Thin titanium oxide films deposited by e-beam evaporation with additional rapid thermal oxidation and annealing for ISFET applications

Titanium oxide (TiO(2)) has been extensively applied in the medical area due to its proved biocompatibility with human cells [1]. This work presents the characterization of titanium oxide thin films as a potential dielectric to be applied in ion sensitive field-effect transistors. The films were obtained by rapid thermal oxidation and annealing (at 300, 600, 960 and 1200 degrees C) of thin titanium films of different thicknesses (5 nm, 10 nm and 20 nm) deposited by e-beam evaporation on silicon wafers. These films were analyzed as-deposited and after annealing in forming gas for 25 min by Ellipsometry, Fourier Transform Infrared Spectroscopy (FTIR), Raman Spectroscopy (RAMAN), Atomic Force Microscopy (AFM), Rutherford Backscattering Spectroscopy (RBS) and Ti-K edge X-ray Absorption Near Edge Structure (XANES). Thin film thickness, roughness, surface grain sizes, refractive indexes and oxygen concentration depend on the oxidation and annealing temperature. Structural characterization showed mainly presence of the crystalline rutile phase, however, other oxides such Ti(2)O(3), an interfacial SiO(2) layer between the dielectric and the substrate and the anatase crystalline phase of TiO(2) films were also identified. Electrical characteristics were obtained by means of I-V and C-V measured curves of Al/Si/TiO(x)/Al capacitors. These curves showed that the films had high dielectric constants between 12 and 33, interface charge density of about 10(10)/cm(2) and leakage current density between 1 and 10(-4) A/cm(2). Field-effect transistors were fabricated in order to analyze I(D) x V(DS) and log I(D) x Bias curves. Early voltage value of -1629 V, R(OUT) value of 215 M Omega and slope of 100 mV/dec were determined for the 20 nm TiO(x) film thermally treated at 960 degrees C. (C) 2009 Elsevier B.V. All rights reserved.

Role of the crystallite phase of TiO2 in heterogeneous photocatalysis for phenol oxidation in water

A series of TiO2 samples with different anatase-to-rutile ratios was prepared by calcination, and the roles of the two crystallite phases of titanium(IV) oxide (TiO2) on the photocatalytic activity in oxidation of phenol in aqueous solution were studied. High dispersion of nanometer-sized anatase in the silica matrix and the possible bonding of Si-O-Ti in SiO2/TiO2 interface were found to stabilize the crystallite transformation from anatase to rutile. The temperature for this transformation was 1200 degrees C for the silica-titania (ST) sample, much higher than 700 degrees C for Degussa P25, a benchmarking photocatalyst. It is shown that samples with higher anatase-to-rutile ratios have higher activities for phenol degradation. However, the activity did not totally disappear after a complete crystallite transformation for P25 samples, indicating some activity of the rutile phase. Furthermore, the activity for the ST samples after calcination decreased significantly, even though the amount of anatase did not change much. The activity of the same samples with different anatase-to-rutile ratios is more related to the amount of the surface-adsorbed water and hydroxyl groups and surface area. The formation of rutile by calcination would reduce the surface-adsorbed water and hydroxyl groups and surface area, leading to the decrease in activity.

Semisolid casting of AlSi7Mg0.35 alloy produced by low-temperature pouring

AlSi7Mg0.35 alloy was cast into permanent moulds using different pouring temperatures (725 to 625degreesC). As the pouring temperature decreased, the as-cast microstructure changed from a coarse dendritic structure, through fine equiaxed grains to fine rosette-like grains. The as-cast materials were then partially remelted and isothermally held at 580degreesC prior to semisolid casting into a stepped die. The feedstock material cast from a high temperature filled only half the die, with severe segregation and other defects. The low-temperature-poured material completely filled the die with negligible porosity. The quality of semisolid castings is significantly affected by the microstructure of the semisolid feedstock material that arises from a combination of as-cast and subsequent thermal treatment conditions. The paper describes (a) the influence of pouring temperature on the microstructure of feedstock; (b) microstructure evolution through remelting and (c) the quality of semisolid castings produced with this material. For A17Si0.35Mg alloy, low temperature pouring in the range of 625-650degreesC followed by suitable isothermal holding treatment can result in good quality semisolid casting.

