The reaction of hydroxy-Al interlayers in montmorillonite with monosilicic acid was studied by chemical analysis, X-ray diffractometry (XRD), and Fourier-transform infrared (FTIR) spectroscopy. Hydroxy-Al interlayers in montmorillonite was prepared by treating Ca-montmorillonite (<2) μm) with hydroxy-Al solutions at an initial Al concentration of 0.5 mM and OH/Al molar ratios of 1.0, 2.0, and 2.5. The resultant partially interlayered montmorillonite was reacted with 0.5, 0.9, and 1.4 mM monosilicic acid solutions.

A substantial amount of monosilicic acid was adsorbed by the interlayer hydroxy-Al polymers through the reaction of Si-OH groups with mainly Al-OH groups, resulting in the formation of silicated Al-interlayers with Si/Al molar ratios up to 0.19. The adsorption of silicic acid by interlayer hydroxy-Al polymers increased the basal spacings of the partially interlayered montmorillonite. This effect was most pronounced for the hydroxy-Al interlayered montmorillonite formed in the systems at an OH/Al ratio of 2.0, in which the d(001) reflections (110°C) shifted from 13.6 Å before silication to 14.1 Å with a shoulder at 17.0 Å after silication. The differential IR spectrum of the silicated hydroxy-Al interlayers in montmorillonite exhibited absorption bands at 935 and 3730 cm−1, which can be assigned to Si-O and Si-OH, respectively, of the adsorbed Si(OH)4. An interlayer structure analogous to that of “proto-imogolite” was, thus, proposed for the silicated interlayer hydroxy-Al polymers in montmorillonite. This study revealed a new mechanism through which Si enters the interlayer spaces of smectite. The silication of hydroxy-Al-interlayered clays in natural environments and the related modifications in surface properties of the clays should receive increasing attention.

Polycarboxylate superplasticizer (PCE) is a widely used water-reducing agent that can reduce significantly the water demand of concrete, which reduces the porosity and enhances the strength and durability of the concrete. (The PCE consists of a single backbone with many long PEO side chains.) Generally, aggregate occupies >70 wt.% of concrete; clay minerals are ubiquitous in nature and are difficult to avoid in mined aggregates. Clay minerals in aggregate often render the PCE ineffective and give rise to rapid loss of the fluidity of the concrete; this phenomenon is referred to as ‘poor clay tolerance of PCE.’ Though the poor clay tolerance of PCE is known widely, the relationship between the clay tolerance and the molecular structure of the PCE, in particular the effect of the side-chain structures, on clay tolerance is not understood completely. The objective of the present study was to determine the effect of different grafting densities of polyethylene oxide (PEO) side chains on the clay tolerance of PCE. The raw materials included mainly PCE, which was synthesized using acrylic acid and isopentenol polyoxyethylene ether, and a natural montmorillonite (Mnt), one of the most common clay minerals. The loss of fluidity of the cement paste was tested to assess the clay tolerance; total organic carbon was used to measure the amount of PCE adsorbed; X-ray diffraction, transmission electron microscopy, Fourier-transform infrared spectroscopy, and thermogravimetric analysis were used to investigate the microstructure of the intercalated Mnt. The results showed that preventing the superficially adsorbed PCE from being intercalated into Mnt was of great importance in terms of the improvement in clay tolerance of PCE, which increased with greater grafting density of PEO in the side chain of the PCE. The results also suggested the possibility that polymers which intercalate preferentially into the Mnt could improve significantly the clay tolerance of the PCE system.