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A novel method for introducing quaternary ammonium-bearing side chains has been developed and applied to a polybenzimidazole backbone to generate new anionic-exchange polymers, TMHA-m-FPBI where m = the degree of substitution of available sites (values ranging from 74 to 100%). These polymers have been shown to exhibit hydroxide ion conductivities up to 34 mS cm-1 in hydrated membranes at ambient temperature and 13 mS cm-1 at 60 °C, RH = 95%. Immersion of these polymers in 2 M KOH at 60 °C has shown they remain stable with no sign of chemical structure degradation to a period of at least 15 days.
A chemical decomposition and related phase transformation have been observed in 2.2 GeV 197Au irradiated SnO2 nanopowder. X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM) were used to characterize the transformation from tetragonal SnO2 (P42/mnm) into tetragonal SnO (P4/nmm). Rietveld refinement of the XRD data determined the structures and proportion of these phases up to a fluence of 2.4×1013 ions/cm2. The initially intense diffraction maxima corresponding to SnO2 gradually decrease in intensity with an increase in fluence. At a fluence of approximately 3.9×1012 ions/cm2, diffraction maxima corresponding to SnO become clearly evident and increase in intensity as fluence increases. Both Raman and TEM analyses confirm the transformation from tetragonal SnO2 to SnO. The XRD refinement results are consistent with a multiple-impact model of transformation, confirmed by TEM as no single tracks were observed. Previous swift heavy ion irradiations of SnO2 have led only to changes in grain size, degrees of crystallinity, and the formation of “holes”. The inconsistency in results is discussed in depth. The proposed mechanism for the currently observed transformation is the interrelation of defect accumulation and thermal-spike mechanisms. The formation of SnO, apparent O loss from the transformation regions, and associated Sn reduction are discussed in terms of thermodynamic, kinetic, and thermal-spike model considerations.
Magnetic nanoparticles have drawn much attention due to their potential in magnetic recording as well as many biological and medical applications such as magnetic separation, hyperthermia treatment, magnetic resonance contrast enhancement and drug delivery. The magnetic fields generated by these nanoparticles can be used for diagnostics in Magnetic Resonance Imaging (MRI) etc. Manganese doped tin dioxide (SnO2:Mn) possess interesting physical and chemical properties. The physical and chemical properties of the particles themselves like the size, shape, crystallinity and composition, will control the magnetic properties and response of the particles to magnetic fields. Our work is rooted to control the properties of the particles as well as tailor their magnetic properties for specific applications. In this study, SnO2: Mn films with different Mn doping concentrations (0-3 mol%) were deposited on the glass substrates by sol-gel dip coating technique. XRD patterns shows tetragonal structure for all the SnO2:Mn films and crystallite size decreased as Mn doping concentration increased from 0 - 3 mol%. The magnetic property shows that pure SnO2 film is diamagnetic and 1- 3 mol% SnO2:Mn films posses room temperature ferromagnetism. The optical properties of the films revealed that transmittance of the films decreased with increase in Mn doping concentration. The optical energy band gap values (3.55 eV-3.71 eV) increased with the increase in Mn doping concentrations. Such SnO2:Mn films with structural, optical and magnetic properties can be used as dilute magnetic semiconductors.
In this paper, we report on a new micropillar sensor array that is stretchable, flexible, and has high sensitivity in the tactile sensing regime (<10 kPa). The sensor array is capable of detecting deformation modes other than pressure such as shear and planar extension. The capacitance-type sensor is fabricated using soft nanolithography whereby the micropillars are individually electroded using a sputtering technique. Buckled gold electrodes are used in this study to enable large sensor stretches up to 55%. Three micropillar aspect ratios were considered in this work (1:1, 1:2, 1:3). Here we present the highest reported sensitivity [0.8 kPa-1] of a capacitance type flexible/stretchable sensor. Our results show that this sensor is also able to detect very low pressures down to 5.4 Pa, which is in the range of ultra-low detection pressures recently reported. Finally, the microstructured sensor array naturally lends itself to the development of pixel-type pressure sensors. We present preliminary results for a 25 pixel array.
More than 50% of total input energy is wasted as heat in various industrial processes. If we could harness a small fraction of the waste heat while satisfying the economic demands of cost versus performance, then thermoelectric (TE) power generation could bring substantial positive impacts. To meet these demands single-crystal semiconductor nanowire networks have been investigated as a method to achieve advanced TE devices because of their predicted large reduction in thermal conductivity and increase in power factor.
