Use of room temperature ionic liquids in gas sensor design

The attainable steady-state limiting currents and time responses of membrane-covered and membrane-independent gas sensors incorporating different electrode and electrolyte materials have been compared. A new design comprising a membrane-free microelectrode modified with a thin layer of a room temperature ionic liquid is considered. While the use of ionic liquid as electrolyte eliminates the need for a membrane and added supporting electrolyte, the slower diffusion of analyte within the more viscous medium results in slower time responses. Such sensors do, however, have potential application in more extreme operating conditions, such as high temperature and pressure, where traditional solvents would volatise.

Temperature Dependence of the Primary Relaxation in 1-Hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide

We present results from complementary characterizations of the primary relaxation rate of a room temperature ionic liquid (RTIL), 1-hexyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl} imide, [C(6)mim][Tf2N], over a wide temperature range. This extensive data set is successfully merged with existing literature data for conductivity, viscosity, and NMR diffusion coefficients thus providing, for the case of RTILs, a unique description of the primary process relaxation map over more than 12 decades in relaxation rate and between 185 and 430 K. This unique data set allows a detailed characterization of the VTF parameters for the primary process, that are: B = 890 K, T-0 = 155.2 K, leading to a fragility index m = 71, corresponding to an intermediate fragility. For the first time neutron spin echo data from a fully deuteriated sample of RTIL at the two main interference peaks, Q = 0.76 and 1.4 angstrom(-1) are presented. At high temperature (T > 250 K), the collective structural relaxation rate follows the viscosity behavior; however at lower temperatures it deviates from the viscosity behavior, indicating the existence of a faster process.

Novel low-temperature photocatalytic titania films produced by plasma-assisted reactive dc magnetron sputtering

Robust, active, anatase titania films, 250 nm thick, are deposited onto glass at low temperatures, i.e., 2.0 for the photocatalytic mineralization of stearic acid. These films are typically 6.9 times more active than a sample of commercial self-cleaning glass, comprising a 15 nm layer of fitania deposited by CVD, mainly because they are much thicker and, therefore, absorb more of the incident UV light. The most active of the films tested comprised particles of P25, but lacked any significant physical robustness. Similar results, but much more quickly obtained, were generated using a photocatalyst- sensitive ink, based on the redox dye, resazurin, Rz. All fitania films tested, including those produced by magnetrom sputtering exhibited photo-induced superhydrophilicity. The possible future application of PAR-DG-MS for producing very active photocatalytic films on substrates not renowned for their high temperature stabilities, such as plastics, is noted. (c) 2006 Elsevier B.V All rights reserved.

A two-tier model of polymyxin B resistance in Burkholderia cenocepacia

P>Burkholderia cenocepacia is an environmental bacterium causing serious human opportunistic infections and is extremely resistant to multiple antibiotics including antimicrobial peptides, such as polymyxin B (PmB). Extreme antibiotic resistance is attributed to outer membrane impermeability ('intrinsic' resistance). Previous work showed that production of full-length lipopolysaccharide (LPS) prevents surface binding of PmB. We hypothesized that two tiers of resistance mechanisms rendering different thresholds of PmB resistance exist in B. cenocepacia. To test this notion, candidate genes were mutated in two isogenic strains expressing full-length LPS or truncated LPS devoid of heptose ('heptoseless LPS') respectively. We uncovered various proteins required for PmB resistance only in the strain with heptoseless LPS. These proteins are not involved in preventing PmB binding to whole cells or permeabilization of the outer membrane. Our results support a two-tier model of PmB resistance in B. cenocepacia. One tier sets a very high threshold mediated by the LPS and the outer membrane permeability barrier. The second tier sets a lower threshold that may play a role in PmB resistance only when outer membrane permeability is compromised. This model may be of general applicability to understanding the high antimicrobial peptide resistance of environmental opportunistic pathogens.

Comments and Additional Work on “High-Pressure Volumetric Properties of Imidazolium-Based Ionic Liquids: Effect of the Anion”

This works follows a publication of our group in J. Chem. Eng. Data2007, 52, 2204–2211 presenting high temperature and pressure density data for five imidazolium-based ionic liquids. At this period, very few ionic liquid density data were available in the literature, especially at high pressure, and the uncertainty of published results was calculated with respect to the literature data available for three of the five ionic liquids studied. Since 2007, the ionic liquid density databank has largely increased. In this work, a comparison of our published data in J. Chem. Eng. Data2007, 52, 2204–2211, with more than 1800 high pressure data coming from the literature up to December 2011 is presented to assess the uncertainty of our published values. The claimed uncertainty is close to 0.31 % for all IL density data sets except in the case of the [C1C2Im][EtSO4], where the uncertainty is up to 1.1 %. Reported data in J. Chem. Eng. Data2007, 52, 2204–2211, for this particular ionic liquid cannot be used as a reference. For this ionic liquid, new density measurements of the same sample batch have been remeasured by using the same experimental technique, and new experimental data presented herein are clearly higher than our previous published results. A 1H NMR analysis of the sample has confirmed hydrolysis of the ethylsulfate anion to ethanol and hydrogenate anion which explains the differences observed between our density data and the literature.

