Determination of the degree of dissociation in an inductively coupled hydrogen plasma using optical emission spectroscopy and laser diagnostics

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (~25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

Space and time resolved rotational state populations and gas temperatures in an inductively coupled hydrogen RF discharge

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (similar or equal to 25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

P(rho)T Measurements of Imidazolium-Based Ionic Liquids

Experimental density measurements are reported, and the derived thermodynamic properties, such as the isothermal compressibility, the isobaric expansivity, and the thermal pressure coefficient are presented as Supporting Information for several imidazolium-based ionic liquids (ILs), namely, 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C2mim][NTf2], 1-heptyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C7mim][NTf2], 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [C8mim][NTf2], 1-ethyl-3-methyl-imidazolium tetrafluoroborate [C2mim][BF4], and 1-butyl-3-methyl-imidazolium tricyanomethane [C4mim][C(CN)3] in the pressure (0.10 <p/MPa <30.00) and temperature (293.15 <T/K <393.15) domains. These ILs were chosen to provide an understanding of the influence of the cation alkyl chain length and the anion influence on the properties under study. Experimental densities are correlated with the Tait equation with an average absolute deviation (AAD) less than 0.04 %. Experimental densities are in good agreement with the densities obtained by some recent predictive methods proposed in the literature.

Densities and Derived Thermodynamic Properties of Imidazolium-, Pyridinium-, Pyrrolidinium-, and Piperidinium-Based Ionic Liquids

In the present work, experimental density measurements are reported along with the derived thermodynamic properties, such as the isothermal compressibility (?T), the isobaric expansivity (ap), and the thermal pressure coefficient (?v) for imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs), namely, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate [C2mim][CF3SO3], 3-methyl-1-propylpyridinium bis(trifluoromethylsulfonyl)imide [C3mpy][NTf2], 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C3mpyr][NTf2], 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide [C4mpyr][NTf2], and 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide [C3mpip][NTf2] in the pressure (0.10 <P/MPa <35.00) and temperature (293.15 <T/K <393.15) domains. These ILs were chosen to provide an understanding of the influence of the cation and anion on the properties under study. Experimental densities are correlated with the Tait equation with an average absolute relative deviation (AARD) better than 0.02 %. It is shown that experimental densities are in good agreement with the densities obtained by the predictive method previously proposed by us.

Non-ideal behaviour of a room temperature ionic liquid in an alkoxyethanol or poly ethers at T = (298.15 to 318.15) K

Non-ideal behaviour of 1-butyl-3-methylimidazolium hexafluorophosphate [bmim][PF6] in ethylene glycol monomethyl ether; CH3OCH2CH2OH (EGMME), ethylene glycol dimethyl ether; CH3OCH2CH2OCH3 (EGDME) and diethylene glycol dimethyl ether; CH3(OCH2CH2)2OCH3 (DEGDME) have been investigated over the whole composition range at T = (298.15 to 318.15) K. To gain insight into the mixing behaviour, results of density measurements were used to estimate excess molar volumes, image, apparent molar volumes, Vphi,i, partial molar volumes, image, excess partial molar volumes, image, and their limiting values at infinite dilution, image, image, and image, respectively. Volumetric results have been analyzed in the light of Prigogine–Flory–Patterson (PFP) statistical mechanical theory. Measurements of refractive indices n were also performed for all the binary mixtures over whole composition range at T = 298.15 K. Deviations in refractive indices ?phin and the deviation of molar refraction ?xR have been calculated from experimental data. Refractive indices results have been correlated with volumetric results and have been interpreted in terms of molecular interactions. Excess properties are fitted to the Redlich–Kister polynomial equation to obtain the binary coefficients and the standard errors.

Extension of the Ye and Shreeve group contribution method for density estimation of ionic liquids in a wide range of temperatures and pressures

An extension of the Ye and Shreeve group contribution method [C. Ye, J.M. Shreeve, J. Phys. Chem. A 111 (2007) 1456–1461] for the estimation of densities of ionic liquids (ILs) is here proposed. The new version here presented allows the estimation of densities of ionic liquids in wide ranges of temperature and pressure using the previously proposed parameter table. Coefficients of new density correlation proposed were estimated using experimental densities of nine imidazolium-based ionic liquids. The new density correlation was tested against experimental densities available in literature for ionic liquids based on imidazolium, pyridinium, pyrrolidinium and phosphonium cations. Predicted densities are in good agreement with experimental literature data in a wide range of temperatures (273.15–393.15 K) and pressures (0.10–100 MPa). For imidazolium-based ILs, the mean percent deviation (MPD) is 0.45% and 1.49% for phosphonium-based ILs. A low MPD ranging from 0.41% to 1.57% was also observed for pyridinium and pyrrolidinium-based ILs.

