Low temperature synthesis of zeolite N from kaolinites and montmorillonites

Zeolite N was produced from a variety of kaolinites and montmorillonites at low temperature (b100 °C) in a constantly stirred reactor using potassic and potassic+sodic mother liquors with chloride or hydroxyl anions. Reactions were complete (N95% product) in less than 20 h depending on initial batch composition and type of clay minerals. Zeolite N with 1.0bSi/Alb2.2 was produced under these conditions using KOH in the presence of KCl, NaCl, KCl+NaCl and KCl+NaOH. Zeolite N was also formed under high potassium molarities in the absence of KCl. Zeolite synthesis was more sensitive to water content and temperature when sodium was used in initial batch compositions. Syntheses of zeolite N by these methods were undertaken at bench, pilot and industrial scales.

Low temperature CO sensitive nanostructured WO3 thin films doped with Fe

Nanostructured tungsten oxide thin film based gas sensors have been developed by thermal evaporation method to detect CO at low operating temperatures. The influence of Fe-doping and annealing heat treatment on microstructural and gas sensing properties of these films have been investigated. Fe was incorporated in WO3 film by co-evaporation and annealing was performed at 400oC for 2 hours in air. AFM analysis revealed a grain size of about 10-15 nm in all the films. GIXRD analysis showed that as-deposited films are amorphous and annealing at 400oC improved the crystallinity. Raman and XRD analysis indicated that Fe is incorporated in the WO3 matrix as a substitutional impurity, resulting in shorter O-W-O bonds and lattice cell parameters. Doping with Fe contributed significantly towards CO sensing performance of WO3 thin films. A good response to various concentrations (10-1000 ppm) of CO has been achieved with 400oC annealed Fe-doped WO3 film at a low operating temperature of 150oC.

Microanalysis of clays at low temperature

Accurate thin-film energy dispersive spectroscopic (EDS) analyses of clays with low-atomic-number (low Z) elements (e.g. Na, Al, Si), presents a challenge to the microscopist not only because of the spatial resolution required, but also because of their susceptibility to electron beam-induced radiation damange and very low X-ray count rates. Most common clays, such as kaolinite, smectite and illite occur as submicrometer crystallites with varying degrees of structural disorder in at least two directions and may have dimensions as small as one or two unit cells along the basal direction. Thus, even clays with relatively large a-b dimenstions (e.g., 100 x 100 nm) may be <5nm in the c-axis direction. For typical conditions in an analytical electron microscope (AEM), this sample thickness gives rise to very poor count rates (<200cps) and necessitates long counting times (>300s) in order to obtain satisfactory statistical precision. Unfortunately, beam damage rates for the common clays are very rapid (<10s in imaging mode) between 100kV and 200kV. With a focussed probe for elemental analyses, the damage rate is exacerbated by a high current density and may result in loss of low-Z elements during data collection and consequent loss of analytical accuracy.

Low temperature response of nanostructured tungsten oxide thin films toward hydrogen and ethanol

Semiconducting metal oxide based gas sensors usually operate in the temperature range 200–500 °C. In this paper, we present a new WO3 thin film based gas sensor for H2 and C2H5OH, operating at 150 °C. Nanostructured WO3 thin films were synthesized by thermal evaporation method. The properties of the as-deposited films were modified by annealing in air at 300 °C and 400 °C. Various analytical techniques such as AFM, TEM, XPS, XRD and Raman spectroscopy have been employed to characterize their properties. A clear indication from TEM and XRD analysis is that the as-deposited WO3 films are highly amorphous and no improvement is observed in the crystallinity of the films after annealing at 300 °C. Annealing at 400 °C significantly improved the crystalline properties of the films with the formation of about 5 nm grains. The films annealed at 300 °C show no response to C2H5OH (ethanol) and a little response to H2, with maximum response obtained at 280 °C. The films annealed at 400 °C show a very good response to H2 and a moderate response to C2H5OH (ethanol) at 150 °C. XPS analysis revealed that annealing of the WO3 thin films at 400 °C produces a significant change in stoichiometry, increasing the number of oxygen vacancies in the film, which is highly beneficial for gas sensing. Our results demonstrate that gas sensors with significant performance at low operating temperatures can be obtained by annealing the WO3 films at 400 °C and optimizing the crystallinity and nanostructure of the as-deposited films.

Low temperature pretreatment of sugarcane bagasse at atmospheric pressure using mixtures of ethylene carbonate and ethylene glycol

A low temperature lignocellulose pretreatment process was developed using acid-catalysed mixtures of alkylene carbonate and alkylene glycol. Pretreatment of sugarcane bagasse with mixtures of ethylene carbonate (EC) and ethylene glycol (EG) was more effective than that with mixtures of propylene carbonate (PC) and propylene glycol (PG). These mixtures were more effective than the individual components in making bagasse cellulose more amenable to cellulase digestion. Glucan digestibilities of ≥87% could be achieved with a wide range of EC to EG ratios from 9:1 to 1:1 (w/w). Pretreatment of bagasse by the EC/EG mixture with a ratio of 4:1 in the presence of 1.2% H2SO4 at 90 °C for 30 min led to the highest glucan enzymatic digestibility of 93%. The high glucan digestibilities obtained under these acidic conditions were due to (a) the ability of alkylene carbonate to cause significant biomass size reduction, (b) the ability of alkylene glycol to cause biomass defibrillation, (c) the ability of alkylene carbonate and alkylene glycol to remove xylan and lignin, and (d) the magnified above attributes in the mixtures of alkylene carbonate and alkylene glycol.

