High porosity silica xerogels prepared by a particulate sol–gel route: pore structure and proton conductivity

The lower cost and higher hydrophilicity of silica xerogels could make them potential substitutes for perfluorosulfonic polymeric membranes in proton exchange membrane fuel cells (PEMFCs). For that purpose, we need to obtain micro or micro and mesoporous silica xerogels with a high porosity. The preparation of micro (<2 nm) and micro and mesoporous silica xerogels (2<d_poresize10 nm) from particulate as oppossed to polymeric suspensions of silica using tetraethyl orthosilicate (TEOS) as precursor is used. Two techniques of varying packing density have been performed in this work: (1) Control of the aggregation degree in the sol by adjusting its pH before gelation (pH 5, 6 and 8) and (2) Mixture of sols with a different average particle size (particles formed under acid and base catalyzed reactions). Proton conductivity of the obtained xerogels was studied as a function of temperature and relative humidity (RH). High pore volume, high porosity and small pore size SiO₂ xerogels have been achieved in the calcination temperature range from 250 to 550 °C. The calcined xerogels showed microporosity or micro and mesoporosity in the whole range of calcination temperatures. By mixing sols (molar ratio: acid/base=4.8) porosities up to 54.7±0.1% are achieved, at 250 °C of firing temperature. According to EMF measurements, electrical transport is due to protons in this kind of materials. The proton conductivity of the studied xerogels increased linear with measured temperature. A S-shaped dependence of the conductivity with the RH was observed with the greatest increase noted between 58% and 81% RH. Xerogels with a low porosity (40.8±0.1%) and an average pore size less than 2.0 nm showed lower values of proton conductivity than that of xerogels with a higher porosity and a higher average pore size in the whole range of temperature and RH. When silica xerogels, with the highest conductivity, are treated at pH 1.5, that property increased from 2.84×10⁻³±5.11×10⁻⁵ S/cm to 4.0×10⁻³±7.2×10⁻⁵ S/cm, at 81% RH and 80 °C. It indicates that the surface site density of these materials has a strong effect on conductivity. Proton conductivity values achieved are less than one order of magnitude lower than that of Nafion, under the same conditions of temperature and RH.     

ASTRA 4.0 Program: Data Reduction for Obtaining Structure Results of Extreme Accuracy

Crystallography Reports - Unique methods for processing diffraction data, which guarantee extreme accuracy and reliability, have been implemented in the ASTRA 4.0 software package. The central...     

Thermal and chemical methods for producing zinc silicate (willemite): A review

Thermal and chemical methods for producing zinc silicate, Zn₂SiO₄ phosphor on industrial and laboratory scales are reviewed. Zinc silicate has a promising future in advanced materials as a highly versatile luminescent material due to the wide range of multi-colors that can be obtained from various guest ions. Candidates for future industrial methods of producing zinc silicate are critically reviewed from the point of view of phase formation and compared with the conventional solid-state reaction. Conventional methods require calcination at temperatures higher than 1000 °C and long reaction times to form Zn₂SiO₄ phase and these processes limit particle shape and size. Sol–gel methods are performed in a solvent at ambient pressure, while hydrothermal and solvothermal methods tend use high temperatures and high pressures, and especially supercritical water methods tend use conditions higher than 400 °C and 25 MPa. Hydrothermal and sol–gel literature shows that crystallization of Zn₂SiO₄ requires at least temperatures of around 100 °C. Of all the growth methods, supercritical water is able to bring about phase formation in the shortest reaction time. Vapor methods are performed with a gas phase as the reaction medium. Vapor and sol–gel methods require post-calcination for crystallization and have the advantage of providing characteristic particles such as uniform shapes, spherical particles, or nano-sized particles by varying the experimental conditions; they may be combined with the other crystallization routes in the future.     

Lasing Pixels: A New Application for PDLCs

Abstract

Pixels in an intracavity polymer dispersed liquid crystal can switch lasing action on and off, yielding addressable lasing pixels for projection applications. The marriage between an efficient PDLC display element and laser illumination consolidates the positive attributes of two different approaches to projection into a very capable technology with greater application potential. This radically different approach to projection certainly meets many of the market needs where current technologies fall short. With these needs met, a new application of PDLC technology is on the horizon.     

Grain size distribution in the Kolmogorov model for nucleation and growth: Heterogeneous versus homogeneous nucleation

A theory of grain size distribution in nucleation and growth reactions described by the KOLMOGOROV model is developed. The distribution of agglomerates of growing and impinging nuclei is explicitely calculated for the two cases of heterogeneous and homogeneous nucleation. The results are compared and discussed with respect to the investigation of the nucleation mechanism in crystallization processes.     