Applying a QSPR correlation to the prediction of surface tensions of ionic liquids

Ionic liquids (ILs) have attracted large amount of interest due to their unique properties. Although large effort has been focused on the investigation of their potential application, characterization of ILs properties and structure–property relationships of ILs are poorly understood. Computer aided molecular design (CAMD) of ionic liquids (ILs) can only be carried if predictive computational methods for the ILs properties are available. The limited availability of experimental data and their quality have been preventing the development of such tools. Based on experimental surface tension data collected from the literature and measured at our laboratory, it is here shown how a quantitative structure–property relationship (QSPR) correlation for parachors can be used along with an estimation method for the densities to predict the surface tensions of ILs. It is shown that a good agreement with literature data is obtained. For circa 40 ionic liquids studied a mean percent deviation (MPD) of 5.75% with a maximum deviation inferior to 16% was observed. A correlation of the surface tensions with the molecular volumes of the ILs was developed for estimation of the surface tensions at room temperature. It is shown that it can describe the experimental data available within a 4.5% deviation. The correlations here developed can thus be used to evaluate the surface tension of ILs for use in process design or in the CAMD of new ionic liquids.

A group contribution method for viscosity estimation of ionic liquids

Based on experimental viscosity data collected from the literature and using density data obtained from a predictive method previously proposed by the authors, a group contribution method is proposed to estimate viscosity of imidazolium-, pyridinium-, and pyrrolidinium-based ILs containing hexafluorophosphate (PF6), tetrafluoroborate (BF4), bis(trifluoromethanesulfonyl) amide (Tf2N), chloride (Cl), acetate (CH3COO), methyl sulfate (MeSO4), ethyl sulfate (EtSO4), and trifluoromethanesulfonate (CF3SO3) anions, covering wide ranges of temperature, 293–393 K and viscosity, 4–21,000 cP. It is shown that a good agreement with literature data is obtained. For circa 500 data points of 29 ILs studied, a mean percent deviation (MPD) of 7.7% with a maximum deviation smaller than 28% was observed. 71.1% of the estimated viscosities present deviations smaller than 10% of the experimental values while only 6.4% have deviations larger than 20%. The group contribution method here developed can thus be used to evaluate the viscosity of new ionic liquids in wide ranges of temperatures at atmospheric pressure and, as data for new groups of cations and anions became available, can be extended to a larger range of ionic liquids.

Estimation of speed of sound of ionic liquids using surface tensions and densities: A volume based approach

The limited availability of experimental data and their quality have been preventing the development of predictive methods and Computer Aided Molecular Design (CAMD) of ionic liquids (ILs). Based on experimental speed of sound data collected from the literature, the inter-relationship of surface tension (s), density (?), and speed of sound (u) has been examined for imidazolium based ILs containing hexafluorophosphate (PF6), tetrafluoroborate (BF4), bis(trifluoromethanesulphonyl) amide (NTf2), methyl sulphate (MeSO4), ethyl sulphate (EtSO4), and trifluoromethanesulphonate (CF3SO3) anions, covering wide ranges of temperature, 278.15–343.15 K and speed of sound, 1129.0–1851.0 m s-1. The speed of sound was correlated with a modified Auerbach's relation, by using surface tension and density data obtained from volume based predictive methods previously proposed by the authors. It is shown that a good agreement with literature data is obtained. For 133 data points of 14 ILs studied a mean percent deviation (MPD) of 1.96% with a maximum deviation inferior to 5% was observed. The correlations developed here can thus be used to evaluate the speeds of sound of new ionic liquids.

2.4 GHz Class-E power amplifier with transmissionline harmonic terminations

The design procedure, fabrication and measurement of a Class-E power amplifier with excellent second- and third-harmonic suppression levels are presented. A simplified design technique offering compact physical layout is proposed. With a 1.2 mm gate-width GaAs MESFET as a switching device, the amplifier is capable of delivering 19.2 dBm output power at 2.41 GHz, achieves peak PAE of 60% and drain efficiency of 69%, and exhibits 9 dB power gain when operated from a 3 V DC supply voltage. When compared to the classical Class-E two-harmonic termination amplifier, the Class-E amplifier employing three-harmonic terminations has more than 10% higher drain efficiency and 23 dB better third-harmonic suppression level. Experimental results are presented and good agreement with simulation is obtained. Further, to verify the practical implementation in communication systems, the Bluetooth-standard GFSK modulated signal is applied to both two- and three-harmonic amplifiers. The measured RMS FSK deviation error and RMS magnitude error were, for the three-harmonic case, 1.01 kHz and 0.122%, respectively, and, for the two-harmonic case, 1.09 kHz and 0.133%. © 2007 The Institution of Engineering and Technology.

