Microstructural evolution in silicon implanted with chlorine ions

In the present work p-type Si specimens were implanted with Cl ions of 100 keV to successively increasing fluences of 1 x 10(15), 5 x 10(15), 1 x 10(16) and 5 x 10(16) ions cm(-2) and subsequently annealed at 1073 K for 30 min. The microstructure was investigated with the transmission electron microscopy (TEM) in both the plane-view and the cross-sectional view. The implanted layer was amorphized after chlorine implantation even at the lowest ion fluence, while re-crystallization of the implanted layer occurs on subsequent annealing at 1073 K. In the annealed specimens implanted above the lowest fluence three layers along depth with different microstructures were found, which include a shallow polycrystalline porous layer, a deeper single-crystalline layer containing high density of gas bubbles, a well separated deeper layer composed of dislocation loops in low density. With increasing ion fluence the thickness of the porous polycrystalline layer increases. It is indicated that chlorine can suppress the epitaxial re-crystallization of implanted silicon, when the implant fluence of Cl ions exceeds a certain level.

Formation and characterisation of ordered porous vanadium oxide inverse opal materials for Li-ion batteries

This thesis presents several routes towards achieving artificial opal templates by colloidal self-assembly of polystyrene (PS) or poly(methyl methacrylate) (PMMA) spheres and the use of these template for the fabrication of V2O5 inverse opals as cathode materials for lithium ion battery applications. First, through the manipulation of different experimental factors, several methods of affecting or directing opal growth towards realizing different structures, improving order and/or achieving faster formation on a variety of substrates are presented. The addition of the surfactant sodium dodecyl sulphate (SDS) at a concentration above the critical micelle concentration for SDS to a 5 wt% solution of PMMA spheres before dip-coating is presented as a method of achieving ordered 2D PhC monolayers on hydrophobic Au-coated silicon substrates at fast and slow rates of withdrawal. The effect that the degree of hydrophilicity of glass substrates has on the ordering of PMMA spheres is next investigated for a slow rate of withdrawal under noise agitation. Heating of the colloidal solution is also presented as a means of affecting order and thickness of opal deposits formed using fast rate dip coating. E-beam patterned substrates are shown as a means of altering the thermodynamically favoured FCC ordering of polystyrene spheres (PS) when dip coated at slow rate. Facile routes toward the synthesis of ordered V2O5 inverse opals are presented with direct infiltration of polymer sphere templates using liquid precursor. The use of different opal templates, both 2D and 3D partially ordered templates, is compared and the composition and arrangement of the subsequent IO structures post infiltration and calcination for various procedures is characterised. V2O5 IOs are also synthesised by electrodeposition from an aqueous VOSO4 solution at constant voltage. Electrochemical characterisation of these structures as cathode material for Li-ion batteries is assessed in a half cell arrangement for samples deposited on stainless steel foil substrates. Improved rate capabilities are demonstrated for these materials over bulk V2O5, with the improvement attributed to the shorter Li ion diffusion distances and increased electrolyte infiltration provided by the IO structure.

Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.

EFFECT of DIFFERENT SOLID AMOUNTS IN THE PHYSICAL and MICROSCOPICAL PROPERTIES of SiC POROUS CERAMICS

The presence of pores in ceramics is directly related to the chosen forming process. So, in the starch consolidation method, the ceramics show, after burning, pores with morphology similar to that presented by this organic material. on the other hand, the increase in solid load leads up to alterations in dispersion viscosity, increasing the thermal stresses during drying and sintering processes. In order to verify the solid percentage influence in ceramic final properties, samples were prepared with silicon carbide in different compositions using or not starch as binder agent and pore forming element. The characterization of the ceramic pieces was performed by superficial roughness measurements, porosity besides by optical and scanning electron microscopy. The results showed ceramics with SiC and starch presented physical and microscopic properties slightly higher in relation to those with only ceramic powder in their composition. The presence of organic material, agglomerated and foam during the forming were essential for the final properties of the studied samples.

