The nanostructure and degradation of C-S-H in Portland and blended cements

The microstructure and composition of water and KOH activated hardened pastes of commercial neat white Portland cement (WPC) and blends with 30% fly ash (PFA) have been characterised using a multi-technique approach, With particular emphasis on the nature of the C-S-H phase. The neat and fly ash blended pastes were activated with water or a 5M KOH solution and cured for one year at 25'C, one month at 55'C and one month at 85'C. The mean length of the aluminosilicate anion structure of C-S-H (29 Si MAS NMR) increased with age and it was higher in the fly ash blended systems. Formulae were presented for the average structural units in the C-S-H present in the systems analysed by TEM-EDX. SEM micrographs showed that as hydration occurred,
the microstructure became denser because outer product C-S-H was formed in the water filled spaces and additional C-S-H resulted from the pozzolanic reaction. The chemical
composition of C-S-H could not be determined by SEM-EDX because of intermixing with other phases; TEM-EDX was necessary. Inner product C-S-H morphology was fine and homogeneous and that of outer product C-S-H was fibrillar in the water activated systems and foil-like with alkali activation. Fly ash replacement did not change the morphology of lp and Op C-S-H. Small fully hydrated cement and PFA particles were filled with a less dense lp C-S-H with morphology very similar to the foil-like one. TEM-EDX showed that, in general, the mean Ca/(AI+Si) atomic ratio was lower in the water activated blends than that in the neat cement pastes due to the fly ash reaction. The composition- structure data were discussed in terms of models for the nanostructure of C-S-H.

Higher curing temperature accelerated the rate of the cement hydration. The mean length of the aluminosilicate of the C-S-H anions was much higher than that of C-S-H formed at lower temperatures, and it was also higher in the blended pastes than with neat cement. Backscattered electron images showed that the grey level of C-S-H in the
systems cured at 55T and 85T was in places quite similar to that of the calcium hydroxide: that is, it was brighter than in pastes cured at lower temperature. SEM also showed that the microstructure of the systems cured at higher temperature exhibited non uniform porosity. Inner product C-S-H with a fine scale, homogeneous morphology,
was abundant in all systems cured at 55'C and 85'C. Op C-S-H was generally fibrillar with Nvater, and foil-like with alkali. However, the higher temperature curing did result
in coarser fibrillar morphology (water activated systems) than that formed at lower temperatures.

The C-S-H gel formed in the commercial WPC-30% PFA blended paste hydrated for one year at 25'C and water leached for twelve weeks was also characterised in this work. A matrix effect was clearly observed by 29 Si MAS NMR. Cross-linking of the aluminosilicate anion structure of C-S-H occurred after leaching the sample for four weeks. Formulae were also presented for the average structural units in the C-S-H
present in the unleached and four weeks water leached systems analysed by TEM-EDX. lp C-S-H morphology was fine and homogeneous and Op C-S-H had fibrillar morphology. There were many areas in the microstructure of the leached sample where Op C-S-H with foil-like morphology coexisted with fibrillar Op C-S-H.