Transmission electron microscopy of a transformation toughened white cast iron

Transmission electron microscopy has been used to study the microstructure of an experimental white cast iran, in which a combination of modified alloy composition and unconventional heat treatment has resulted in a fracture toughness of 40 MPa m(-1/2). Microstructural features of the alloy that contribute to the toughness improvement and hence distinguish it from conventional white irons have been investigated. In the as-cast condition the dendrites are fully austenitic and the eutectic consists of M7C3 carbides and martensite. During heat treatment at 1130 degrees C the austenite is partially destabilized by precipitation of chromium-rich M7C3 carbides. This results in a dendritic microconstituent consisting of bulk retained austenite and secondary carbides which are sheathed with martensite. The martensite sheaths, which contain interlath films of retained austenite, are irregular in shape with some laths extending into the bulk retained austenite. Emphasis has been placed on the morphology, distribution, and stability of the retained austenite and its transformation products in the dendrites. The implications of these findings on the transformation toughening mechanism in this alloy are discussed.

Effect of processing induced particle alignment on the fracture toughness and fracture behavior of multiphase dental ceramics

Objective. To investigate the processing induced particle alignment on fracture behavior of four multiphase dental ceramics (one porcelain, two glass-ceramics and a glass-infiltrated-alumina composite). Methods. Disks (empty set12mm x 1.1 mm-thick) and bars (3 mm x 4 mm x 20 mm) of each material were processed according to manufacturer instructions, machined and polished. Fracture toughness (K(IC)) was determined by the indentation strength method using 3-point bending and biaxial flexure fixtures for the fracture of bars and disks, respectively. Microstructural and fractographic analyses were performed with scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction. Results. The isotropic microstructure of the porcelain and the leucite-based glass-ceramic resulted in similar fracture toughness values regardless of the specimen geometry. On the other hand, materials containing second-phase particles with high aspect ratio (lithium disilicate glass-ceramic and glass-infiltrated-alumina composite) showed lower fracture toughness for disk specimens compared to bars. For the lithium disilicate glass-ceramic disks, it was demonstrated that the occurrence of particle alignment during the heat-pressing procedure resulted in an unfavorable pattern that created weak microstructural paths during the biaxial test. For the glass-infiltrated-alumina composite, the microstructural analysis showed that the large alumina platelets tended to align their large surfaces perpendicularly to the direction of particle deposition during slip casting of green preforms. Significance. The fracture toughness of dental ceramics with anisotropic microstructure should be determined by means of biaxial testing, since it results in lower values. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of curing protocol on selected properties of light-curing polymers: Degree of conversion, volume contraction, elastic modulus, and glass transition temperature

Objectives. The purpose of this study was to investigate the effect of light-curing protocol on degree of conversion (DC), volume contraction (C), elastic modulus (E), and glass transition temperature (T(g)) as measured on a model polymer. It was a further aim to correlate the measured values with each other. Methods. Different light-curing protocols were used in order to investigate the influence of energy density (ED), power density (PD), and mode of cure on the properties. The modes of cure were continuous, pulse-delay, and stepped irradiation. DC was measured by Raman micro-spectroscopy. C was determined by pycnometry and a density column. E was measured by a dynamic mechanical analyzer (DMA), and T(g) was measured by differential scanning calorimetry (DSC). Data were submitted to two-and three-way ANOVA, and linear regression analyses. Results. ED, PD, and mode of cure influenced DC, C, E, and T(g) of the polymer. A significant positive correlation was found between ED and DC (r = 0.58), ED and E (r = 0.51), and ED and T(g) (r = 0.44). Taken together, ED and PD were significantly related to DC and E. The regression coefficient was positive for ED and negative for PD. Significant positive correlations were detected between DC and C (r = 0.54), DC and E (r = 0.61), and DC and T(g) (r = 0.53). Comparisons between continuous and pulse-delay modes of cure showed significant influence of mode of cure: pulse-delay curing resulted in decreased DC, decreased C, and decreased T(g). Influence of mode of cure, when comparing continuous and step modes of cure, was more ambiguous. A complex relationship exists between curing protocol, microstructure of the resin and the investigated properties. The overall performance of a composite is thus indirectly affected by the curing protocol adopted, and the desired reduction of C may be in fact a consequence of the decrease in DC. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Protective effect of different tetrafluorides on erosion of pellicle-free and pellicle-covered enamel and dentine

