Enhanced Dispersion of TiO2 Nanoparticles in a TiO2/PEDOT:PSS Hybrid Nanocomposite via Plasma-Liquid Interactions

A facile method to synthesize a TiO2/PEDOT:PSS hybrid nanocomposite material in aqueous solution through direct current (DC) plasma processing at atmospheric pressure and room temperature has been demonstrated. The dispersion of the TiO2 nanoparticles is enhanced and TiO2/polymer hybrid nanoparticles with a distinct core shell structure have been obtained. Increased electrical conductivity was observed for the plasma treated TiO2/PEDOT:PSS nanocomposite. The improvement in nanocomposite properties is due to the enhanced dispersion and stability in liquid polymer of microplasma treated TiO2 nanoparticles. Both plasma induced surface charge and nanoparticle surface termination with specific plasma chemical species are proposed to provide an enhanced barrier to nanoparticle agglomeration and promote nanoparticle-polymer binding.

Magnetospheric Structure and Atmospheric Joule Heating of Habitable Planets Orbiting M-dwarf Stars

We study the magnetospheric structure and the ionospheric Joule Heating of planets orbiting M-dwarf stars in the habitable zone using a set of magnetohydrodynamic models. The stellar wind solution is used to drive a model for the planetary magnetosphere, which is coupled with a model for the planetary ionosphere. Our simulations reveal that the space environment around close-in habitable planets is extreme, and the stellar wind plasma conditions change from sub- to super-Alfvénic along the planetary orbit. As a result, the magnetospheric structure changes dramatically with a bow shock forming in the super-Alfvénic sectors, while no bow shock forms in the sub-Alfvénic sectors. The planets reside most of the time in the sub-Alfvénic sectors with poor atmospheric protection. A significant amount of Joule Heating is provided at the top of the atmosphere as a result of the intense stellar wind. For the steady-state solution, the heating is about 0.1%-3% of the total incoming stellar irradiation, and it is enhanced by 50% for the time-dependent case. The significant Joule Heating obtained here should be considered in models for the atmospheres of habitable planets in terms of the thickness of the atmosphere, the top-side temperature and density, the boundary conditions for the atmospheric pressure, and particle radiation and transport. Here we assume constant ionospheric Pedersen conductance similar to that of the Earth. The conductance could be greater due to the intense EUV radiation leading to smaller heating rates. We plan to quantify the ionospheric conductance in future study.

Non-thermal Plasma Exposure Rapidly Attenuates Bacterial AHL-Dependent Quorum Sensing and Virulence.

The antimicrobial activity of atmospheric pressure non-thermal plasma has been exhaustively characterised, however elucidation of the interactions between biomolecules produced and utilised by bacteria and short plasma exposures are required for optimisation and clinical translation of cold plasma technology. This study characterizes the effects of non-thermal plasma exposure on acyl homoserine lactone (AHL)-dependent quorum sensing (QS). Plasma exposure of AHLs reduced the ability of such molecules to elicit a QS response in bacterial reporter strains in a dose-dependent manner. Short exposures (30-60 s) produce of a series of secondary compounds capable of eliciting a QS response, followed by the complete loss of AHL-dependent signalling following longer exposures. UPLC-MS analysis confirmed the time-dependent degradation of AHL molecules and their conversion into a series of by-products. FT-IR analysis of plasma-exposed AHLs highlighted the appearance of an OH group. In vivo assessment of the exposure of AHLs to plasma was examined using a standard in vivo model. Lettuce leaves injected with the rhlI/lasI mutant PAO-MW1 alongside plasma treated N-butyryl-homoserine lactone and n-(3-oxo-dodecanoyl)-homoserine lactone, exhibited marked attenuation of virulence. This study highlights the capacity of atmospheric pressure non-thermal plasma to modify and degrade AHL autoinducers thereby attenuating QS-dependent virulence in P. aeruginosa.

Germanium MOS Capacitors with Hafnium Dioxide and Silicon Dioxide Dielectrics

Germanium (Ge) does not grow a suitable oxide for MOS devices. The Ge/dielectric interface is of prime importance to the operation of photo-detectors and scaled MOSTs. Therefore there is a requirement for deposited or bonded dielectric materials. MOS capacitors have been formed on germanium substrates with three different dielectric materials. Firstly, a thermally grown and bonded silicon dioxide (SiO2) layer, secondly, SiO2 deposited by atmospheric pressure CVD ‘silox’, and thirdly a hafnium oxide (HfO2) high-k dielectric deposited by atomic layer deposition (ALD). Ge wafers used were p-type 1 0 0 2 O cm. C–V measurements have been made on all three types of capacitors to assess the interface quality. ALD HfO2 and silox both display acceptable C–V characteristics. Threshold voltage and maximum and minimum capacitance values closely match expected values found through calculation. However, the bonded SiO2 has non-ideal C–V characteristics, revealing the presence of a high density of interface states. A H2/N2 post metal anneal has a detrimental effect on C–V characteristics of HfO2 and silox dielectrics, causing a shift in the threshold voltage and rise in the minimum capacitance value. In the case of hafnium dioxide, capacitor properties can be improved by performing a plasma nitridation of the Ge surface prior to dielectric deposition.