To further our goal of developing practical and economical TE devices, we designed and developed a material platform that combined a semiconductor nanowire network and a semiconductor thin film integrated directly on a mechanically flexible metallic substrate. We assessed the potential of this platform by using indium phosphide (InP) nanowire networks and a doped poly-silicon (poly-Si) thin film combined on copper sheets. InP nanowires were grown by metal organic chemical vapor deposition (MOCVD). In the nanowire network, InP nanowires were grown in three-dimensional networks in which electrical charges and heat travel under the influence of their characteristic scattering mechanisms over a distance much longer than the mean length of the constituent nanowires. Subsequently, plasma-assisted CVD was utilized to form a poly-Si thin film to prevent electrical shorting when an ohmic copper top contact was made. An additional facet to this design is the utilization of multiple materials to address the various temperature ranges at which each material is most efficient at heat-to-energy conversion. The utilization of multiple materials could enable the enhancement of total power generation for a given temperature gradient. We investigated the use of poly-Si thin films combined with InP nanowires to enhance TE properties. TE power production and challenges of a large area nanowire device on a flexible metallic substrate were presented.
Colloidal dispersion of nanocarbon (NC) materials in dilute solutions or pastes is prerequisite for applications of NC-based electrodes from flexible electronics and flexible conducting fibers to electrochemical devices. Here, we show a straightforward method for fabricating NC suspensions with >10% weight concentrations in absence of organic dispersants. The method involves introducing supramolecular quadruple hydrogen bonding motifs into the NC materials without sacrificing the electrical conductivity.
A cross-linked copolymer was designed and synthesized bythe imidation of poly(oxyethylene)-diamine and 4,4’-oxydiphthalic anhydride, and followed by a late-stage curing to generate the cross-linked gels. The copolymers consisting of crosslinking sites and multiple functionalities such aspoly(oxyethylene)-segments, amido-acids, imides, and amine termini, characterized by Fourier Transform Infrared Spectroscopy. After the self-curing at 80 °C, the gel-like material enabled to absorb liquid form of electrolytesin the medium of propylene carbonate(PC), dimethylformamide(DMF),and N-methyl-2-pyrrolidone(NMP).By using a field emission scanning electronic microscope, we observed a 3D interconnected nanochannel microstructure, within which, the liquid electrolytes were absorbed. When the novel polymer gel electrolyte (PGE) was fabricated into a dye-sensitized solar cell (DSSC), an extremely high photovoltaic performance was demonstrated. The PGE, absorbed 76.7 wt% of the liquid electrolyte (soaking in the PC solution) based on the polymer’s weight gave rise to a power conversion efficiency of 8.31%, superior to that (7.89%) of the DSSC with liquid electrolytes. It was further demonstrated that the cell had a long-term stabilityduring the test of 1000hat-rest at room temperature or only slightly decreasing in efficiency of 5%.This is the first time demonstration for a PGE exhibiting a higher performance than its liquid counterpart cell. The observation is ascribed to the suppression of the back electron transfer through the unique morphology of the polymer microstructures.
Results are presented of a study of {113}-defect formation in Si nanowires withdiameters ranging from 50 to 500 nm. The Si nanowires, used for the processingof tunnel-FET's, are etched into a moderately doped epitaxial Si layeron a heavily doped n-type Si substrate. {113}- defects are created in situ by 2MeV e-irradiation at temperatures between room temperature and 375 °Cin an ultra high voltage electron microscope. The observations are discussed inthe frame of intrinsic point defect out-diffusion and interaction with dopantatoms.
The formation of native point defects in layered multicomponent InAMO4 oxides with A3+=Al or Ga, and M2+=Ca, Mg, or Zn, is investigated using first-principles density functional calculations. We calculated the formation energy of acceptor (cation vacancies, acceptor antisites) and donor (oxygen vacancy, donor antisites) defects within the structurally and chemically distinct layers of InAMO4 oxides. We find that the antisite donor defect, in particular, the A atom substituted on the M atom site (AM) in InAMO4 oxides, have lower formation energies, hence, higher concentrations, as compared to those of the oxygen vacancy which is know to be the major donor defect in binary constituent oxides. The major acceptor (electron “killer”) defects are cation vacancies except for InAlCaO4 where the antisite CaAl is the most abundant acceptor defect. The results of the defect formation analysis help explain the changes in the observed carrier concentrations as a function of chemical composition in InAMO4, and also why the InAlZnO4 samples are unstable under a wide range of growing conditions.
