Electrochemical chloride extraction to halt corrosion of reinforcement

This thesis presents results of experiments designed to study the effect of applying electrochemical chloride extraction (ECE) to a range of different hardened cement pastes. Rectangular prism specimens of hydrated cement paste containing sodium chloride at different concentrations were subjected to electrolysis between the embedded steel cathodes and external anodes of activated titanium mesh. The cathodic current density used was in the range of 1 to 5 A/m2 with treatment periods of 4 to 12 weeks. After treatment, the specimens were cut into sections which were subjected to pore-solution expression and analysis in order to determine changes in the distribution of free and total ionic species. The effect of the ECE treatment on the physical and microstructural properties of the cements was studied by using microhardness and MIP techniques. XRD was employed to look at the possibility of ettringite redistribution as a result of the accumulation of soluble sulphate ions in the cement matrix near the cathode during ECE. Remigration of chloride which remains after the ECE treatment and distribution of other ions were studied by analysing specimens which had been stored for several months, after undergoing ECE treatment. The potentials of the steel cathodes were also monitored over the period to detect any changes in their corrosion state. The main findings of this research were as follows: 1, ECE, as applied in this investigation, was capable of removing both free and bound chloride. The removal process occurred relatively quickly and an equilibrium between free and bound chlorides in the specimens was maintained throughout. At the same time, alkali concentrations in the pore solution near the steel cathode increased. The soluble sulphate ionic concentration near the cathode also increased due to the local increase in the pH of the pore solution. 2, ECE caused some changes in physical and microstructural of the cement matrix. However these changes were minimal and in the case of microhardness, the results were highly scattered. Ettringite in the bulk material well away from the cathode was found not to increase significantly with the increase in charge passed.3, Remigration of chloride and other ionic species occurred slowly after cessation of ECE with a resultant gradual increase in the Cl-/OH- ratio around the steel.4, The removal of chloride from blended cements was slower than that from OPC.

Synthesis of hydrazine by the fixation process

A critical review of the literature concerning organic derivatives of hydrazine, the ammonia-chlorine reaction and the electrolytic formation of hydrazine has been carried out. Apparatus was constructed to study the electrolysis of liquid ammonia, the formation of chloramine and the fixation of chloramine with a ketone to form an isohydrazone. In the latter case the reaction was carried out in a 3" diameter stirred tank and also in a 1" diameter, 2' high column reactor where the liquid phase was continuously recirculated. Two methods of analysis of azines and isohydrazones in a ketone solution have been developed. One is a colorimetric technique using p-dimethylaminobenzaldehyde and the other involves the hydrolysis of the organic derivative to hydrazine sulphate. Hydrazine was detected in low concentration in some of the electrolytic experiments carried out but it was concluded that this method did not show sufficient promise to warrant further investigation. The gas phase formation of chloramine and acetone isohydrazone has also been studied but in this system difficulties were encountered with the chlorine jet blocking with ammonium chloride. The formation of isohydrazones in a stirred tank reactor has been investigated in some detail and the effect of several parameters was determined. The yield was found to be extremely sensitive to chlorine concentration and in order to obtain yields of more than 90 per cent, the molar concentration of chlorine in the gas phase had to be of the order of 5 per cent. An optimum temperature in the region of 0°C was also detected. These results disagree with those quoted in previous studies but extensive experimental work has confirmed the information presented in this thesis. It has also been shown that at high yields the chloramine formation reaction took place in the gas phase.

Electrocoating of carbon fibres:a route for interface control in carbon fibre reinforced poly methylmethacrylate?

A simple method of creating defined PMMA and poly (MMA-co-Cz) electrocoatings on carbon fibres is described. The electrodeposition of poly methylmethacrylate (PMMA) onto unsized, unmodified carbon fibres was performed by simple constant current electrolyses of methylmethacrylate (MMA) monomer in dimethylformamide (DMF) solutions and the 'pur' liquid monomer using sodium nitrate and lithium perchlorate as supporting electrolytes. The presence of polymeric coatings successfully attached to the carbon fibres was verified by scanning electron microscopy and photoelectron spectroscopy (XPS). Performing the electrolysis in dilute MMA in DMF solutions ([MMA]