Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.

Role of La0.5Sr0.5COO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O-3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg1/3Nb2/3)O-3-0.3PbTiO(3) (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO2/Si substrates. The films were initially grown at 300 degreesC using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 degreesC to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 degreesC. Films with highest perovskite content were found to form at 820-840 degreesC on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La0.5Sr0.5CoO3 (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 degreesC. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan delta) of 0.035 at a frequency of 1 kHz at room temperature. (C) 2002 Elsevier Science B.V. All rights reserved.

Temperature effect on hydrocarbon-enhanced nitric oxide conversion using a dielectric barrier discharge reactor

Experimental investigations into the effect of temperature on conversion of NO in the presence of hydrocarbons (ethylene, acetylene and n-hexane) are presented. An AC energized dielectric barrier discharge reactor was used as the plasma reactor. The experiments were carried out at different temperatures up to 200 degreesC. The discharge powers were measured at all the temperatures. The discharge power was found to increase with temperature. NO conversion in the presence of ethylene and n-hexane was better than that of acetylene at all temperatures. The addition of acetylene at room temperature showed no better conversion of NO compared to no additive case. While at higher temperatures, it could enhance the conversion of NO. A slight enhancement in NO and NOx removal was observed in the presence of water vapor. (C) 2003 Elsevier Science B.V. All rights reserved.

Optical, electrical and dielectric properties of TiO(2)-SiO(2) films prepared by a cost effective sol-gel process

Titanium dioxide (TiO(2)) and silicon dioxide (SiO(2)) thin films and their mixed films were synthesized by the sol-gel spin coating method using titanium tetra isopropoxide (TTIP) and tetra ethyl ortho silicate (TEOS) as the precursor materials for TiO(2) and SiO(2) respectively. The pure and composite films of TiO(2) and SiO(2) were deposited on glass and silicon substrates. The optical properties were studied for different compositions of TiO(2) and SiO(2) sols and the refractive index and optical band gap energies were estimated. MOS capacitors were fabricated using TiO(2) films on p-silicon (1 0 0) substrates. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were studied and the electrical resistivity and dielectric constant were estimated for the films annealed at 200 degrees C for their possible use in optoelectronic applications. (C) 2011 Elsevier B.V. All rights reserved.

Effect of substrate bias voltage on the structure, electric and dielectric properties of TiO(2) thin films by DC magnetron sputtering

Titanium dioxide (TiO(2)) films have been deposited on glass and p-silicon (1 0 0) substrates by DC magnetron sputtering technique to investigate their structural, electrical and optical properties. The surface composition of the TiO(2) films has been analyzed by X-ray photoelectron spectroscopy. The TiO(2) films formed on unbiased substrates were amorphous. Application of negative bias voltage to the substrate transformed the amorphous TiO(2) into polycrystalline as confirmed by Raman spectroscopic studies. Thin film capacitors with configuration of Al/TiO(2)/p-Si have been fabricated. The leakage current density of unbiased films was 1 x10(-6) A/cm(2) at a gate bias voltage of 1.5 V and it was decreased to 1.41 x 10(-7) A/cm(2) with the increase of substrate bias voltage to -150 V owing to the increase in thickness of interfacial layer of SiO(2). Dielectric properties and AC electrical conductivity of the films were studied at various frequencies for unbiased and biased at -150 V. The capacitance at 1 MHz for unbiased films was 2.42 x 10(-10) F and it increased to 5.8 x 10(-10) F in the films formed at substrate bias voltage of -150 V. Dielectric constant of TiO(2) films were calculated from capacitance-voltage measurements at 1 MHz frequency. The dielectric constant of unbiased films was 6.2 while those formed at -150 V it increased to 19. The optical band gap of the films decreased from 3.50 to 3.42 eV with the increase of substrate bias voltage from 0 to -150 V. (C) 2011 Elsevier B. V. All rights reserved.

