Mechanisms of chromium deposition and dissolution under direct and pulse reverse plating conditions

Baths containing sulphuric acid as catalyst and others with selected secondary catalysts (methane sulphonic acid - MSA, SeO2, a KBrO3/KIO3 mixture, indium, uranium and commercial high speed catalysts (HEEF-25 and HEEF-405)) were studied. The secondary catalysts influenced CCE, brightness and cracking. Chromium deposition mechanisms were studied in Part II using potentiostatic and potentiodynamic electroanalytical techniques under stationary and hydrodynamic conditions. Sulphuric acid as a primary catalyst and MSA, HEEF-25, HEEF-405 and sulphosalycilic acid as co-catalysts were explored for different rotation, speeds and scan rates. Maximum current was resolved into diffusion and kinetically limited components, and a contribution towards understanding the electrochemical mechanism is proposed. Reaction kinetics were further studied for H2SO4, MSA and methane disulphonic acid catalysed systems and their influence on reaction mechanisms elaborated. Charge transfer coefficient and electrochemical reaction rate orders for the first stage of the electrodeposition process were determined. A contribution was made toward understanding of H2SO4 and MSA influence on the evolution rate of hydrogen. Anodic dissolution of chromium in the chromic acid solution was studied with a number of techniques. An electrochemical dissolution mechanism is proposed, based on the results of rotating gold ring disc experiments and scanning electron microscopy. Finally, significant increases in chromium electrodeposition rates under non-stationary conditions (PRC mode) were studied and a deposition mechanisms is elaborated based on experimental data and theoretical considerations.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

The magnetic exchange interactions in chromium chalcogenide spinels

The chromium chalcogenide spinels, MCr2X4 (M = Zn, Cd, Hg; X = O, S, Se), have been the subject of considerable interest in recent years. In each case the crystal structure is that of a normal spinel with the chromium ions exclusively occupying the octahedral (B) sites, so that when diamagnetic ions are located at the tetrahedral (A) sites the only magnetic interactions present are those between B-site ions. Despite such apparently simple circumstances a rich variety of magnetic behaviour is exhibited. For the oxides the ground state spin configurations are antiferromagnetic whilst for the selenides ferromagnetic interactions dominate and several authors have drawn attention to the fact that the nature of the dominant interaction is a function of the nearest neighbour chromium - chromium separation. However, at least two of the compounds exhibit spiral structures and it has been proved difficult to account for the various spin configurations within a unified theory of the magnetic interactions involved. More recently, the possibility of formulating a simplified interpretation of the magnetic interactions has been provided by the discovery that the crystal struture of spinels does not always conform to the centrosymmetrical symmetry Fd3m that has been conventionally assumed. The deviation from this symmetry is associated with small < 111> displacements of the octahedrally coordinated metal ions and the structures so obtained are more correctly referred to the non-centrosymmetrical space group F43m. In the present study, therefore, extensive X-ray diffraction data have been collected from four chromium chalcogenide specimens and used to refine the corresponding structural parameters assuming F43m symmetry and also with conventional symmetry. The diffracted intensities from three of the compounds concerned cannot be satisfactorily accounted for on the basis of conventional symmetry and new locations have been found for the chromium ions in these cases. It is shown, however, that these displacements in chromium positions only partially resolve the difficulties in interpreting the magnetic behaviour. A re-examination of the magnetic data from different authors indicates much greater uncertainty in their measurements than they had claimed. By taking this into consideration it is shown that a unified theory of magnetic behaviour for the chromium chalcogenide spinels is a real possibility.

Preferred orientation in 18/10, 18/12 and 18/14 chromium/nickel steels and its relation to tensile and press forming properties

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Precipitation of chromium containing phases in aluminide coated nickel-base superalloy single crystals

The precipitation of chromium-containing phases, in both the B2 type β-phase coating matrix (nominally NiAl) and the substrate of high-activity-pack-aluminized single crystals of a nickel-base superalloy, is considered in this paper. An ‘edge-on’ transmission electron microscopy (TEM) technique is employed to examine the precipitation of M23X6, σ, α-Cr and other phases after coating and diffusion treatment and subsequent post-coating treatment at 850 and 950 °C. Initial precipitation is dominated by the formation of M23X6 in both the coating and substrate, however, in the case of single-crystal substrates the formation of this carbon-rich phase is not sustained. M23X6 precipitation is superceded by the formation of coherent precipitates of the α-Cr phase which effectively retains the basis but removes the superlattice of the β-matrix. Extensive precipitation of α-Cr has the effect of changing the balance of chromium to molybdenum in solution in the β-phase and further precipitation is dominated by Σ-phase intermetallics and other Cr-Mo-containing phases.