Synthesis and characterization of implants for bone substitutions made of biomedical apatites containing silicon

In the last decades the development of bone substitutes characterized by a superior biomimetism has become of particular interest, owing to the increasing economic and societal impact of the bone diseases. In the present work of research the development of bone substitutes characterized by improved biomimetism, has been faced in a chemical, structural and morphological perspective. From a chemical point of view, it has been developed the synthesis of hydroxyapatite powders, exhibiting multiple ionic substitutions in both cationic and anionic sites, so to simulate the chemical composition of the natural bone. Particular emphasis has been given to the effect of silicon on the chemical-physical and solubility properties of the obtained hydroxyapatites. From a structural point of view, it has been developed the synthesis of ceramic composite materials, based on hydroxyapatite and calcium silicates, employed both as a reinforcing phase, to raise the mechanical strength of the composite compared to hydroxyapatite, and as a bioactive phase, able to increase the bioactivity properties of the whole ceramic. Finally the unique morphological features of the bone were mimicked by taking inspiration by Nature, so that native wood structures were treated in chemical and thermal way to obtain hydroxyapatite porous materials characterized by the same morphology as the native wood. The results obtained in the present work were positive in all the three different areas of investigation, so to cover the three different aspects of biomimetism, chemical, structural and morphological. Anyway, only at the convergence of the three different fields it is possible to find out the best solutions to develop the ideal bone-like scaffold. Thus, the future activity should be devoted to solve the problems at the borderline between the different research lines, which hamper this convergence and in consequence, the achievement of a bone scaffold able to mimic the various aspects exhibited by the bone tissue

Surface growth for molten silicon infiltration into carbon millimeter-sized channels: Lattice–Boltzmann simulations, experiments and models

The process of liquid silicon infiltration is investigated for channels with radii from 0.25 to 0.75 [mm] drilled in compact carbon preforms. The advantage of this setup is that the study of the phenomenon results to be simplified. For comparison purposes, attempts are made in order to work out a framework for evaluating the accuracy of simulations. The approach relies on dimensionless numbers involving the properties of the surface reaction. It turns out that complex hydrodynamic behavior derived from second Newton law can be made consistent with Lattice-Boltzmann simulations. The experiments give clear evidence that the growth of silicon carbide proceeds in two different stages and basic mechanisms are highlighted. Lattice-Boltzmann simulations prove to be an effective tool for the description of the growing phase. Namely, essential experimental constraints can be implemented. As a result, the existing models are useful to gain more insight on the process of reactive infiltration into porous media in the first stage of penetration, i.e. up to pore closure because of surface growth. A way allowing to implement the resistance from chemical reaction in Darcy law is also proposed.

Pitting and porous layer formation on n-InP anodes

Surface pitting occurs when InP electrodes are anodized in KOH electrolytes at concentrations in the range 2 - 5 mol dm-3. The process has been investigated using atomic force microscopy (AFM) and the results correlated with cross-sectional transmission electron microscopy (TEM) and electroanalytical measurements. AFM measurements show that pitting of the surface occurs and the density of pits is observed to increase with time under both potentiodynamic and potentiostatic conditions. This indicates a progressive pit nucleation process and implies that the development of porous domains beneath the surface is also progressive in nature. Evidence for this is seen in plan view TEM images in which individual domains are seen to be at different stages of development. Analysis of the cyclic voltammograms of InP electrodes in 5 mol dm-3 KOH indicates that, above a critical potential for pit formation, the anodic current is predominantly time dependent and there is little differential dependence of the current on potential. Thus, pores continue to grow with time when the potential is high enough to maintain depletion layer breakdown conditions.

Micropolar flow in a porous channel with high mass transfer

Two dimensional flow of a micropolar fluid in a porous channel is investigated. The flow is driven by suction or injection at the channel walls, and the micropolar model due to Eringen is used to describe the working fluid. An extension of Berman's similarity transform is used to reduce the governing equations to a set of non-linear coupled ordinary differential equations. The latter are solved for large mass transfer via a perturbation analysis where the inverse of the cross-flow Reynolds number is used as the perturbing parameter. Complementary numerical solutions for strong injection are also obtained using a quasilinearisation scheme, and good agreement is observed between the solutions obtained from the perturbation analysis and the computations.

Effect of surface conditions on flow of a micropolar fluid driven by a porous stretching sheet

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Note on porous rotating disk flow

We revisit the classical Karman rotating disk problem. A series analysis is used to derive estimates of boundary conditions at the surface. Using these estimates, computed thermal and flow fields for large mass transfer through the disk are readily obtained using a shooting method. The relevance of the problem to practical flows is discussed briefly.