Pore structure and diffusional properties of hardened cement pastes

This study has investigated the inclusion of pulverised fuel ash (PFA) and blast furnace slag (BFS) into hardened cement pastes (HCP) in retarding the ingress of chloride ions and oxygen molecules from the external environment. The influence of environmental factors such as drying and carbonation on the pore structure and diffusional properties of OPC, OPC/30%PFA and OPC/65%BFS hardened pastes was investigated. Specimens were desorbed from a saturated surface dry condition to a near constant weight at 65% relative humidity (RH) while others were simultaneously exposed to a 65% RH atmosphere and a carbon dioxide atmosphere of up to 5% by volume until there were fully carbonated. The presence of the interfacial zone at the cement paste-aggregate interface was critically reviewed and identified. The influence of the interfacial zone on porosity and chloride ingress in assumed periodic composites of glass bead mortars was also studied. The investigations have demonstrated the following: (a) The use of fly ash and slag in blended cement pastes has resulted in a marked reduction in capillary porosity and rate of chloride ingress. (b) The ratio of oxygen to chloride diffusion coefficients increased from values close to 1 in permeable pastes, to values of around 15 in low-permeability blended fly ash and slag pastes. This supports the view that the diffusion of chloride ions is retarded by the surface charge of the hydrated cement gel in low-permeability pastes. (c) Compared with plain OPC pastes, the carbonation of blended fly ash and slag pastes resulted in a marked increase in the coarse capillary porosity and a corresponding increase in the oxygen and chloride diffusion rates.

Interactions between organic polymers and cement hydration products

Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

Effects of fibre reinforcement on the mechanical properties of brushite cement

In this study the effect of structure and amount of polyglactin fibre incorporation into a brushite forming calcium phosphate cement system and the effect of mechanical compaction on the fibre modified system were investigated. In comparison the effect of resorbable polycaprolactone surface coating of cement specimens was investigated. The results showed that, apart from the mechanical properties of the reinforcing material, the structure of the incorporated fibres, regular or random, is crucial for the resulting flexural strength and modulus of elasticity. Fibre reinforcement could also be combined with mechanical compaction of the cement/fibre composite paste leading to a possible 7-fold increase in flexural strength or an almost 5-fold increase in modulus of elasticity. Reinforcement of the tensile surface of cement grafts may ultimately improve strength where required, especially in conjunction with bone fixation devices. © 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Low frequency dielectric spectroscopy of bitumen binders as an indicator of adhesion potential to quartz aggregates using Portland cement

The purpose of this investigation was to interpret the bitumen-aggregate adhesion based on the dielectric spectroscopic response of individual material components utilizing their dielectric constants, refractive indices and average tangent of the dielectric loss angle (average loss tangent). Dielectric spectroscopy of bitumen binders at room temperature was performed in the frequency range of 0.01–1000 Hz. Dielectric spectroscopy is an experimental method for characterizing the dielectric permittivity of a material as a function of frequency. Adhesion data has been determined using the Rolling bottle method. The results show that the magnitude of the average tangent of the dielectric loss angle (average loss tangent) depends on bitumen type. The average loss tangent in the frequency range 0.01–1 Hz is introduced as a potential indicator for predicting polarizability and, thereby, adhesion potential of bitumen binders to quartz aggregates when using Portland cement. In order to obtain acceptable adhesion of 70/100 penetration grade bitumen binders and quartz aggregates when using Portland cement, it is suggested that the binder have an average tan δ > 0.035 in the frequency range 0.01–1 Hz.