Low threshold voltage ZnO thin film transistor with a Zn0.7Mg0.3O gate dielectric for transparent electronics

A highly transparent all ZnO thin film transistor (ZnO-TFT) with a transmittance of above 80% in the visible part of the spectrum, was fabricated by direct current magnetron sputtering, with a bottom gate configuration. The ZnO-TFT with undoped ZnO channel layers deposited on 300 nm Zn0.7Mg0.3O gate dielectric layers attains an on/off ratio of 104 and mobility of 20 cm2/V s. The capacitance-voltage (C−V) characteristics of the ZnO-TFT exhibited a transition from depletion to accumulation with a small hysteresis indicating the presence of oxide traps. The trap density was also computed from the Levinson’s plot. The use of Zn0.7Mg0.3O as a dielectric layer adds additional dimension to its applications. The room temperature processing of the device depicts the possibility of the use of flexible substrates such as polymer substrates. The results provide the realization of transparent electronics for next-generation optoelectronics.

Structural and dielectric behavior of pulsed laser ablated Sr(0.6)Ca(0.4)TiO(3) thin film and asymmetric multilayer of SrTiO(3) and CaTiO(3)

Homogeneous thin films of Sr(0.6)Ca(0.4)TiO(3) (SCT40) and asymmetric multilayer of SrTiO(3) (STO) and CaTiO(3) (CTO) were fabricated on Pt/Ti/SiO(2)/Si substrates by using pulsed laser deposition technique. The electrical behavior of films was observed within a temperature range of 153 K-373 K. A feeble dielectric peak of SCT40 thin film at 273 K is justified as paraelectric to antiferroelectric phase transition. Moreover, the Curie-Weiss temperature, determined from the epsilon'(T) data above the transition temperature is found to be negative. Using Landau theory, the negative Curie-Weiss temperature is interpreted in terms of an antiferroelectric transition. The asymmetric multilayer exhibits a broad dielectric peak at 273 K. and is attributed to interdiffusion at several interfaces of multilayer. The average dielectric constants for homogeneous Sr(0.6)Ca(0.4)TiO(3) films (similar to 650) and asymmetric multilayered films (similar to 350) at room temperature are recognized as a consequence of grain size effect. Small frequency dispersion in the real part of the dielectric constants and relatively low dielectric losses for both cases ensure high quality of the films applicable for next generation integrated devices. (C) 2011 Elsevier B.V. All rights reserved.

Structural, dielectric relaxation and piezoelectric characterization of Sr2+ substituted modified PMS-PZT ceramic

Pyrochlore phase free [Pb0.94Sr0.06] [(Mn1/3Sb2/3)(0.05)(Zr0.53Ti0.47)(0.95)] O-3 ceramics has been synthesized with pure Perovskite phase by semi-wet route using the columbite precursor method. The field dependences of the dielectric response and the conductivity have been measured in a frequency range from 50 Hz to 1 MHz and in a temperature range from 303 K to 773 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency has been performed, assuming a distribution of relaxation times. The scaling behavior of the dielectric loss spectra suggests that the distribution of the relaxation times is temperature independent. The SEM photographs of the sintered specimens present the homogenous structures and well-grown grains with a sharp grain boundary. The material exhibits tetragonal structure. When measured at frequency (100 Hz), the polarization shows a strong field dependence. Different piezoelectric figures of merit (k(p), d(33) and Q(m)) of the material have also been measured obtaining their values as 0.53, 271 pC/N and 1115, respectively, which are even higher than those of pure PZT with morphotropic phase boundary (MPB) composition. Thus the present ceramics have the optimal overall performance and are promising candidates for the various high power piezoelectric applications. (C) 2011 Elsevier B.V. All rights reserved.