Magnetic nanoparticle-vesicle aggregates (MNPVs), a controlled release nanostructure, have been enhanced with the inclusion of a novel galactose terminated lipid for cell targeting. Quartz crystal microgravimetry with dissipation (QCM-D) demonstrated that the galactose headgroup was available to bind Erythrina Crista-galli lectin (ECL) when the lipid was incorporated into a lipid bilayer. Similarly, UV-visible spectrophotometry indicated that ECL recognized the galactose headgroup in vesicles, leading to vesicle adhesion and aggregation. Finally, confocal fluorescence microscopy was used to assess the galactose-mediated interaction of both vesicles and MNPVs with HepG2 human hepatocellular carcinoma cells expressing the asialoglycoprotein (ASGPR) galactose receptor.
This article reports on a new composite gypsum binder (CGB) with nanostructured silica-based admixture (NSS). NSS is obtained by a wet ultrafine milling of quartz sand resulting in the formation of an inorganic polydisperse binding system, which has a high concentration of active nanoscale phase (about 10%). Developed CGB contains hemihydrate gypsum and nano-component based on quartz sand. It is observed that the addition of 15–20 % of NSS improves the rheological properties of gypsum systems through the formation of solvate shells hindering the access of water to gypsum particles; this process also retards the setting of binder.
The experimental program used infrared IR spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) to reveal the contribution of NSS. The porosity of CGB is analyzed by the kinetics of water adsorption and BET. The XRD and IR investigations determined the formation of a new sulfosilicate phase, hydroxyellestadite during the hydration of CGB. With the addition of NSS an overall reduction in pore volume, as well as the shifts in macro-, meso- and nano- porosity values are observed.
Analysis of CGB microstructure reveals that in the presence of the NSS the size and morphology of crystals are changed contributing to the formation of dense fine-grained structure. Experimental studies have demonstrated that the composite gypsum binders with NSS are characterized by reduced water absorption and increased density, as well as improved mechanical performance especially, higher compressive strength.
It has been found that the hybrid materials are a compatible matrix for numerous organic compounds, such as organic dyes, laser dyes, and compounds that exhibit photo-chromic behavior and many more The epoxy-silica system seems to be an excellent matrix for organic dyes and a hybrid material suitable for to be used as coating on glass substrates with good adhesion properties. This work presents a systematic study of the effects of the different amount of using rhodamine 6G as dye on the structure and properties of epoxy–silica hybrids coatings synthesized by the sol-gel process. We have taken advantage on the high solubility of organic dyes in a hybrid organic–inorganic epoxy resin–silica (epoxy–SiO2) matrix to obtain homogeneous, hard and high optical quality red color films on glass substrates. The effects of the content of rhodamine 6 G on the optical and thermal properties of epoxy-silica hybrid films were also examined. Epoxy resin DER 332 cured with an amine (4,4 diamino diphenyl methane) was used as organic component and tetraethyl orthosilicate (TEOS) was used as precursor of the inorganic component. The results showed that at a concentration of rhodamine 0.05% coatings retain adhesion properties similar to coatings without colorant and the coatings are uniform and free of defects. These coatings have the potential to be used as filters and ornamental coatings.
Chondroitin sulfate (CS) is one of the major glycosaminoglycans (GAGs) present in the connective tissue extracellular matrix (ECM) and is responsible for the regulation of cellular activities as well as providing mechanical support for the surrounding tissue. Due to presence of CS in the natural tissues including cartilage, hydrogels of CS and other GAGs have been widely used in cartilage regeneration. Due to their polyelectrolyte nature, GAG-based hydrogels are brittle and require modifications to overcome the weak mechanical properties. In this work, we showed copolymerization of methacrylated chondroitin sulfate with oligo(ethylene glycol)s improved the crosslink density of the gels from 2 to 20 times depending on the methacrylation degree of CS and length of the crosslinking monomer. Copolymerization of CS with oligo(ethylene glycol) acrylates is a method to design hydrogels with tunable swelling and mechanical properties.
The improvement of concrete workability can provide a considerable reduction of production expenses and also leads to significant improvement of construction quality. This paper reports on the development of self-consolidating concrete (SCC) based on local materials, such as metakaolin (MK) and aggregate fines. The use of metakaolin in SCC is found to be very promising, due to its ability to increase the flowability and segregation resistance of concrete mixtures. Furthermore, due to pozzolanic properties, the application of MK provides an improvement of concrete microstructure, strength and durability. The proposed SCC design includes the optimization of aggregates and combined aggregate-binder powders to target 0.45- and 0.3- power particle size distributions, respectively.
