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12.1.5 Composite cements and other topics
Partial replacement of cement by silica fume increases the strength in concrete, but not in pastes (B169). This supports the view that the effect is due to a strengthening of the paste-aggregate bond (B169,R81,S128). Studies of concretes by backscattered electron imaging showed that the increase in porosity in the ITZ is much less marked if silica fume is present (B169,B170,R82,S133). Scrivener and Gartner (S128) found some increase in porosity, but attributed it almost entirely to the presence of hollow-shell grains. With pastes vibrated against a single piece of aggregate, in contrast, the replacement had no significant effect on the distribution of porosity within the ITZ, and some clumping of the silica fume was observed. Clumping was found to occur in pastes even when a superplasticizer was used (S133), suggesting that the coarse aggregate breaks up the clumps by crushing or shearing during mixing.
Computer modelling of the ITZ (B171) confirmed that silica fume would be expected to decrease the gradient of capillary porosity in the ITZ but indicated that it would not eliminate it completely. The model also predicted that the effectiveness of mineral additions in increasing the integrity of the ITZ would depend on both their particle size and their reactivity. Inert additions would, with some reservations, have little effect, and flyash would be less effective than silica fume, because of its larger particle size and lower reactivity. The porosity in the ITZ may also be increased by dissolution of CH (B170). An experimental study showed that partial replacement of cement by flyash can either increase or decrease the width of the ITZ, depending on the characteristics of the flyash, but that slag had relatively little effect (C74).
Interfaces of calcium aluminate cements with aggregates are discussed in Chapter 10. The ITZ between Portland cement paste and steel has been studied by SEM, using various techniques of specimen preparation (e.g. A38,B172). The major features observed have been substantial deposits of CH and, further away from the interface, a relatively weak, porous zone. Bentur et al. (B172) also reported the occurrence of a duplex film. Interfaces of cement or C3S pastes with zinc (A39,T64) or copper (T64) have been studied.

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