Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon

Deb, S. K., Wilding, M. C., Somayazulu, M., McMillan, P. F. (2001). Pressure-induced amorphization and an amorphous-amorphous transition in densified porous silicon. Nature, 414, 528-530. RAE2008

Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

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.

Artificial opal photonic crystals and inverse opal structures - fundamentals and applications from optics to energy storage

Photonic crystals (PhCs) influence the propagation of light by their periodic variation in dielectric contrast or refractive index. This review outlines the attractive optical qualities inherent to most PhCs namely the presence of full or partial photonic band gaps and the possibilities they present towards the inhibition of spontaneous emission and the localization of light. Colloidal self-assembly of polymer or silica spheres is one of the most favoured and low cost methods for the formation of PhCs as artificial opals. The state of the art in growth methods currently used for colloidal self-assembly are discussed and the use of these structures for the formation of inverse opal architectures is then presented. Inverse opal structures with their porous and interconnected architecture span several technological arenas - optics and optoelectronics, energy storage, communications, sensor and biological applications. This review presents several of these applications and an accessible overview of the physics of photonic crystal optics that may be useful for opal and inverse opal researchers in general, with a particular emphasis on the recent use of these three-dimensional porous structures in electrochemical energy storage technology. Progress towards all-optical integrated circuits may lie with the concepts of the photonic crystal, but the unique optical and structural properties of these materials and the convergence of PhC and energy storage disciplines may facilitate further developments and non-destructive optical analysis capabilities for (electro)chemical processes that occur within a wide variety of materials in energy storage research.

Transesterification of vegetable oils on basic large mesoporous alumina supported alkaline fluorides-Evidences of the nature of the active site and catalytic performances

KF, LiF and CsF/A(2)O(3) catalysts with different loadings from 1 to 20 wt% were prepared using aqueous solutions of the alkaline fluoride compounds by wet impregnation of basic mesoporous MSU-type alumina. The catalysts were activated under At at 400 degrees C for 2 h and monitored by in situ XRD measurements. The catalysts were also characterized using several techniques: N-2 adsorption/desorption isotherms at -196 degrees C, FTIR, DR-UV-vis, CO2-TPD, XRD, Al-27 CP/MAS NMR. These characterizations led to the conclusion that the deposition of alkaline fluorides on the alumina surface generates fluoroaluminates and aluminate species. The process is definitivated at 400 degrees C. The fluorine in these structures is less basic than in the parent fluorides, but the oxygen becomes more basic. The catalysts were tested for the transesterification of fatty esters under different experimental conditions using conventional heating, microwave and Ultrasound irradiation. Recycling experiments showed that these catalysts are stable for a limited number of cycles. (C) 2009 Elsevier Inc. All rights reserved.

Three-Dimensional Analysis of Seepage below and around Hydraulic Structures

This paper investigates the problem of seepage under the floor of hydraulic structures considering the compartment of flow that seeps through the surrounding banks of the canal. A computer program, utilizing a finite-element method and capable of handling three-dimensional (3D) saturated–unsaturated flow problems, was used. Different ratios of canal width/differential head applied on the structure were studied. The results produced from the two-dimensional (2D) analysis were observed to deviate largely from that obtained from 3D analysis of the same problem, despite the fact that the porous medium was isotropic and homogeneous. For example, the exit gradient obtained from 3D analysis was as high as 2.5 times its value obtained from 2D analysis. Uplift force acting upwards on the structure has also increased by about 46% compared with its value obtained from the 2D solution. When the canal width/ differential head ratio was 10 or higher, the 3D results were comparable to the 2D results. It is recommended to construct a core of low permeability soil in the banks of canal to reduce the seepage losses, uplift force, and exit gradient.

Liquid Structure and Dynamics of Aqueous Isopropanol over gamma-Alumina

The liquid structures of thin films of aqueous solutions of 0, 7, 19, 50, and 100 mol % isopropanol above O/Al-terminated gamma-alumina surfaces have been investigated by means of classical molecular dynamics simulations. The structuring effect of the oxide oil the liquid mixtures is strong and heavily dependent on the local structure of the oxide. Two distinct re-ions are found oil the oxide Surface characterized by the degree of coordination of Al atoms. Above octahedral Al atoms, water and isopropanol molecules adsorb via the oxygen atoms to maximize the electrostatic interaction, whereas above tetrahedral Al sites the solvent molecules adsorb via hydrogen atoms with the oxygen atoms away front the surface. More mobility is found in the second layer compared with the first; however, its structure is still influenced significantly by the orientation of molecules in the first adsorbed layer. Qualitatively, the displacement of water from the surface by the adsorption of isopropanol occurs with 2.6 Water molecules lost for every alcohol molecule present based on the effective surface areas of the two species calculated from the pure simulations.