Effect of calcium stoichiometry on the dielectric response of CaCu3Ti4O12 ceramics

CaxCu3Ti4O12 (x=0.90, 0.97, 1.0, 1.1 and 1.15) polycrystalline powders with variation in calcium content were prepared via the oxalate precursor route. The structural, morphological and dielectric properties of the ceramics fabricated using these powders were studied using X-ray diffraction, scanning electron microscope along with energy dispersive X-ray analysis, transmission electron microscopy, electron spin resonance (ESR) spectroscopy and impedance analyzer. The X-ray diffraction patterns obtained for the x = 0.97, 1.0 and 1.1 powdered ceramics could be indexed to a body-centered cubic perovskite related structure associated with the space group Im3. The ESR studies confirmed the absence of oxygen vacancies in the ceramics that were prepared using the oxalate precursor route. The dielectric properties of these suggest that the calcium deficient sample (x = 0.97) has a reduced dielectric loss while retaining the high dielectric constant which is of significant industrial relevance. (C) 2012 Elsevier Ltd. All rights reserved.

Dielectric properties of DC reactive magnetron sputtered Al2O3 thin films

Alumina (Al2O3) thin films were sputter deposited over well-cleaned glass and Si < 100 > substrates by DC reactive magnetron sputtering under various oxygen gas pressures and sputtering powers. The composition of the films was analyzed by X-ray photoelectron spectroscopy and an optimal O/Al atomic ratio of 1.59 was obtained at a reactive gas pressure of 0.03 Pa and sputtering power of 70 W. X-ray diffraction results revealed that the films were amorphous until 550 degrees C. The surface morphology of the films was studied using scanning electron microscopy and the as-deposited films were found to be smooth. The topography of the as-deposited and annealed films was analyzed by atomic force microscopy and a progressive increase in the rms roughness of the films from 3.2 nm to 4.53 nm was also observed with increase in the annealing temperature. Al-Al2O3-Al thin film capacitors were then fabricated on glass substrates to study the effect of temperature and frequency on the dielectric property of the films. Temperature coefficient of capacitance. AC conductivity and activation energy were determined and the results are discussed. (C) 2011 Elsevier B.V. All rights reserved.

Dual functional performance of fiber Bragg gratings coated with metals using flash evaporation technique

Metallic and other type of coatings on fiber Bragg grating (FBG) sensors alter their sensitivity with thermal and mechanical stress while protecting the fragile optical fiber in harsh sensing surroundings. The behavior of the coated materials is unique in their response to thermal and mechanical stress depending on the thickness and the mode of coating. The thermal stress during the coating affects the temperature sensitivity of FBG sensors. We have explored the thermal response of FBGs coated with Al and Pb to an average thickness of 80 nm using flash evaporation technique where the FBG sensor is mounted in a region at room temperature in an evacuated chamber having a pressure of 10(6) Torr which will minimize any thermal stress during the coating process. The coating thickness is chosen in the nanometer region with the aim to study thermal behavior of nanocoatings and their effect on FBG sensitivity. The sensitivity of FBGs is evaluated from the wavelengths recorded using an optical sensing interrogator sm 130 (Micron Optics) from room temperature to 300 degrees C both during heating and cooling. It is observed that the sensitivity of the metal coated fibers is better than the reference FBG with no coating for the entire range of temperature. For a coating thickness of 80 nm, Al coated FBG is more sensitive than the one coated with Pb up to 170 degrees C and it reverses at higher temperatures. This point is identified as a reversible phase transition in Pb monolayers as the 2-dimensional aspects of the metal layers are dominant in the nanocoatings of Pb. On cooling, the phase transition reverses and the FBGs return to the original state and for repeated cycles of heating and cooling the same pattern is observed. Thus the FBG functions as a sensor of the phase transitions of the coatings also. (C) 2012 Elsevier Inc. All rights reserved.

