A promising candidate material for a H2 permeable membrane is SiC due to its many unique properties. Ahydrogen-selective SiC membrane was successfully fabricated on the outer surface of an intermediate multilayer γ-Al2O3 witha graded structure. The γ-Al2O3 multilayer was formed on top of a macroporous α-Al2O3 support by consecutively dipping intoa set of successive solutions containing boehmite sols of different particle sizes and then calcining. The boehmite sols wereprepared from an aluminum isopropoxide precursor and heated to 80oC with high speed stirring for 24 hrs to hydrolyze theprecursor. Then the solutions were refluxed at 92oC for 20 hrs to form a boehmite precipitate. The particle size of the boehmitesols was controlled according to various experimental parameters, such as acid types and acid concentrations. The topmost SiClayer was formed on top of the intermediate γ-Al2O3 by pyrolysis of a SiC precursor, polycarbosilane, in an Ar atmosphere. Theresulting amorphous SiC-on-Al2O3 composite membrane pyrolyzed at 900oC possessed a high H2 permeability of 3.61×10−7mol·m−2·s−1·Pa−1 and the H2/CO2 selectivity was much higher than the theoretical value of 4.69 in all permeation temperatureranges. Gas permeabilities through a SiC membrane are affected by Knudsen diffusion and a surface diffusion mechanism,which are based on the molecular weight of gas species and movement of adsorbed gas molecules on the surface of the pores.
Adsorption of a water molecule on a Si (001) surface and its dissociation were studied using density functional theory to study the distribution of -OH fragments on the Si surface. The Si (001) surface was composed of Si dimers, which buckle in a zigzag pattern below the order-disorder transition temperature to reduce the surface energy. When a water molecule approached the Si surface, the O atom of the water molecule favored the down-buckled Si atom, and the H atom of the water molecule favored the up-buckled Si atom. This is explained by the attractions between the negatively charged O of the water and the positively charged down-buckled Si atom and between the positively charged H of the water and the negatively charged up-buckled Si atom. Following the adsorption of the first water molecule on the surface, a second water molecule adsorbed on either the inter-dimer or intra-dimer site of the Si dimer. The dipole-dipole interaction of the two adsorbed water molecules led to the formation of the water dimer, and the dissociation of the water molecules occurred easily below the order-disorder transition temperature. Therefore, the 1/2 monolayer of -OH on the water-terminated Si (001) surface shows a regular distribution. The results shed light on the atomic layer deposition process of alternate gate dielectric materials, such as HfO2.
We studied the initial reaction mechanism of Zn precursors, namely, di-methylzinc (Zn(CH3)2, DMZ) and diethylzinc (Zn(C2H5)2, DEZ), for zinc oxide thin-film growth on a Si (001) surface using density functional theory. We calculated the migration and reaction energy barriers for DMZ and DEZ on a fully hydroxylized Si (001) surface. The Zn atom of DMZ or DEZ was adsorbed on an O atom of a hydroxyl (-OH) due to the lone pair electrons of the O atom on the Si (001) surface. The adsorbed DMZ or DEZ migrated to all available surface sites, and rotated on the O atom with low energy barriers in the range of 0.00-0.13 eV. We considered the DMZ or DEZ reaction at all available surface sites. The rotated and migrated DMZs reacted with the nearest -OH to produce a uni-methylzinc (-ZnCH3, UMZ) group and methane (CH4) with energy barriers in the range of 0.53-0.78 eV. In the case of the DEZs, smaller energy barriers in the range of 0.21-0.35 eV were needed for its reaction to produce a uni-ethylzinc (-ZnC2H5, UEZ) group and ethane (C2H6). Therefore, DEZ is preferred to DMZ due to its lower energy barrier for the surface reaction.
Composites of ceramic powders and an elastomer-based matrix were prepared by mixing CaCO3 powders with polyethylene and polypropylene elastomers, and their mechanical and sound insulation properties were measured. CaCO3 powders with 0.7 μm and 35 μm particle size were added to elastomers up to 80 wt%. Scanning electron microscopy photographs showed uniform distribution of the CaCO3 powders in the matrix. While density and surface hardness increased, melt index, tensile strength and elongation of the composites decreased as the amount of added CaCO3 powders increased. As more CaCO3 powders were added sound transmission loss of the composites increased owing to the increase of density. Addition of 0.7 μm sized CaCO3 powders resulted in a slightly higher transmission loss than the addition of 35 μm sized powders because of the increased interface area between the elastomer matrix and the CaCO3 powders. Composites with a polyethylene matrix showed higher transmission loss than those with a polypropylene matrix because the tensile strength and hardness of the polyethylene-based composites were low and their elongation was high.
Al2O3 has received wide attention with established use as a catalyst and growing application in structural or functional ceramic materials. On the other hand, the boehmite (AlO(OH)) obtained by sol-gel process has exhibited a decrease in surface area during phase transformation due to a decline in surface active site at high temperature. In this work, Al2O3-CuO/ZnO (ACZ) and Al2O3-CuO/CeO (ACC) composite materials were synthesized with aluminum isopropoxide, copper (II) nitrate hemi (pentahydrate), and cerium (III) nitrate hexahydrate or zinc (II) nitrate hexahydrate. Moreover, the Span 80 as the template block copolymer was added to the ACZ/ACC composition to make nano size particles and to keep increasing the surface area. The ACZ/ACC synthesized powders were characterized by Thermogravimetry-Differential Thermal analysis (TG/DTA), X-ray Diffractometer (XRD), Field-Emmision Scanning Electron Microscope (FE-SEM), Bruner-Emmett-Teller (BET) surface analysis and thermal electrical conductivity (ZEM-2:M8/L). An enhancement of surface area with the addition to Span 80 surfactant was observed in the ACZ powders from 105 m2/g to 142 m2/g, and the ACC powders from 103 m2/g to 140 m2/g, respectively.