A Lead-Free and High-Energy Density Ceramic for Energy Storage Applications

In this work, we demonstrate a very high-energy density and high-temperature stability capacitor based on SrTiO3-substituted BiFeO3 thin films. An energy density of 18.6 J/cm3 at 972 kV/cm is reported. The temperature coefficient of capacitance (TCC) was below 11% from room temperature up to 200°C. These results are of practical importance, because it puts forward a promising novel and environmentally friendly, lead-free material, for high-temperature applications in power electronics up to 200°C. Applications include capacitors for low carbon vehicles, renewable energy technologies, integrated circuits, and for the high-temperature aerospace sector. © 2013 Crown copyright

A theoretical assessment of surface defect machining and hot machining of nanocrystalline silicon carbide

In this paper, a newly proposed machining method named “surface defect machining” (SDM) [Wear, 302, 2013 (1124-1135)] was explored for machining of nanocrystalline beta silicon carbide (3C-SiC) at 300K using MD simulation. The results were compared with isothermal high temperature machining at 1200K under the same machining parameters, emulating ductile mode micro laser assisted machining (µ-LAM) and with conventional cutting at 300 K. In the MD simulation, surface defects were generated on the top of the (010) surface of the 3C-SiC work piece prior to cutting, and the workpiece was then cut along the <100> direction using a single point diamond tool at a cutting speed of 10 m/sec. Cutting forces, sub-surface deformation layer depth, temperature in the shear zone, shear plane angle and friction coefficient were used to characterize the response of the workpiece. Simulation results showed that SDM provides a unique advantage of decreased shear plane angle which eases the shearing action. This in turn causes an increased value of average coefficient of friction in contrast to the isothermal cutting (carried at 1200 K) and normal cutting (carried at 300K). The increase of friction coefficient however was found to aid the cutting action of the tool due to an intermittent dropping in the cutting forces, lowering stresses on the cutting tool and reducing operational temperature. Analysis shows that the introduction of surface defects prior to conventional machining can be a viable choice for machining a wide range of ceramics, hard steels and composites compared to hot machining.

Studies of the Room-Temperature Multiferroic Pb(Fe0.5Ta0.5)0.4(Zr0.53Ti0.47)0.6O3: Resonant Ultrasound Spectroscopy, Dielectric, and Magnetic Phenomena

Recently, lead iron tantalate/lead zirconium titanate (PZTFT) was demonstrated to possess large, but unreliable, magnetoelectric coupling at room temperature. Such large coupling would be desirable for device applications but reproducibility would also be critical. To better understand the coupling, the properties of all 3 ferroic order parameters, elastic, electric, and magnetic, believed to be present in the material across a range of temperatures, are investigated. In high temperature elastic data, an anomaly is observed at the orthorhombic mm2 to tetragonal 4mm transition, Tot = 475 K, and a softening trend is observed as the temperature is increased toward 1300 K, where the material is known to become cubic. Thermal degradation makes it impos- sible to measure elastic behavior up to this temperature, however. In the low temperature region, there are elastic anomalies near ≈40 K and in the range 160–245 K. The former is interpreted as being due to a magnetic ordering transition and the latter is interpreted as a hysteretic regime of mixed rhom- bohedral and orthorhombic structures. Electrical and magnetic data collected below room temperature show anomalies at remarkably similar temperature ranges to the elastic data. These observations are used to suggest that the three order parameters in PZTFT are strongly coupled.

Processing, microstructure and mechanical properties of air plasma-sprayed ceria-yttria co-stabilized zirconia coatings

Thermal barrier coatings (TBCs) are widely adopted to protect mechanical components in gas turbine engines operating at high temperature. Basically, the surface temperature of these components must be low enough to retain material properties within acceptable bounds and to extend component life. From this standpoint, air plasma-sprayed (APS) ceria and yttria co-stabilized zirconia (CYSZ) is particularly promising because it provides enhanced thermal insulation capabilities and resistance to hot corrosion. However, essential mechanical properties, such as hardness and Young's modulus, have been less thoroughly investigated. Knowledge of Young's modulus is of concern because it has a significant effect on strain tolerance and stress level and, hence, on durability. The focus of the present study was to determine the mechanical properties of APS CYSZ coatings. In particular, X-ray diffraction (XRD) is adopted for phase analysis of powders and as-sprayed coatings. In addition, scanning electron microscopy (SEM) and image analysis (IA) are employed to explore coating microstructure and porosity. Finally, the Young's modulus of the coating is determined using nanoindentation and a resonant method. The results obtained are then discussed and a cross-check on their consistency is carried out by resorting to a micromechanical model. © 2010 Blackwell Publishing Ltd.