Morphological and molecular characters reveal differentiation in a Neotropical social bee, Melipona beecheii (Apidae : Meliponini)

Morphometrics and DNA microsatellites were used to analyse the genetic structure of populations of the stingless bee M. beecheii from two extremes of its geographic range. The results showed that populations from Costa Rica and Yucatan exhibit substantial phenotypic and molecular differentiation. Bees from Yucatan were smaller and paler than those from Costa Rica. The value of multilocus F-ST = 0.280 (P <0.001) confirmed that there were significant molecular genetic differences between the two populations. Populations showed significant deviation from Hardy Weinberg equilibrium and the values of FIS (the inbreeding coefficient) were positive for Costa Rica = 0.416 and the Yucatan Peninsula = 0.193, indicating a lack of heterozygotes in both populations possibly due to inbreeding. The DNA sequence of 678 bp of the mitochondrial gene COI differed between populations by 1.2%. The results of this study should be considered in conservation programmes, particularly with regard to the movement of colonies between regions.

A DFT study of the chain growth probability in Fischer-Tropsch synthesis

The chain growth probability (alpha value) is one of the most significant parameters in Fischer-Tropsch (FT) synthesis. To gain insight into the chain growth probability, we systematically studied the hydrogenation and C-C coupling reactions with different chain lengths on the stepped Co(0001) surface using density functional theory calculations. Our findings elucidate the relationship between the barriers of these elementary reactions and the chain length. Moreover, we derived a general expression of the chain growth probability and investigated the behavior of the alpha value observed experimentally. The high methane yield results from the lower chain growth rate for C-1 + C-1 coupling compared with the other coupling reactions. After C-1, the deviation of product distribution in FT synthesis from the Anderson-Schulz-Flory distribution is due to the chain length-dependent paraffin/olefin ratio. (C) 2008 Elsevier Inc. All rights reserved.

Right-left discrimination among medical students: Getting it right all of the time?

Objective To determine medical students’ self awareness and ability to discriminate right from left; to identify characteristics associated with this ability; and to identify any techniques used to aid discrimination. Design Questionnaire and psychometric study. Setting Undergraduate medical school, Northern Ireland. Participants 290 first year undergraduate students. Main outcome measure Medical students’ ability to discriminate right from left using the Bergen right-left discrimination test. Results Test scores ranged from 31 to 143 on a scale of 0- 144 (mean 112 (standard deviation 22.2)). Male students significantly outperformed female students (117.18 (26.96) v 110.80 (28.94)). Students who wanted to be surgeons performed significantly better than those who wanted to be general practitioners or medical doctors (119.87 (25.15) v 110.55 (27.36) v 112.50 (26.88)). The interaction effect for sex and career wishes was not significant (P=0.370). Students who used learnt techniques to help them discriminate scored significantly less than those who did not (P

The contribution of visual feedback to visuomotor adaptation: How much and when?

We investigated the role of visual feedback in adapting to novel visuomotor environments. Participants produced isometric elbow torques to move a cursor towards visual targets. Following trials with no rotation, participants adapted to a 60 degrees rotation of the visual feedback before returning to the non-rotated condition. Participants received continuous visual feedback (CF) of cursor position during task execution or post-trial visual feedback (PF). With training, reductions of the angular deviations of the cursor path occurred to a similar extent and at a similar rate for CF and PF groups. However, upon re-exposure to the non-rotated environment only CF participants exhibited post-training aftereffects, manifested as increased angular deviation of the cursor path, with respect to the pre-rotation trials. These aftereffects occurred despite colour cues permitting identification of the change in environment. The results show that concurrent feedback permits automatic recalibration of the visuomotor mapping while post-trial feedback permits performance improvement via a cognitive strategy. (C) 2008 Elsevier B.V. All rights reserved.

The interference effects of non-rotated versus counter-rotated trials in visuomotor adaptation

An isometric torque-production task was used to investigate interference and retention in adaptation to multiple visuomotor environments. Subjects produced isometric flexion-extension and pronation-supination elbow torques to move a cursor to acquire targets as quickly as possible. Adaptation to a 30 degrees counter-clockwise (CCW) rotation (task A), was followed by a period of rest (control), trials with no rotation (task B0), or trials with a 60 degrees clockwise (CW) rotation (task B60). For all groups, retention of task A was assessed 5 h later. With initial training, all groups reduced the angular deviation of cursor paths early in the movements, indicating feedforward adaptation. For the control group, performance at commencement of the retest was significantly better than that at the beginning of the initial learning. For the B0 group, performance in the retest of task A was not dissimilar to that at the start of the initial learning, while for the B60 group retest performance in task A was markedly worse than initially observed. Our results indicate that close juxtaposition of two visuomotor environments precludes improved retest performance in the initial environment. Data for the B60 group, specifically larger angular errors upon retest compared with initial exposures, are consistent with the presence of anterograde interference. Furthermore, full interference occurred even when the visuomotor environment encountered in the second task was not rotated (B0). This latter novel result differs from those obtained for force field learning, where interference does not occur when task B does not impose perturbing forces, i.e., when B consists of a null field (Brashers-Krug et al., Nature 382:252-255, 1996). The results are consistent with recent proposals suggesting different interference mechanisms for visuomotor (kinematic) compared to force field (dynamic) adaptations, and have implications for the use of washout trials when studying interference between multiple visuomotor environments.