Dielectric relaxations above room temperature in DMPU derived polyaniline film

Dielectric measurements carried out on drop casted from solution of emeraldine base form of polyaniline films in the temperature range 30-300 degrees C revealed occurrence of two maxima in the loss tangent as a function of temperature. The activation energies corresponding to these two relaxation processes were found to be similar to 0.5 eV and similar to 1.5 eV. The occurrence of one relaxation peak in the dispersion curve of the imaginary part of the electric modulus suggests the absence of microphase separation in the film. Thermogravimetric analysis and infrared spectroscopic measurements showed that the films retained its integrity up to 300 degrees C. The dielectric relaxation at higher temperatures with large activation energy of 1.5 eV is attributed to increase in the barrier potential due to decrease in the polymer conjugation as a result of wide amplitude motion of the chain segments well above the glass transition temperature. (c) 2012 Elsevier B.V. All rights reserved.

Raman scattering, microstructural and dielectric studies on Ba1-xCaxBi4Ti4O15 ceramics

Polycrystalline powders of Ba1-xCaxBi4Ti4O15 (where x = 0, 0.25, 0.50, 0.75 and 1) were prepared via the conventional solid-state reaction route. X-ray diffraction (XRD) and Raman scattering techniques have been employed to probe into the structural changes on changing x. XRD analyses confirmed the formation of monophasic bismuth layered structure of all the above compositions with an increase in orthorhombic distortion with increase in x. Raman spectra revealed a redshift in A(1g) peak and an increase in the B-2g/B-3g splitting with increasing Ca content. The average grain size was found to increase with increasing x. The temperature of the maximum dielectric constant (T-m) increased linearly with increasing Ca-content whereas the diffuseness of the phase transition was found to decrease with the end member CaBi4Ti4O15 showing a frequency independent sharp phase transition around 1048 K. Ca doping resulted in a decrease in the remnant polarization and an increase in the coercive field. Ba0.75Ca0.25Bi4Ti4O15 ceramics showed an enhanced piezoelectric coefficient d(33) of 15 pC N-1 at room temperature. Low values of dielectric losses and tunability of temperature coefficient of dielectric constant (tau(epsilon)) in the present solid-solution suggest that these compounds can be of potential use in microwave dielectrics at high temperatures. (C) 2012 Elsevier B.V. All rights reserved.

Low dimensional fabrication of giant dielectric CaCu3Ti4O12 through soft e-beam lithography

We report low-dimensional fabrication of technologically important giant dielectric material CaCu3Ti4O12 (CCTO) using soft electron beam lithographic technique. Sol-gel precursor solution of CCTO was prepared using inorganic metal nitrates and Ti-isopropoxide. Employing the prepared precursor solution and e-beam lithographically fabricated resist mask CCTO dots with similar to 200 nm characteristic dimension were fabricated on platinized Si (111) substrate. Phase formation, chemical purity and crystalline nature of fabricated low dimensional structures were investigated with X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and selected area electron diffraction (SAED), respectively. Morphological investigations were carried out with the help of scanning electron microscopy (SEM) and transmission electron microscopy (TEM). This kind of solution based fabrication of patterned low-dimensional high dielectric architectures might get potential significance for cost-effective technological applications. (C) 2012 Elsevier B.V. All rights reserved.

Temperature dependent structural and dielectric investigations of PbZr0.5Ti0.5O3 solid solution at the morphotropic phase boundary

PbZr1-xTixO3 ceramics synthesised by low temperature calcination followed by sintering at 1280 degrees C show a Morphotropic Phase Boundary (MPB) for compositions of x=0.44-0.51. The morphotropic phase boundary is wider for samples with smaller grain sizes due to the synthesis route. A Rietveld analysis is performed on a composition of x=0.5 composition to quantify the phase fractions of the tetragonal and monoclinic phases present in the PZT system. Temperature dependent X-ray diffraction and dielectric studies of PbZr0.5Ti0.5O3 composition demonstrated a phase transformation from monoclinic to tetragonal at 270 degrees C followed by a ferroelectric tetragonal to a paraelectric cubic transition at 370 degrees C. Thus, the poling of these ceramics should be performed below 270 degrees C to benefit from the presence of a monoclinic phase. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.