Temperature dependence of the mid-infrared dielectric function of YBCO in the ab plane

We have excited mid-infrared surface plasmons in two YBCO thin films of contrasting properties using attenuated total reflection of light and found that the imaginary part of the dielectric function decreases linearly with reduction in temperature. This result is in contrast with the commonly reported conclusion of infrared normal reflectance studies. If sustained it may clarify the problem of understanding the normal state properties of YBCO and the other cuprates. The dielectric function of the films, epsilon = epsilon(1) + i epsilon(2), was determined between room temperature and 80K: epsilon(1) was found to be only slightly temperature dependent but somewhat sample dependent, probably as a result of surface and grain boundary contamination. The imaginary part, epsilon(2), (and the real part of the conductivity, sigma(1),) decreased linearly with reduction in temperature in both films. Results obtained were: for film 1: epsilon(1) = - 14.05 - 0.0024T and epsilon(2) - 4.11 + 0.086T and for film 2: epsilon(1) = - 24.09 + 0.0013T and epsilon(2) = 7.66 + 0.067T where T is the temperature in Kelvin. An understanding of the results is offered in terms of temperature-dependent intrinsic intragrain inelastic scattering and temperature-independent contributions: elastic and inelastic grain boundary scattering and optical interband (or localised charge) absorption. The relative contribution of each is estimated. A key conclusion is that the interband (or localised charge) absorption is only similar to 10%. Most importantly, the intrinsic scattering rate, 1/tau, decreases linearly with fall in temperature, T, in a regime where current theory predicts dependence on frequency, omega, to dominate. The coupling constant, lambda, between the charge carriers and the thermal excitations has a value of 1.7, some fivefold greater than the far infrared value. These results imply a need to restate the phenomenology of the normal state of high temperature superconductors and seek a corresponding theoretical understanding.

Effect of shotpeening on sliding wear and tensile behavior of titanium implant alloys

Titanium has good biocompatibility and so its alloys are used as implant materials, but they suffer from having poor wear resistance. This research aims to improve the wear resistance and the tensile strength of titanium alloys potentially for implant applications. Titanium alloys Ti–6Al–4V and Ti–6Al–7Nb were subjected to shotpeening process to study the wear and tensile behavior. An improvement in the wear resistance has been achieved due to surface hardening of these alloys by the process of shotpeening. Surface microhardness of shotpeened Ti–6Al–4V and Ti–6Al–7Nb alloys has increased by 113 and 58 HV(0.5), respectively. After shotpeening, ultimate tensile strength of Ti–6Al–4V increased from 1000 MPa to 1150 MPa, higher than improvement obtained for heat treated titanium specimens. The results confirm that shotpeening pre-treatment improved tensile and sliding wear behavior of Ti–6Al–4V and Ti–6Al–7Nb alloys. In addition, shotpeening increased surface roughness.

Micro-scale wear characteristics of electroless Ni-P/SiC composite coating under two different sliding conditions

The electroless nickel composite (ENC) with various silicon carbide contents was deposited onto aluminium alloy (LM24) substrate. The wear behaviour and the microhardness of the composite coating samples were investigated and compared with particles free and aluminium substrate samples using micro-scale abrasion tester and microhardness tester respectively. The wear scar marks and wear volume were analysed by optical microscope. The wear tracks were further studied using scanning electron microscopy (SEM). The embedded particles were found to get pressed into the matrix which helps resisting further wearing process for composite samples. However, random orientation of microcuts and microfallow were seen for ENC sample but more uniform wearing was observed for EN sample. The composite coating with low content of SiC was worn minimum. Early penetration into the substrate was seen for samples with higher SiC content. Microhardness was improved after heat treatment for all the samples containing various SiC content. Under dry sliding condition, inclusion of particles in the matrix did not improve the wearing resistance performance in as-deposited state. The wearing worsened as the content of the particles increased generally. However, on heat treatment, the composite coatings exhibited improved wear resistance and the best result was obtained from the one with low particle contents.

Physicochemical Investigation of Adiponitrile-Based Electrolytes for Electrical Double Layer Capacitor