A series of molecular dynamic (MD), finite element (FE) and ab initio simulations are carried out to establish suitable modeling schemes for the continuum-based analysis of aluminum matrix nanocomposites reinforced with carbon nanotubes (CNTs). From a comparison of the MD with FE models and inferences based on bond structures and electron distributions, we propose that the effective thickness of a CNT wall for its continuum representation should be related to the graphitic inter-planar spacing of 3.4Å. We also show that shell element representation of a CNT structure in the FE models properly simulated the carbon-carbon covalent bonding and long-range interactions in terms of the load-displacement behaviors. Estimation of the effective interfacial elastic properties by ab initio simulations showed that the in-plane interfacial bond strength is negligibly weaker than the normal counterpart due to the nature of the weak secondary bonding at the CNT-Al interface. Therefore, we suggest that a third-phase solid element representation of the CNT-Al interface in nanocomposites is not physically meaningful and that spring or bar element representation of the weak interfacial bonding would be more appropriate as in the cases of polymer matrix counterparts. The possibility of treating the interface as a simply contacted phase boundary is also discussed.
To fabricate TiO2 nanoparticle-based dye sensitized solar cells (DSSCs) at a low-temperature, DSSCs were fabricated using hydropolymer and ZnO nanoparticles composites for the electron transport layer around a low-temperature (200˚C). ZnO nanoparticle with 20 nm and 60 nm diameter were used and Pt was deposited as a counter electrode on ITO/glass using an RF magnetron sputtering. We investigate the effect of ZnO nanoparticle concentration in hydropolymer and ZnO nanoparticle solution on the photoconversion performance of the low temperature fabricated (200˚C) DSSCs. Using cis-bis(isothiocyanato)bis(2,20 bipyridy1-4,40 dicarboxylato) ruthenium (II) bis-tetrabutylammonium (N719) dye as a sensitizer, the corresponding device performance and photo-physical characteristics are investigated through conventional physical characterization techniques. The effect of thickness of the ZnO photoelectrode and the morphology of the ZnO nanoparticles with the variations of hydropolymer to ZnO ratio on the photoconversion performance are also investigated. The morphology of the ZnO layer after sintering was examined using a field emission scanning electron microscope (FE-SEM). 60 nm ZnO nanoparticle DSSCs showed an incident photon-to-current conversion efficiency (IPCE) value of about 7% higher than that of 20 nm ZnO nanoparticle DSSCs. The maximum parameters of the short circuit current density (Jsc), the open circuit potential (Voc), fill factor (ff), and efficiency (η) in the 60 nm ZnO nanoparticle-based DSSC devices were 4.93 mA/cm2, 0.56V, 0.40, and 1.12%, respectively.
Geopolymer is a term covering a class of synthetic aluminosilicate materials with potential use in a number of areas, but mainly as a replacement for Portland cement. In this study, geopolymers with fly ash and meta kaolin were prepared using KOH as an alkali activator and water glass. The effect of water glass on the microstructures and the compressive strength of the geopolymer was investigated. As the amount of water glass increased, the dissolved inorganic binder particles in the geopolymers increased due to polymerization, resulting in a dense microstructure. The meta kaolin-based geopolymer showed a better extent of polymerization and densification than that of the fly ash-based geopolymer. XRD data also suggested that polymerization in meta kaolin-based geopolymers should be active resulting in the formation of an amorphous phase with an increasing amount of water glass. The compressive strength of the geopolymer was also dependent on the amount of water glass. The compressive strength of the geopolymers from both fly ash and meta kaolin increased with an increasing amount of water glass because water glass improved the extent of polymerization of the inorganic binder and resulted in a dense microstructure. However, the addition of water glass to the geopolymer did not seem to be effective for the improvement of compressive strength because the meta kaolin-based geopolymer mainly consisted of a clay component. For this reason, the fly ash-based geopolymer showed a higher value of compressive strength than the meta-kaolin geopolymer.
Tin oxide thin films were prepared on borosilicate glass by rf reactive sputtering at different deposition powers, process pressures and substrate temperatures. The ratio of oxygen/argon gas flow was fixed as 10 sccm / 60 sccm in this study. The structural, electrical and optical properties were examined by the design of experiment to evaluate the optimized processing conditions. The Taguchi method was used in this study. The films were characterized by X-ray diffraction, UV-Vis spectrometer, Hall effect measurements and atomic force microscope. Tin oxide thin films exhibited three types of crystal structures, namely, amorphous, SnO and SnO2. In the case of amorphous thin films the optical band gap was widely spread from 2.30 to 3.36 eV and showed n-type conductivity. While the SnO thin films had an optical band gap of 2.24-2.49 eV and revealed p-type conductivity, the SnO2 thin films showed an optical band gap of 3.33-3.63 eV and n-type conductivity. Among the three process parameters, the plasma power had the most impact on changing the structural, electrical and optical properties of the tin oxide thin films. It was also found that the grain size of the tin oxide thin films was dependent on the substrate temperature. However, the substrate temperature has very little effect on electrical and optical properties.