Silica xerogels of tailored porosity as support matrix for optical chemical sensors. Simultaneous effect of pH, ethanol:TEOS and water:TEOS molar ratios, and synthesis temperature on gelation time, and textural and structural properties

The sensing of a chemical environment is achieved mainly in the surface by interactions of the sensor material with its chemical surroundings. Therefore, porous structure control is key in developing good chemical sensors. The aim of this work was to obtain materials of tailored porosity to be used as support matrix for optical chemical sensors. We studied the simultaneous effect of pH, temperature, ethanol:TEOS, and water:TEOS molar ratios on gelation time, and textural and structural properties. We used a 2⁴ factorial design that evaluates the effect of each independent variable and their interactions. Samples were characterized by XRD, SEM, FTIR, and gas adsorption (N₂ at 77 K and CO₂ at 273 K). The gelation time decreased with increasing temperature, water:TEOS molar ratio, and pH; and with decreasing ethanol:TEOS molar ratios. Synthesis conditions also affected the xerogels porous textures. Xerogels obtained at pH 2.5 were ultramicroporous. In general, samples synthesized at pH 4.5 and ethanol:TEOS molar ratio of 2.25:1 were mesoporous, but the material is not appropriate for use as support in fiber optical sensors.     

New Transport Mechanisms for Conducting Polymers: The Role of Disorder

Abstract

A unified view of the metallic state in polyaniline and heavily-doped polacetylene is presented. We first consider a single randomly-protonated strand of the emeraldine form of polyaniline. We show explicitly that the disorder inherent in this system is described by the random-dimer model of Dunlap, Wu and Phillips¹. The random dimer model is simply a tight-binding model for a binary alloy in which pairs of lattice sites are assigned one of two values at random. The random dimer model is shown to possess a narrow band of conducting states that can ultimately lead to dramatic increases in the conductivity if the Fermi level is appropriately tuned. It is demonstrated explicitly that the location in the energy band of the conducting states of the random-dimer model for polyaniline coincides with recent calculations of the location of the Fermi level in the protonated form of the polymer^2,3. We argue then that the random-dimer model is capable of explaining the insulator-metal transition in polyaniline. In the context of polyacetylene, we propose a ‘dirty metal’ picture for the metallic state which is consistent with both the closing of the band gap and the existence of a band of extended states. Our model is based on the observation that a random distribution of solitons closes the band gap at ～5-6% doping and is formally equivalent to the random dimer model. The location of the extended states in the disordered soliton lattice is computed. It is shown that because these states lie in the vicinity of the band edge, they are capable of explaining the sudden onset of the experimentally-observed Pauli susceptibility and the subsequent depinning of the solitons in the metallic state. We close by noting that because the random dimer model applies to any lattice in which the defects are extended and possess a plane of symmetry, it quite generally describes any polymeric system in which the stable defects are solitonic or bi-polaronic in nature     

New aluminium precursors for MOMBE (CBE): a comparative study

Recently different new Al precursors have been developed to improve the electrical and optical quality of AlGaAs layers grown by MOMBE (CBE), since AlGaAs layers still suffer from the high incorporation of oxygen and carbon. Three approaches are introduced and results obtained from Al_xGa_1−xAs layers (0 < x ≤ 1) are discussed. APAH, a double ring structure molecule, was found to yield AlGaAs layers with high contents of carbon and nitrogen. The use of an Alane-adduct decreases impurity concentrations and improves optical properties. However, TIBAl is superior and provides highest PL response together with carrier concentrations below p = 10¹⁶ cm^-3. Even though the concept of coordinative saturation is promising, results achieved by TIBAl showed that trialkyls could also be well suited for AlGaAs, assuming that they are properly synthesized.     

New approach to capacitance spectroscopy for interface characterization of a-Si:H/c-Si heterojunctions

A new technique for characterization of interface defects in a-Si:H/c-Si heterostructure solar cells from capacitance spectroscopy measurements under illumination at forward bias close to open-circuit voltage is described. The proposed method allows to significantly increase the sensitivity to interface defects compared to conventional capacitance measurements at zero or small negative bias. Results of numerical modelling as well as experimental data obtained on n-type a-Si:H/p-type c-Si heterojunctions are presented. The sensitivity of the proposed method to interface states and the influence of various parameters like band mismatch, density of interface defects, recombination velocity at the back contact are discussed.     

New insights on the thermodynamic barrier for nucleation in glasses: The case of lithium disilicate

An analysis is performed of the temperature dependence of the thermodynamic barrier to nucleation, W*(T), calculated from a fit of lithium disilicate glass data to the classical theory of nucleation. It is shown that, in order to obtain a satisfactory agreement between experimental and theoretical determinations of W*(T), lower values must be assigned to both the thermodynamic driving force and the surface energy as compared with the corresponding macroscopic values. This finding is consistent with theoretical considerations taking into account the effect that, in general, both the bulk and surface properties of the critical nuclei differ considerably from the respective properties of the newly evolving macroscopic phases. In addition, an anomalous increase of W*(T) with decreasing temperature is found near the glass transition interval. This increase is interpreted as a result of the effect of elastic strain on the thermodynamic driving force. The values of elastic strain energy estimated from the low temperature behavior of W*(T) are congruent with those calculated using the elastic constants of glass and crystal.     