Hydroxyapatite-chondroitin sulfate (HAp/ChS) composites were synthesized with calcium hydroxide suspension and phosphoric acid solution containing ChS through a precipitation method, and the microparticles were then fabricated by a spray dry method with the suspension of the composites. Bovine serum albumin (BSA) with negative charge or lysozyme (LYZ) with positive charge at pH7.0 was adsorbed onto the HAp/ChS microparticles. However, the HAp/ChS microparticles adsorbed LYZ more than the HAp microparticles compared with BSA due to the electrostatic interaction from negatively-charged sulfate or carboxyl group of ChS in the composites. The release property of BSA from the HAp/ChS microparticles was evaluated in Dulbecco’s phosphate buffered saline (pH7.2). The HAp/ChS microparticles released quickly 100% of the adsorbed BSA, while HAp microparticles released 45% of BSA. These results indicated that incorporation of ChS in the microparticles controls the adsorption and release properties of protein due to the electrostatic interaction. The HAp/ChS microparticles therefore are a candidate of a carrier for drugs like vaccines.
Electrical performance and reliability of SiC Junction Transistors (SJTs) and Schottky rectifiers are presented. The 650 V/50 A-rated SiC SJTs feature current gains (β) up to 110 at room-temperature, 70 at 250°C, and stable breakdown characteristics. Single current pulse measurements indicate an almost invariant β up to 800 A/cm2 at 175°C – a measure of the SOA boundary for pulsed current SJT operation. Lower than 5 mA/cm2 leakage currents are measured on the SJTs at the rated blocking voltage and at 250°C. 1200 V Schottky rectifiers designed for high-temperature operation display < 3 mA/cm2 leakage currents up to 250°C. A 10x reduction in leakage current and 23% reduction in junction capacitance are observed when compared to the nearest competitor. The high-temperature Schottky rectifiers and SJTs display stable breakdown voltages and on-state characteristics after long-term HTRB stressing. A significant improvement in current gain stability is achieved by fine-tuning the fabrication process.
Nanowire heterostructures comprised of cobalt oxide and tungsten oxide were fabricated in a core/shell configuration. This was achieved by sputter coating tungsten oxide shells on standing cobalt oxide nanowires on a substrate. To ensure the polycrystallinity of tungsten oxide shell, the nanowire heterostructures were subjected to post-sputtering annealing process. The cobalt oxide nanowires for this study were grown employing a thermal method via vapor-solid growth mechanism. The crystal structures, morphologies, dimensions, and phases at various growth stages of nanowire heterostructures were studied using high resolution electron microscopy, energy dispersive spectroscopy, and X-ray diffraction methods. The interfaces of these nanowire heterostructures were also studied and showed variation in the lattice spacing across the heterostructure diameter. Results indicated that the cobalt oxide nanowires survived multiple processing steps and resulted in stable heterostructure configurations. The investigation shows, for the first time, a dry processing route for the formation of such novel nanowire heterostructures.
This work presents a systematic rheological study of the gelatinization process of corn-starch plasticized with glycerol, showing the effects of the glycerol/starch ratio, water/starch ratio, and clay (montmorillonite) content. Gelatinization temperatures at different heating rates in rheological oscillatory temperature-sweep experiments were determined for different corn-starch/glycerol/clay formulations. The influences of the different formulation variables on the gelatinization processes and on the gel properties are analyzed. Some hypotheses postulating how the different intermolecular interactions present in the composites are responsible for these effects are discussed.
A mathematical model is developed to describe deoxidation of water in a physical model of a batch aluminum degassing reactor equipped with the rotor-injector technique, assuming that deoxidation kinetics of water is similar to dehydrogenization of liquid aluminum. Degassing kinetics is described by using mass transport and mass balance principles by assuming that degassing kinetics can be characterized by a mass transfer coefficient, which depends on the process variables. The transport coefficient and the average bubble diameter are estimated with correlations reported in the literature for similar gas-injection systems. The water physical model helped to validate the mathematical model and to perform a process analysis by varying: 1) Gas flow rate (20 and 40 l/min); and 2) Impeller’s angular velocity (290 and 573 rpm). Results from the model agree well with measurements of deoxidation kinetics at low impeller rotating speeds. At high rotating speeds the model is still valid but less reliable because it does not take into account the formation of the vortex at the free surface. Nevertheless, the model provides predictions of the influence of every operating parameter and it can be used as a good approximation for real systems.
Oxide thin films of zinc and titanium materials were deposited by different deposition techniques, to be applied as sensitive layers of pH sensor – EGFET device. The deposition techniques tested were dip-coat, spin-coat, electrodeposition and spray-pyrolysis. The routine and the parameters of each technique were changed aiming optimized the procedures. The pHs buffer solutions tested ranged from 2 to 12. ZnO thin film shows sensitivity about 23 mV/pH, while TiO2 thin films shows only 13.8 mV/pH. The final purpose of this study is to optimize the parameters for each deposition technique for both oxide materials.