Local electronic and electrical properties of functionalized graphene nano flakes

Based on experimental findings models of amorphous graphene related carbon materials were generated using graphene nano flakes. On the optimized structures detailed local electronic properties were investigated using density functional theory. The electrical conductivities of all these models were also estimated using an in-house program based on tight-binding method. The calculated electrical conductivity values of all the models agreed well with the trend of calculated energy gap and graphitic character.     

RF-PACVD of water repellent and protective HMDSO coatings on bell metal surfaces: Correlation between discharge parameters and film properties

Hexamethyldisiloxane (HMDSO) films have been deposited on bell metal using radiofrequency plasma assisted chemical vapor deposition (RF-PACVD) technique. The protective performances of the HMDSO films and their water repellency have been investigated as a function of DC self-bias voltage on the substrates during deposition. Plasma potential measurements during film deposition process are carried out by self-compensated emissive probe. Optical emission spectroscopy (OES) analyses of the plasma during deposition reveal no significant change in the plasma composition within the DC self-bias voltage range of −40 V to −160 V that is used. Raman and X-ray photoelectron spectroscopy (XPS) studies are carried out for film chemistry analysis and indicate that the impinging ion energy on the substrates influences the physio-chemical properties of the HMDSO films. At critical ion energy of 113 qV (corresponding to DC self-bias voltage of −100 V), the deposited HMDSO film exhibits least defective Si-O-Si chemical structure and highest inorganic character and this contributes to its best corrosion resistance behavior. The hardness and elastic modulus of the films are found to be bias dependent and are 1.27 GPa and 5.36 GPa for films deposited at −100 V. The critical load for delamination is also bias dependent and is 11 mN for this film. The water repellency of the HMDSO films is observed to be dependent on the variation in surface roughness. The results of the investigations suggest that HMDSO films deposited by RF-PACVD can be used as protective coatings on bell metal surfaces.     

Oxidative addition of different electrophiles with rhodium(I) carbonyl complexes of unsymmetrical phosphine–phosphine monoselenide ligands

Dimeric chlorobridge complex [Rh(CO)₂Cl]₂ reacts with two equivalents of a series of unsymmetrical phosphine–phosphine monoselenide ligands, Ph₂P(CH₂)_nP(Se)Ph₂ {n = 1( a ), 2( b ), 3( c ), 4( d )}to form chelate complex [Rh(CO)Cl(P∩Se)] ( 1a ) {P∩Se = η²‐(P,Se) coordinated} and non‐chelate complexes [Rh(CO)₂Cl(P～Se)] ( 1b–d ) {P～Se = η¹‐(P) coordinated}. The complexes 1 undergo oxidative addition reactions with different electrophiles such as CH₃I, C₂H₅I, C₆H₅CH₂Cl and I₂ to produce Rh(III) complexes of the type [Rh(COR)ClX(P∩Se)] {where R = ? C₂H₅ ( 2a ), X = I; R = ? CH₂C₆H₅ ( 3a ), X = Cl}, [Rh(CO)ClI₂(P∩Se)] ( 4a ), [Rh(CO)(COCH₃)ClI(P～Se)] ( 5b–d ), [Rh(CO)(COH₅)ClI‐(P～Se)] ( 6b–d ), [Rh(CO)(COCH₂C₆H₅)Cl₂(P～Se)] ( 7b–d ) and [Rh(CO)ClI₂(P～Se)] ( 8b–d ). The kinetic study of the oxidative addition (OA) reactions of the complexes 1 with CH₃I and C₂H₅I reveals a single stage kinetics. The rate of OA of the complexes varies with the length of the ligand backbone and follows the order 1a > 1b > 1c > 1d . The CH₃I reacts with the different complexes at a rate 10–100 times faster than the C₂H₅I. The catalytic activity of complexes 1b–d for carbonylation of methanol is evaluated and a higher turnover number (TON) is obtained compared with that of the well‐known commercial species [Rh(CO)₂I₂]^?. Copyright © 2006 John Wiley & Sons, Ltd.     

Environmental risk modelling under probability-normal interval-valued fuzzy number

In almost all the realistic circumstances, such as health risk assessment and uncertainty analysis of atmospheric dispersion, it is very essential to include all the information into modelling. The parameters associated to a particular model may include different kind of variability, imprecision and uncertainty. More often, it is seen that available informations are interpreted in probabilistic sense. Probability theory is a well-established theory to measure such kind of variability. However, not all of available information, data or model parameters affected by variability, imprecision and uncertainty can be handled by traditional probability theory. Uncertainty or imprecision may occur due to incomplete information or data, measurement errors or data obtained from expert judgement or subjective interpretation of available data or information. Thus, model parameters, data may be affected by subjective uncertainty. Traditional probability theory is inappropriate to represent them. Possibility theory and fuzzy set theory is another branch of mathematics which is used as a tool to describe the parameters with insufficient or vague knowledge. In this paper, an attempt has been made to combine probability knowledge and possibility knowledge and draw the uncertainty. The paper describes an algorithm for combining probability distribution and interval-valued fuzzy number and applied to environmental risk modelling with a case study. The primary aim of this paper is to propagate the proposed method. Computer codes are prepared for the proposed method using MATLAB.     