Preparation and Characterization of 3-Acetamide-4-N-Cyclooctylamino-Nitrobenzene Crystals: A New Organic Material for Nonlinear Optics

The preparation, characterization (UV/VIS, IR, Mass, ¹HNMR, and ¹³CNMR-DEPT, heteronuclear multiple quantum correlation (HMQC), X-ray diffraction and DSC), measurements of optical second-harmonic generation SGH and dielectric studies of 3-acetamide-4-N-cyclooctylamine-mitrobenzene (ACN), a new organic molecular crystal with potential applications in nonlinear optics are reported.     

Benzo-1,3,2-Dithiazol-2-YL and its Derivatives: A New Class of Donor Molecules for Highly Conducting Charge Transfer Complexes

Abstract

Benzo-1,3,2-dithiazol-2-yl and its derivatives form charge transfer complexes with tetracyanoquinodimethane; their powder conductivities are as high as 3 Ω^?1 cm^?1.     

New Structure for Photoconductive Antennas Based on {LTG-GaAs/GaAs:Si} Superlattice on GaAs(111)A Substrate

Crystallography Reports - The structural characteristics of a new structure for photoconductive antennas have been investigated. This structure is a multilayered epitaxial film grown on a...     

New TiO2 precursor for TiO2:poly(N-vinylcarbazole) (PVK) thin film: Synthesis and reactivity to hydrolysis of titanium tetrakis (9H-carbazole-9-yl-ethyl-oxy)

The chemical reactivity of the ligand initially coordinated on the TiO₂ precursor plays a decisive role in the morphology of TiO₂:poly(N-vinylcarbazole) (PVK) thin film elaborated by in situ generation of the inorganic phase in the polymer matrix. The final aim of this study is to prepare a new nanocomposite TiO₂:poly(N-vinylcarbazole) (PVK) thin film from hydrolysis-condensation of titanium alkoxide in polymer thin film. In this context, we synthesized a new TiO₂ precursor, the tetrakis (9H-carbazole-9-yl-ethyl-oxy) [Ti(OeCarb)₄], bearing ligands close to the repetitive unit structure of the PVK to improve the interaction between both materials. In this study, the synthesis and reactivity to hydrolysis of Ti(OeCarb)₄ is presented. Ti(OeCarb)₄ was elaborated from alcoholysis reaction between titanium isopropoxide [Ti(ⁱOPr)₄] and 9H-carbazole-9-ethanol (ECOH) and identified by ¹H and ¹³C NMR spectroscopy. The reactivity to hydrolysis-oxolation of Ti(OeCarb)₄ was evaluated first in aqueous media by in situ ¹H NMR spectroscopy analysis. Moreover, reactivity of Ti(OeCarb)₄ to surrounding humidity was evaluated in thin film by X-ray photoelectron spectroscopy (XPS). Results show that steric hindrance of 9H-carbazole-9-yl-ethyl-oxide ligands do not influence the hydrolysis-condensation process in aqueous media in our experimental conditions when compared to [Ti(ⁱOPr)₄] but decrease the reactivity when the precursor is simply exposed to air humidity.     

New multicell model for describing the atomic structure of La<Subscript>3</Subscript>Ga<Subscript>5</Subscript>SiO<Subscript>14</Subscript> piezoelectric crystal: Unit cells of different compositions in the same single crystal

Accurate X-ray diffraction study of langasite (La₃Ga₅SiO₁₄) single crystal has been performed using the data obtained on a diffractometer equipped with a CCD area detector at 295 and 90.5 K. Within the known La₃Ga₅SiO₁₄ model, Ga and Si cations jointly occupy the 2d site. A new model of a “multicell” consisting of two different unit cells is proposed. Gallium atoms occupy the 2d site in one of these cells, and silicon atoms occupy this site in the other cell; all other atoms correspondingly coordinate these cations. This structure implements various physical properties exhibited by langasite family crystals. The conclusions are based on processing four data sets obtained with a high resolution (sin θ/λ ≤ 1.35 Å^–1), the results reproduced in repeated experiments, and the high relative precision of the study (sp. gr. P321, Z = 1; at 295 K, a = 8.1652(6) Å, c = 5.0958(5) Å, R/wR = 0.68/0.68%, 3927 independent reflections; at 90.5 K, a = 8.1559(4) Å, c = 5.0913(6) Å, R/wR = 0.92/0.93%, 3928 reflections).