The aim was to analyze the protective effects of titanium, zirconium and hafnium tetrafluorides on erosion of pellicle-free and pellicle-covered enamel and dentine in vitro. Eight groups of 20 specimens each of bovine enamel and bovine dentine were prepared. Half the specimens in each group were immersed in human saliva for 2 h for pellicle formation. Specimens were then left untreated (controls) or were treated for 120 s with TiF(4), ZrF(4) or HfF(4) solutions (0.4 or 1%) or 1.25% AmF/NaF gel. All specimens were eroded by exposure to hydrochloric acid, pH 2.6, for 25 min. Cumulative calcium release into the acid was monitored in consecutive 30-second intervals for 5 min, then at 2-min intervals up to a total erosion time of 25 min using the Arsenazo III procedure. Data were analyzed by ANOVA. 1% TiF(4) solution offered the best protective effect, especially in dentine (reduction of calcium loss about 50% at 25 min). 1% ZrF 4, 1% HfF 4 and 0.4% TiF(4) also reduced calcium loss, but to a lesser extent. Long-term effects were limited to dentine, while reduction of enamel erosion (about 25%) was restricted to 1-min erosion. The fluoride gel had a protective effect only in dentine. The efficacy of the tetrafluorides was influenced by the presence of the pellicle layer, in that the protection against dentine erosion by TiF(4) and ZrF(4) was greater on pellicle-covered specimens. Tetrafluoride solutions, especially 1% TiF(4), could decrease dental erosion, but were more effective on dentine than on enamel. Copyright (C) 2008 S. Karger AG, Basel.

Thermal characterization of copolymers obtained by radiation grafting of styrene onto poly(tetrafluoroethyleneperfluoropropylvinylether) substrates: thermal decomposition, melting behavior and low-temperature transitions

Differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA) have been used to study the thermal decomposition, the melting behavior and low-temperature transitions of copolymers obtained by radiation-induced grafting of styrene onto poly (tetrafluoroethylene- perfluoropropylvinylether) (PFA) substrates. PFA with different contents of perfluoropropylvinylether (PPVE) as a comonomer have been investigated. A two step degradation pattern was observed from TGA thermograms of all the grafted copolymers, which was attributed to degradation of PSTY followed by the degradation of the PFA backbone at higher temperature. One broad melting peak can be identified for all copolymers, which has two components in the samples with higher PPVE content. The melting peak, crystal-crystal transition and the degree of crystallinity of the grafted copolymers increases with radiation grafting up to 50 kGy, followed by a decrease at higher doses. No such decrease was observed in the ungrafted PFA samples after irradiation. This indicated that the changes in the heats of transitions and crystallinity at low doses are due to the radiation effects on the microstructure of PFA (chain scission), whereas at higher doses the grafted PSTY is the driving force behind these changes. (C) 2001 Elsevier Science Ltd. All rights reserved.

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO2) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO2 based oxides. In addition, the true microstructure of doped CeO2 was observed at atomic scale for conclusion of conduction mechanism. Doped CeO2 had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO2 electrolyte.

The essential work of fracture through the wall of uPVC pipe

The specific essential work of fracture, w(e), has been measured for a relatively thick walled uPVC pipe as a function of position through the wall of the pipe. w(e) was highest at the surface of the pipe and decreased significantly at the centre of the pipe wall. The variation in w(e) through the wall of the pipe correlated with the processing level of the uPVC material as measured by the critical temperature, T-c. The variability in the measured values of w(e) was substantially higher in the centre of the pipe where the processing levels were lower. This was likely to be a result of the variability in the microstructure of the material where poor processing had introduced regions of poor fusion of primary PVC particles. (C) 2002 Kluwer Academic Publishers.