High-temperature growth of graphene films on copper foils by ethanol chemical vapour deposition

Chemical vapor deposition (CVD) is widely utilized to synthesize graphene with controlled properties for many applications, especially when continuous films over large areas are required. Although hydrocarbons such as methane are quite efficient precursors for CVD at high temperature (∼1000 °C), finding less explosive and safer carbon sources is considered beneficial for the transition to large-scale production. In this work, we investigated the CVD growth of graphene using ethanol, which is a harmless and readily processable carbon feedstock that is expected to provide favorable kinetics. We tested a wide range of synthesis conditions (i.e., temperature, time, gas ratios), and on the basis of systematic analysis by Raman spectroscopy, we identified the optimal parameters for producing highly crystalline graphene with different numbers of layers. Our results demonstrate the importance of high temperature (1070 °C) for ethanol CVD and emphasize the significant effects that hydrogen and water vapor, coming from the thermal decomposition of ethanol, have on the crystal quality of the synthesized graphene.

Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium) phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me3N+)C6H4 center dot + O-2] = 2.8 x 10(-11) cm(3) molecule(-1) s(-1), Phi = 4.9%; k(2)[(-O2C)C6H4 center dot + O-2] = 5.4 x 10(-1)1 cm(3) molecule(-1) s(-1), Phi = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Synthesis of MgB2 at low temperature and autogenous pressure

High quality, micron-sized interpenetrating grains of MgB2 with high density are produced at low temperatures (~420oC < T < ~500oC) under autogenous pressure by pre-mixing Mg powder and NaBH4 and heating in an Inconel 601 alloy reactor for 5−15 hours. Optimum production of MgB2 with yields greater than 75% occurs for autogenous pressure in the range 1.0 MPa to 2.0 MPa with the reactor at ~500oC. Autogenous pressure is induced by the decomposition of NaBH4 in the presence of Mg and/or other Mg-based compounds. The morphology, transition temperature and magnetic properties of MgB2 are dependent on the heating regime. Significant improvement in physical properties accrues when the reactor temperature is held at 250oC for >20minutes prior to a hold at 500oC.

Distribution of ion-current density on substrate between carbon nanotubes grown from low-temperature plasma

Using Monte Carlo simulation technique, we have calculated the distribution of ion current extracted from low-temperature plasmas and deposited onto the substrate covered with a nanotube array. We have shown that a free-standing carbon nanotube is enclosed in a circular bead of the ion current, whereas in square and hexagonal nanotube patterns, the ion current is mainly concentrated along the lines connecting the nearest nanotubes. In a very dense array (with the distance between nanotubes/nanotube-height ratio less than 0.05), the ions do not penetrate to the substrate surface and deposit on side surfaces of the nanotubes.

Inductively coupled Ar/CH₄/H₂plasmas for low-temperature deposition of ordered carbon nanostructures

The study of inductively coupled Ar/CH 4/H 2 plasmas in the plasma enhanced chemical vapor deposition (PECVD) of self-assembled carbon nanostructures (CN) was presented. A spatially averaged (global) discharge model was developed to study the densities and fluxes of the radical neutrals and charged species, the effective electron temperature, and methane conversion factors under various conditions. It was found that the deposited cation fluxes in the PECVD of CNs generally exceed those of the radical neutrals. The agreement with the optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS) was also derived through numerical results.

Electron transport across magnetic field in low-temperature plasmas : an alternative approach for obtaining evidence of Bohm mechanism

A comparative study involving both experimental and numerical investigations was made to resolve a long-standing problem of understanding electron conductivity mechanism across magnetic field in low-temperature plasmas. We have calculated the plasma parameters from experimentally obtained electric field distribution, and then made a 'back' comparison with the distributions of electron energy and plasma density obtained in the experiment. This approach significantly reduces an influence of the assumption about particular phenomenology of the electron conductivity in plasma. The results of the experiment and calculations made by this technique have showed that the classical conductivity is not capable of providing realistic total current and electron energy, whereas the phenomenological anomalous Bohm mobility has demonstrated a very good agreement with the experiment. These results provide an evidence in favor of the Bohm conductivity, thus making it possible to clarify this pressing long-living question about the main driving mechanism responsible for the electron transport in low-temperature plasmas.

Electron/ion energy loss to discharge walls revised : a case study in low-temperature, thermally nonequilibrium plasmas

Reliable calculations of the electron/ion energy losses in low-pressure thermally nonequilibrium low-temperature plasmas are indispensable for predictive modeling related to numerous applications of such discharges. The commonly used simplified approaches to calculation of electron/ion energy losses to the chamber walls use a number of simplifying assumptions that often do not account for the details of the prevailing electron energy distribution function (EEDF) and overestimate the contributions of the electron losses to the walls. By direct measurements of the EEDF and careful calculation of contributions of the plasma electrons in low-pressure inductively coupled plasmas, it is shown that the actual losses of kinetic energy of the electrons and ions strongly depend on the EEDF. It is revealed that the overestimates of the total electron/ion energy losses to the walls caused by improper assumptions about the prevailing EEDF and about the ability of the electrons to pass through the repulsive potential of the wall may lead to significant overestimates that are typically in the range between 9 and 32%. These results are particularly important for the development of power-saving strategies for operation of low-temperature, low-pressure gas discharges in diverse applications that require reasonably low power densities. © 2008 American Institute of Physics.

Electrostatic nanoparticle filter for atomic scale fabrication in low-temperature plasmas

The means of reducing nanoparticle contamination in the synthesis of carbon nanostructures in reactive Ar + H2 + CH4 plasmas are studied. It is shown that by combining the electrostatic filtering and thermophoretic manipulation of nanoparticles, one can significantly improve the quality of carbon nanopatterns. By increasing the substrate heating power, one can increase the size of deposited nanoparticles and eventually achieve nanoparticle-free nanoassemblies. This approach is generic and is applicable to other reactive plasma-aided nanofabrication processes.