypsum) and mixtures of Type I cement, liigh-aiumina cement, CaSO, 2H O, Ca(OH) and CaO [75], 4 2... 

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). 

Fig. 7.2 Backscattered electron image of a mature Portland cement paste, aged 2 months. Successively darker areas are of unreacted cement grains (bright), sometimes with visible rims of hydration products, CafOH), other ( undesignated ) regions of hydration products, and pores (black). Scrivener and Pratt (S28).

Silicate anion structures in Portland cement pastes have been studied by the methods described in Section 5.3.2 for calcium silicate pastes. Trimethylsily- i lation (TMS) studies (L20,T12,S69,T36,L31,M43,M44) show that, as with C,S. the proportion of the silicon present as monomer decreases with age and that the hydration products contain dimer, which is later accompanied and eventually partly replaced by polymer (>5Si). Some results have i indicated that fully hydrated pastes of cement differ from those of CjS in that substantial proportions of the silicate occur as monomer (S69,L31), but the results of a study in which pastes of CjS, P-CjS and cement were compared (M44) suggest that the differences between the anion structures of cement and CjS pastes are probably within the considerable experimental errors inherent in the method. The recovery of monomer from unhydrated P-CjS was only 66% and results for cement pastes can only be considered semiquantitative. 

Copeland et al. (C39,C25) treated CjS pastes, and C-S-H prepared in other ways, with various sources of AP, Fe or S04 ions. The XRD peaks of the phases providing the ions disappeared, and changes occurred in the micromorphology of the gels and in the non-evaporable water contents and fractions of the CaO extractable by an organic solvent. It was concluded that the ions were taken up by the C-S-H and that up to about one silicon atom in six could be replaced by aluminium, iron or sulphur, and that aluminium and iron could also replace calcium. These results suggested that the principal hydration product in Portland cement pastes was a substituted C-S-H, a conclusion that later appeared to be supported by the results of the... 

The content of non-evaporable water, relative to that in a fully hydrated paste of the same cement, was used as a measure of the degree of hydration. Portland cement paste takes up additional water during wet curing, so that its total water content in a saturated, surface dry condition exceeds the initial w/c ratio. Evidence from water vapour sorption isotherms indicated that the properties of the hydration product that were treated by the model were substantially independent of w/c and degree of hydration, and only slightly dependent on the characteristics of the individual cement. The hydration product was thus considered to have a fixed content of non-evaporable water and a fixed volume fraction, around 0.28, of gel pores. 

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