The Hydration chemistry of blended portland blastfurnace slag cements for radiactive waste encapsulation

Blended Portland-blastfumace slag cements provide a suitable matrix for the encapsulation of low and intermediate level waste due to their inherantly low connective porosity and provide a highly alkaline and strongly reduced chemical environment. The hydration mechanism of these materials is complex and involves several competing chemical reactions. This thesis investigates three main areas: 1) The developing chemical shrinkage of the system shows that the underlying kinetics are dominantly linear and estimates of the activation energy of the slag made by this method and by conduction calorimetry show it to be c.53 kJ/mol. 2) Examination of the soUd phase reveals that caldum hydroxide is initially precipitated and subsequently consumed during hydration. The absolute rate of slag hydration is investigated by chemical and thermal methods and an estimation of the average silicate chain length (3 silicate units) by NMR is presented. 3) The developing pore solution chemistry shows that the system becomes rapidly alkaline (pH 13 - 13.5) and subsequently strongly reduced. Ion chromatography shows the presence of reduced sulphur species which are associated with the onset of reducing conditions. In the above studies, close control of the hydration temperature was maintained and the operation of a temperature controlled pore fluid extration press is reported.

Fluid mechanical and electrostatic study on the osmotic flow through cylindrical pores

When two solutions differing in solute concentration are separated by a porous membrane, the osmotic pressure will generate a net volume flux of the suspending fluid across the membrane; this is termed osmotic flow. We consider the osmotic flow across a membrane with circular cylindrical pores when the solute and the pore walls are electrically charged, and the suspending fluid is an electrolytic solution containing small cations and anions. Under the condition in which the radius of the pores and that of the solute molecules greatly exceed those of the solvent as well as the ions, a fluid mechanical and electrostatic theory is introduced to describe the osmotic flow in the presence of electric charge. The interaction energy, including the electrostatic interaction between the solute and the pore wall, plays a key role in determining the osmotic flow. We examine the electrostatic effect on the osmotic flow and discuss the difference in the interaction energy determined from the nonlinear Poisson-Boltzmann equation and from its linearized equation (the Debye-Hückel equation).