Porous organic-inorganic hybrid aerogels based on Cr3+/Fe3+ and rigid bridging carboxylates

A general method to prepare organic-inorganic hybrid aerogels has been presented. A series of organic-inorganic hybrid aerogels were successfully produced from 3d trivalent transition metals (Cr3+, Fe3+) and bridging carboxylic acids. Gelation of the Cr(III) gels was achieved by heating the precursor solution to temperatures above 80 degrees C, which is in sharp contrast to usual supramolecular gels. Among a range of ligands used, highly porous aerogels could be prepared from rigid carboxylate, e.g. 1,4-benzenedicarboxylate and 1,3,5-benzenetricarboxylate. The porous aerogels can be described as a coherent, rigid spongy network of continuous nanometre-sized particles, which is significantly different from the usual fibrous network of supramolecular gels. The aerogels have tunable porous structures with micro-and mesoporosity depending on their reactant concentrations. Their surface areas, pore volumes, and average pore sizes were analysed by using nitrogen sorption, and the accessibility of the pores to bulky molecules was also evaluated. It represents a strategy to prepare hybrid materials with large porosity utilising structurally simple building blocks as precursors.

Porous organic cages for sulfur hexafluoride separation

A series of porous organic cages is examined for the selective adsorption of sulphur hexafluoride (SF6) over nitrogen. Despite lacking any metal sites, a porous cage, CC3, shows the highest SF6/N2 selectivity reported for any material at ambient temperature and pressure, which translates to real separations in a gas breakthrough column. The SF6 uptake of these materials is considerably higher than would be expected from the static pore structures. The location of SF6 within these materials is elucidated by x-ray crystallography, and it is shown that cooperative diffusion and structural rearrangements in these molecular crystals can rationalize their superior SF6/N2 selectivity.

A Novel Method for Switching and Tuning of PBG Structures

Photonic band-gap (PBG) structures are utilized in microwave components as filters to suppress unwanted signals. In this work, rectangular perforations were created in the ground plane of a microstrip line to construct a PBG structure. A gold-coated alumina substrate was utilized to switch or tune the bandstop characteristics of this structure. It was demonstrated that the bandstop characteristics were switched off from - 35 to - 1 dB at 16 GHz. Tuning of the bandstop edge with a shift of 1.5 GHz was also shown

Crumpet structures: experimental and modelling studies

Crumpets are made by heating fermented batter on a hot plate at around 230°C. The characteristic structure dominated by vertical pores develops rapidly: structure has developed throughout around 75% of the product height within 30s, which is far faster than might be expected from transient heat conduction through the batter. Cooking is complete within around 3 min. Image analysis based on results from X-ray tomography shows that the voidage fraction is approximately constant and that there is continual coalescence between the larger pores throughout the product although there is also a steady level of small bubbles trapped within the solidified batter. We report here experimental studies which shed light on some of the mechanisms responsible for this structure, together with some models of key phenomena.Three aspects are discussed here: the role of gas (carbon dioxide and nitrogen) nuclei in initiating structure development; convective heat transfer inside the developing pores; and the kinetics of setting the batter into an elastic solid structure. It is shown conclusively that the small bubbles of carbon dioxide resulting from the fermentation stage play a crucial role as nuclei for pore development: without these nuclei, the result is not a porous structure, but rather a solid, elastic, inedible, gelatinized product. These nuclei are also responsible for the tiny bubbles which are set in the final product. The nuclei form the source of the dominant pore structure which is largely driven by the, initially explosive, release of water vapour from the batter together with the desorption of dissolved carbon dioxide. It is argued that the rapid evaporation, transport and condensation of steam within the growing pores provides an important mechanism, as in a heat pipe, for rapid heat transfer, and models for this process are developed and tested. The setting of the continuous batter phase is essential for final product quality: studies using differential scanning calorimetry and on the kinetics of change in the visco-elastic properties of the batter suggest that this process is driven by the kinetics of gelatinization. Unlike many thermally driven food processes the rates of heating are such that gelatinization kinetics cannot be neglected. The implications of these results for modelling and for the development of novel structures are discussed.