Enhanced gas-sensing behaviour of Ru-doped SnO2 surface: A periodic density functional approach

A theoretical study on Ru-doped rutile SnO₂(1 1 0) surface has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA-RPBE) level with a periodic supercell approach. Electronic structure analysis was performed based on the band structure and partial density of states. The results provide evidence that the electronic structures of SnO₂(1 1 0) surface are modified by the surface Ru dopant, in which Ru 4d orbital are located at the edge of the band gap region. It is demonstrated that molecular oxygen adsorption characteristics on stoichiometric SnO₂(1 1 0) surface are changed from endothermic to exothermic due to the existence of surface Ru dopant. The dissociative adsorption of molecular oxygen on the Ru_5c/SnO₂(1 1 0) surface is exothermic, which indicates that Ru could act as an active site to increase the oxygen atom species on SnO₂(1 1 0) surface. Our present study reveals that the Ru dopant on surface is playing both electronic and chemical role in promoting the SnO₂ gas-sensing property.     

Possibility of weakly charged nonlinear solitary dust clouds near the continuum threshold of dust population in a quasi-neutral dusty plasma

Considering the Boltzmann response of the plasma ions and electrons and inertial dynamics of the charged dust grains, the possibility of very weak compressive soliton near the continuum limit of the dust population has been inferred. It is concluded that the behaviour of such coherent structures could be well described by the numerical analysis of the derived nonlinear classical energy integral equation for bounded solutions. These seem to be higher order dispersive structures within acoustic limit of the nonlinear turbulence. It is observed that the dust density enhancement beyond the continuum threshold causes regular increment in width and amplitude of the soliton structures. It is found that the soliton amplitude sensitively depends on the massive impurity’s population. These coherent structures could be visualized as weakly charged solitary dust clouds of finite extension (∼ plasma Debye length) within Boltzmann environment of plasma particles in their local surroundings. The seeding mechanism of such clouds may be attributed to some plasma instabilities driven by either internal or external free energy sources. Numerical analysis of the problem concludes that the experimental observations of such clouds could be possible in low density plasma regime. It is deduced that for plasma density ∼ 10⁶ cm^-3 at temperatures of a few electron volts and for micron to l0nm sized dust grains, the observation of such structures could be possible within wide range variability of the dust population density.     

Self-similarity of electrostatic fluctuations in a linear magnetised plasma system

In this Letter the long-range time correlations present in the fluctuation data in presence of electrostatic instability in a magnetised dc discharge plasma is presented. The electrostatic instability is generated due to the effect of crossed electric and magnetic field (E×B flow) and has intermediate frequency ranging from 50 to 100 MHz. Hurst exponent, the self-similarity parameter is calculated with the help of different statistical methods suggested by many researchers to determine the long-range time correlation present in fluctuation dynamics in the plasma column. The fluctuation in the ion saturation current is measured by a Langmuir probe for the study and the measurement is done both radially and axially in the plasma system. Estimated results clearly expose the self-similar character of the fluctuations with self-similarity parameters having values from 0.65 to 0.90 through the presence of long-range time correlation.     

Extended Conjugation in Polyaniline Like Structure Prepared by Plasma Polymerization Suitable for Optoelectronic Applications

Plasma polymerization of aniline is carried out in a radiofrequency plasma reactor and the effect of polymerization time is examined in the structural, optical and optoelectronic properties of deposited films. Conjugated structures of polyaniline like films are obtained with unique and broad optical absorption band in the ultraviolet and entire visible region. The width of the absorption band increases and hence the optical band gap decreases with polymerization time. The optical constants are extracted by Swanepoel method and the optical dispersion parameters are determined by employing the Wemple-DiDomenico single oscillator model. The films exhibit similar thermal stability in air and argon atmosphere in the region of interest for optoelectronic applications. The photoluminescence study suggests, like the chemically synthesized polyaniline, the benzenoid units to be responsible for fluorescence. The fluorescence peaks due to defect states confirm the formation of spectroscopic units in the plasma polyaniline films.     

Effect of E × B electron drift and plasma discharge in dc magnetron sputtering plasma

Study of electron drift velocity caused by Etimes B motion is done with the help of a Mach probe in a dc cylindrical magnetron sputtering system at different plasma discharge parameters like discharge voltage, gas pressure and applied magnetic field strength. The interplay of the electron drift with the different discharge parameters has been investigated. Strong radial variation of the electron drift velocity is observed and is found to be maximum near the cathode and it decreases slowly with the increase of radial distance from the cathode. The sheath electric field, E measured experimentally from potential profile curve using an emissive probe is contributed to the observed radial variation of the electron drift velocity. The measured values of the drift velocities are also compared with the values from the conventional theory using the experimental values of electric and magnetic fields. This study of the drift velocity variation is helpful in providing a useful insight for determining the discharge conditions and parameters for sputter deposition of thin film.