Columnar to equiaxed transition of eutectic in hypoeutectic aluminium-silicon alloys

Directional solidification of unmodified and strontium modified binary, high-purity aluminium-7 wt% silicon and commercial A356 alloys has been carried out to investigate the mechanism of eutectic solidification. The microstructure of the eutectic growth inter-face was investigated with optical microscopy and Electron Backscattering Diffraction (EBSD). In the commercial alloys, the eutectic solidification inter-face extends in the growth direction and creates a eutectic mushy zone. A planar eutectic growth front is observed in the high-purity alloys. The eutectic aluminium has mainly the same crystallographic orientation as the dendrites in the unmodified alloys and the strontium modified high-purity alloy. A more complex eutectic grain structure is found in the strontium modified commercial alloy. A mechanism involving constitutional undercooling and a columnar to equiaxed transition explains the differences between pure and commercial alloys. It is probably caused by the segregation of iron and magnesium and the activation of nucleants in the commercial alloy. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Close packed transitions in slit-shaped pores: Density functional theory study of methane adsorption capacity in carbon

An important feature of improving lattice gas models and classical isotherms is the incorporation of a pore size dependent capacity, which has hitherto been overlooked. In this paper, we develop a model for predicting the temperature dependent variation in capacity with pore size. The model is based on the analysis of a lattice gas model using a density functional theory approach at the close packed limit. Fluid-fluid and solid-fluid interactions are modeled by the Lennard-Jones 12-6 potential and Steele's 10-4-3, potential respectively. The capacity of methane in a slit-shaped carbon pore is calculated from the characteristic parameters of the unit cell, which are extracted by minimizing the grand potential of the unit cell. The capacities predicted by the proposed model are in good agreement with those obtained from grand canonical Monte Carlo simulation, for pores that can accommodate up to three adsorbed layers. Single particle and pair distributions exhibit characteristic features that correspond to the sequence of buckling and rhombic transitions that occur as the slit pore width is increased. The model provides a useful tool to model continuous variation in the microstructure of an adsorbed phase, namely buckling and rhombic transitions, with increasing pore width. (C) 2002 American Institute of Physics.

Novel composites of TiO2 (anatase) and silicate nanoparticles

Thermally stable composite nanostructures of titanium dioxide (anatase) and silicate nanoparticles were prepared from Laponite clay and a sol of titanium hydrate in the presence of poly(ethylene oxide) (PEO) surfactants. Laponite is a synthetic clay that readily disperses in water and exists as exfoliated silicate layers of about 1-nm thick in transparent dispersions of high pH. The acidic sol solution reacts with the clay platelets and leaches out most of the magnesium in the clay, while the sol particles hydrolyze further due to the high pH of the clay dispersion. As a result, larger precursors of TiO2 nanoparticles form and condense on the fragmentized pieces of the leached silicate. Introducing PEO surfactants into the synthesis can significantly increase the porosity and surface area of the composite solids. The TiO2 exists as anatase nanoparticles that are separated by silicate fragments and voids such that they are accessible to organic molecules. The size of the anatase particle can be tailored by manipulating the experimental parameters at various synthesis stages. Therefore, we can design and engineer composite nanostructures to achieve better performance. The composite solids exhibit superior properties as photocatalysts for the degradation of Rhodamine 6G in aqueous solution.

Effect of fiber alignment in gelled electrospun membranes based on poly(vinylidene fluoride) for battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of 272 nm and a degree of porosity of 87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.

Effect of fiber orientation in gelled poly (vinylience fluoride) electrospun membranes for Li-ion battery applications

Battery separators based on electrospun membranes of poly(vinylidene fluoride) (PVDF) have been prepared in order to study the effect of fiber alignment on the performance and characteristics of the membrane. The prepared membranes show an average fiber diameter of ~272 nm and a degree of porosity of ~87 %. The gel polymer electrolytes are prepared by soaking the membranes in the electrolyte solution. The alignment of the fibers improves the mechanical properties for the electrospun membranes. Further, the microstructure of the membrane also plays an important role in the ionic conductivity, being higher for the random electrospun membrane due to the lower tortuosity value. Independently of the microstructure, both membranes show good electrochemical stability up to 5.0 V versus Li/Li+. These results show that electrospun membranes based on PVDF are appropriate for battery separators in lithium-ion battery applications, the random membranes showing a better overall performance.