Low temperature surface nitridation processes for dielectric-Ge interfaces

Germanium MOS capacitors have been fabricated with a high-? HfO dielectric using ALD. An in-situ low temperature (250°C) nitrogen plasma treatment on the germanium surface prior to the deposition of HfO was found to be beneficial to the electrical properties of the devices. Germanium MOS capacitors have also been fabricated with a SiO dielectric deposited by an atmospheric pressure CVD 'silox' process. The same low temperature plasma nitridation was found to degrade the electrical properties of the silox devices. The effect of a post-metal anneal in H and N on both types of capacitor structure was also found to degrade device electrical properties. copyright The Electrochemical Society.

Rotation of a nanoparticle cloud in an inductively coupled plasma induced by weak static magnetic fields

Hydrocarbon nanoparticles with diameters between 10 and 30 nanometres are created in a low pressure plasma combining capacitive and inductive power coupling. The particles are generated in the capacitive phase of the experiment and stay confined in the plasma in the inductive phase. The presence of these embedded particles induces a rotation of a particle-free region (void) around the symmetry axis of the reactor. The phenomenon is analysed using optical emission spectroscopy both line integrated and spatially resolved via an intensified charge coupled device camera. From these data, electron temperatures and densities are deduced. We find that the rotation of the void is driven by a tangential component of the ion drag force induced by an external static magnetic field. Two modes are observed: a fast rotation of the void in the direction opposite to that of the tangential component and a slow rotation in the same direction. The rotation speed decreases linearly with the size of the particles. In the fast mode the dependence on the applied magnetic field is weak and consequently the rotation speed can serve as a monitor to detect particle sizes in low temperature plasmas.

The challenge of revealing and tailoring the dynamics of radio-frequency plasmas

The complex dynamics of ionization and excitation mechanisms in capacitively coupled radio-frequency plasmas is discussed for single- and dual-frequency operations in low-pressure and atmospheric pressure plasmas. Electrons are energized through the dynamics of electric fields in the vicinity of the plasma boundary sheaths. Distinctly different power dissipation mechanisms can either co-exist or initiate mode transitions exhibiting characteristic spatio-temporal ionization structures. Phase resolved optical emission spectroscopy, in combination with adequate modelling of the population dynamics of excited states, and numerical simulations reveal dissipation associated with sheath expansion, sheath collapse, transient electron avalanches and wave–particle interactions. In dual-frequency systems the relative phase between the two frequency components provides additional strategies to tailor the plasma dynamics.

Low pressure carbon dioxide solubility in pure electrolyte solvents for lithium-ion batteries as a function of temperature. Measurement and prediction

Experimental values for the carbon dioxide solubility in eight pure electrolyte solvents for lithium ion batteries – such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), ?-butyrolactone (?BL), ethyl acetate (EA) and methyl propionate (MP) – are reported as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility data, the Henry’s law constant of the carbon dioxide in these solvents was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOthermX software and those calculated by the Peng–Robinson equation of state implemented into Aspen plus. From this work, it appears that the CO2 solubility is higher in linear carbonates (such as DMC, EMC, DEC) than in cyclic ones (EC, PC, ?BL). Furthermore, the highest CO2 solubility was obtained in MP and EA solvents, which are comparable to the solubility values reported in classical ionicliquids. The precision and accuracy of the experimental values, considered as the per cent of the relative average absolute deviations of the Henry’s law constants from appropriate smoothing equations and from literature values, are close to (1% and 15%), respectively. From the variation of the Henry’s law constants with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs free energy, the enthalpy, and the entropy are calculated, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state.

Low pressure carbon dioxide solubility in lithium-ion batteries based electrolytes as a function of temperature. Measurement and prediction

We present in this study the effect of nature and concentration of lithium salt, such as the lithium hexafluorophosphate, LiPF6; lithium tris(pentafluoroethane)-trifluorurophosphate LiFAP; lithium bis(trifluoromethylsulfonyl)imide, LiTFSI, on the CO2 solubility in four electrolytes for lithium ion batteries based on pure solvent that include ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), as well as, in the EC:DMC, EC:EMC and EC:DEC (50:50) wt.% binary mixtures as a function of temperature from (283 to 353) K and atmospheric pressure. Based on experimental solubility values, the Henry’s law constant of the carbon dioxide in these solutions with the presence or absence of lithium salt was then deduced and compared with reported values from the literature, as well as with those predicted by using COSMO-RS methodology within COSMOThermX software. From this study, it appears that the addition of 1 mol · dm-3 LiPF6 salt in alkylcarbonate solvents decreases their CO2 capture capacity. By using the same experimental conditions, an opposite CO2 solubility trend was generally observed in the case of the addition of LiFAP or LiTFSI salts in these solutions. Additionally, in all solutions investigated during this work, the CO2 solubility is greater in electrolytes containing the LiFAP salt, followed by those based on the LiTFSI case. The precision and accuracy of the experimental data reported therein, which are close to (1 and 15)%, respectively. From the variation of the Henry’s law constant with temperature, the partial molar thermodynamic functions of dissolution such as the standard Gibbs energy, the enthalpy, and the entropy, as well as the mixing enthalpy of the solvent with CO2 in its hypothetical liquid state were calculated. Finally, a quantitative analysis of the CO2 solubility evolution was carried out in the EC:DMC (50:50) wt.% binary mixture as the function of the LiPF6 or LiTFSI concentration in solution to elucidate how ionic species modify the CO2 solubility in alkylcarbonates-based Li-ion electrolytes by investigating the salting effects at T = 298.15 K and atmospheric pressure.

Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions

The speeds of sound in dibromomethane, bromochloromethane, and dichloromethane have been measured in the temperature range from 293.15 to 313.15 K and at pressures up to 100 MPa. Densities and isobaric heat capacities at atmospheric pressure have been also determined. Experimental results were used to calculate the densities and isobaric heat capacities as the function of temperature and pressure by means of a numerical integration technique. Moreover, experimental data at atmospheric pressure were then used to determine the SAFT-VR Mie molecular parameters for these liquids. The accuracy of the model has been then evaluated using a comparison of derived experimental high-pressure data with those predicted using SAFT. It was found that the model provide the possibility to predict also the isobaric heat capacity of all selected haloalkanes within an error up to 6%.

A facile method for the synthesis of Au/PEDOT:PSS nanocomposite

In this work, we have successfully synthesized Au nanoparticles (NPs) in situ in PEDOT:PSS deploying a room temperature atmospheric pressure microplasma. The size of the AuNPs is a function of the gold salt precursor concentration and the plasma processing time. The Au/polymer colloids after processing remain well dispersed over a prolonged period of time. Both gold salt concentration and the plasma processing time have influence on the electrical conductivity of the dried Au/PEDOT:PSS nanocomposite films. An enhanced electrical conductivity of the Au/PEDOT:PSS nanocomposite films has been attributed to (i) the interfacial ligand formation between the S atoms in PEDOT:PSS molecules and the Au surface and (ii) charge transfer from the AuNPs to the holes of PEDOT:PSS molecules.

Driving high energy ion beams with light pressure

State-of-the-art high power lasers can exert immense pressure on thin foils which can be used to accelerate energetic ion beams efficiently at the laser plasma interface.

Microplasma Processed Ultrathin Boron Nitride Nanosheets for Polymer Nanocomposites with Enhanced Thermal Transport Performance

This paper reports on the enhancement of the thermal transport properties of nanocomposite materials containing hexagonal boron nitride in poly (vinyl alcohol)through room-temperature atmospheric pressure direct-current microplasma processing. Results show that the microplasma treatment leads to exfoliation of the hexagonal boron nitride in isopropyl alcohol, reducing the number of stacks from >30to a few or single layers. The thermal diffusivity of the resulting nanocomposites reaches 8.5 mm2 s-1, 50 times greater than blank poly (vinyl alcohol) and twice that ofnanocomposites containing non-plasma treated boron nitride nanosheets. From TEM analysis, we observe much less aggregation of the nanosheets after plasma processing along with indications of an amorphous carbon interfacial layer which may contribute to stable dispersion of boron nitride nanosheets in the resulting plasma treated colloids.

Mutual Solubilities of Water and the [Cnmim][Tf2N] Hydrophobic Ionic Liquids

Ionic liquids (ILs) have recently garnered increased attention because of their potential environmental benefits as "green" replacements over conventional volatile organic solvents. While ILs cannot significantly volatilize and contribute to air pollution, even the most hydrophobic ones present some miscibility with water posing environmental risks to the aquatic ecosystems. Thus, the knowledge of ILs toxicity and their water solubility must be assessed before an accurate judgment of their environmental benefits and prior to their industrial applications. In this work, the mutual solubilities for [C2-C8mim][Tf2N] (n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) and water between 288.15 and 318.15 K at atmospheric pressure were measured. Although these are among the most hydrophobic ionic liquids known, the solubility of water in these compounds is surprisingly large, ranging from 0.17 to 0.36 in mole fraction, while the solubility of these ILs in water is much lower ranging from 3.2 × 10-5 to 1.1 × 10-3 in mole fraction, in the temperature and pressure conditions studied. From the experimental data, the molar thermodynamic functions of solution and solvation such as Gibbs energy, enthalpy, and entropy at infinite dilution were estimated, showing that the solubility of these ILs in water is entropically driven. The predictive capability of COSMO-RS, a model based on unimolecular quantum chemistry calculations, was evaluated for the description of the binary systems investigated providing an acceptable agreement between the model predictions and the experimental data both with the temperature dependence and with the ILs structural variations.

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.