Specific surface area and structures of aluminas from fibrillar pseudoboehmite

By heating powders of the aluminum monohydroxide fibrillar pseudoboehmite from 200 degrees C to 1400 degrees C several high surface area aluminas are prepared and characterized by X-ray diffraction and electron optical methods. Aqueous sols with pseudoboehmite fibrils of different lengths were dried by two methods: at room temperature and spray-dried. The following aluminas were obtained after treatment of the powders at increasing temperatures and having a range of specific surface areas: gamma-Al(2)O(3) (470 degrees C - 770 degrees C; 179 m(2)/g 497 m(2)/g); delta-Al(2)O(3) (770 degrees C - 930 degrees C; 156 m(2)/g - 230 m(2)/g); theta-Al(2)O(3) (930 degrees C - 1050 degrees C; 11 m(2)/g - 200 m(2)/g); alpha-Al(2)O(3) (1050 degrees C - 1400 degrees C; 2 m(2)/g - 17 m(2)/g). Spray-dried powders, fired at the same temperature than the ground powders, showed higher specific surface areas. The higher surface area alumina have values of the same order of magnitude of the commercial ""ad-cat"" aluminas.

Processing and mechanical properties of porous titanium-niobium shape memory alloy for biomedical applications

Ti-26 at.%Nb (hereafter Ti-26Nb) alloy foams were fabricated by space-holder sintering process. The porous structures of the foams were characterized by scanning electron microscopy (SEM). The mechanical properties of the Ti-26Nb foam samples were investigated using compressive test. Results indicate that mechanical properties of Ti-26Nb foam samples are influenced by foam porosity. The plateau stresses and elastic moduli of the foams under compression decrease with the increase of their porosities. The plateau stresses and elastic moduli are measured to be from 10~200 MPa and 0.4~5.0 GPa for the Ti-26Nb foam samples with porosities ranged from 80~50 %, respectively.

Mechanical properties and bioactive surface modification via alkali-heat treatment of a porous ti-18Nb-4Sn alloy for biomedical applications

A porous Ti–18 at.%Nb–4 at.%Sn (hereafter, Ti–18Nb–4Sn) alloy was prepared by powder metallurgy. The porous structures were examined by scanning electron microscopy and the phase constituents were analysed by X-ray diffraction. Mechanical properties of the porous alloy were investigated using a compressive test. To enhance the bioactivity of the alloy surface, alkali-heat treatment was used to modify the surface. The bioactivity of the pre-treated alloy sample was investigated using a biomimetic process by soaking the sample into simulated body fluid (SBF). Results indicate that the elastic modulus and plateau stress of the porous Ti–18Nb–4Sn alloy decrease with decreasing relative density. The mechanical properties of the porous alloy can be tailored to match those of human bone. After soaking in SBF for 7 days, a hydroxyapatite layer formed on the surface of the pre-treated porous Ti–18Nb–4Sn alloy. The pre-treated porous Ti–18Nb–4Sn alloy therefore has the potential to be a bioactive implant material.

Inverse opal structure of SnO2 and SnO2 : Zn for gas sensing

In the present work, we propose a low cost synthetic sol-gel route that allows to produce high quality oxide nanostructures with inverse opal architecture which, transferred on alumina substrates provided with Pt interdigitated contacts and heater, are tested as gas sensing devices. An opal template of sintered monodisperse polystyrene spheres was filled with alcoholic solutions of metal oxide precursors and transferred on the alumina substrate. The polystyrene template was removed by thermal treatment, leading to the simultaneous sintering of the oxide nanoparticles. Beside SnO₂, a binary oxide well known for gas sensing application, a Zn containing ternary solid solution (SnO₂:Zn, with Zn 10% molar content) was taken into account for sensor preparation. The obtained high quality macro and meso-porous structures, characterized by different techniques, were tested for pollutant (CO, NO₂) and interfering (methanol) gases, showing that very good detection can be reached through the increase of surface area offered by the inverse opal structure and the tailoring of the chemical composition. The electrical characterization performed on the tin dioxide based sensors shows an enhancement of the relative response towards NO₂ at low temperatures in comparison with conventional SnO₂ sensors obtained with sputtering technique. The addition of Zn increases the separation between the operating temperatures for reducing and oxidizing gases and results in a further enhancement of the selectivity to NO₂ detection.