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Although pyrite (FeS2) is abundant, getting a single-phase pyrite thin film is difficult due to the coexistence of various phases of iron and sulfur in nature. We propose an ink-based process for attaining the pyrite phase of iron sulfide. This work involves degassing Iron (II) chloride in an octadecylamine solution and later reflux with addition of sulfur in diphenyl ether at 200°C. The process yielded phase-pure single crystalline pyrite nanocrystals which were later cleaned and dispersed in chloroform for uniform suspension. Thus obtained nanocrystals were deposited as thin films using drop casting and spin coating. Solar cells were fabricated using CdS as an n-type window layer in a superstrate configuration. When tested, the superstrate type FeS2 nanoparticle cell showed 0.03% with high Voc of 565 mV.
One of the most important problems in the synthesis of carbon nanotubes is the problem of controlling their morphology, namely: length, aspect ratio, alignment, etc. Catalytic synthesis of carbon nanotubes in a suspended bed reactor allowed to study the possibilities of controlling the growth of nanotubes by introducing a certain amount of water vapor and carbon-containing materials in the reaction zone. The synthesized long carbon nanotubes were studied by Raman spectroscopy, transmission and scanning electron microscopy. We found that water concentration influences both yield and the structure of nanotubes. It is shown that the yield of centimeter-long nanotubes can be maximized at an optimum H2O/C ratio, while deviations dramatically change morphology and thickness of the nanotubes.
Luminescence nanocrystals or quantum dots give grate potential for bio-analysis as well as optoelectronics. Here we report an effective and non-expensive fabrication method of silicon carbide nanocrystals, with diameter below 10 nm, based on electroless wet chemical etching. Our samples show strong violet-blue emission in the 410-450 nm region depending on the used solvents and particle size. Raman and infrared measurements suggest the varied nature of surfaces of silicon carbide nanocrystals which elucidate the behavior of the silicon carbide colloid solvents and also give opportunity to modify the surface easily for specific biological, medical or other application.
Titanium diboride has been sintered using spark plasma sintering (SPS). With the addition of tetragonal Al3Ti or cubic (Al,Ni)3Ti, the Vickers hardness, Hv, of TiB2 increases up to as high as 2000 by the sintering at 1273K, while that of the sample sintered without additives is as low as 20. Such a remarkable improvement is caused by the improvement of direct link between TiB2 grains in addition to the effect that Al3Ti or (Al,Ni)3Ti fills in the space between TiB2 grains and act as a binder.
We have investigated the photoluminescence properties of ZnO grown on sapphire substrates via the thermal oxidation of Zn-metal films at various temperatures and thicknesses. X-ray diffraction (XRD) spectra indicate that the resulting films possess a polycrystalline hexagonal wurtzite structure without preferred orientation. For films having a thickness of 200 nm, crystal grain size was observed to decrease with increasing annealing temperature up to 600ºC, and then increase at higher temperatures. Thicker films demonstrated a modest increase in grain size as temperature increased from 300ºC to 1200ºC. The influence of film thickness on the optical properties was investigated using room temperature photoluminescence (PL). Specifically, PL spectra indicate four emission bands: excitonic ultraviolet, blue, and deep-level green and yellow emission. The strongest UV emission and narrowest full width at half maximum (0.09 eV) was observed for films having a thickness of 200 nm and annealed at low temperature (300ºC). As film thickness decreased, we observed the emergence of blue emission. The emergence of blue emission when depletion width grows relative to the bulk suggests that the origin of the blue emission is related to the negatively charged Zinc interstitials found within the deletion region near the interface.
The phase formation in the zone of directional laser irradiation of compacted Al2O3–TiO2–Y2O3 mixtures has been investigated. It is established that phase formation is carried out within the framework of binary mixtures Al2O3 – Y2O3 and Y2O3 – TiO2.
Ta doped SnO2 (TTO) films prepared on quartz glass substrates at 200 °C were annealed in the air to investigate the annealing effect on the structural, the optical, and the electrical properties. It is shown that the annealing for TTO films resulted in beneficial effect on the electrical resistivity by improving the carrier density and Hall mobility. The lowest resistivity was 1.4 × 10-3Ω cm obtained at 400 °C annealing temperature. The scattering mechanism in TTO films was discussed from the optical and electrical perspectives. The variation in Hall mobility with increasing the annealing temperature may be attributed to the scattering from the ionized and neutral impurities in TTO films.
We study the photocurrent from photoexcited charged carriers excited with lasers of energy both above and below the energy gap in CdS nanostructures. We observe non-linear photocurrents in CdS nanosheet devices in the metal-semiconductor-metal configuration with Schottky contacts for sub-band gap excitations. Analysis of two-photon absorption dominated photocurrents reveals a nonlinear coefficient of β = 2 cm/GW for these nanosheet devices, which is comparable to those of bulk CdS. We demonstrate the use of the photocurrent polarization measurements to determine the orientation of atoms in the nanosheet.
To develop alternative and low cost photovoltaic technologies we have synthesized CuInS2 nanocrystals with tunable optical properties and characterization was carried out thoroughly with TEM, SEM, EDAX and XRD. Furthermore large self-organized arrays of TiO2 nanotubes were fabricated on Ti foil followed by simple electrochemical anodization technique and characterized their structure by SEM and then for the first time coupled both the nanocrystals and nanotubes to form a p-n junction type photovoltaic device. The current-voltage (I-V) characteristics of photovoltaic cells were measured to test the proof of concept. Some preliminary experiments showed that device generates some current upon illumination. However, in our case we fabricated a device without sandwiching any buffer or barrier layers in between nanocrystals and nanotube arrays. We have been optimizing our solar cells efficiency by improving quality of nanotubes and nanocrystals. Some of the interesting finding are presented and discussed.
In this work, thermoluminescence (TL) characteristics of roof tile ceramic samples previously exposed to beta radiation are reported for the very first time. TL measurements were carried out using powdered samples obtained by the the fine-grained method, with grain size ranged from 300 nm to 5 μm. Characteristic thermoluminescence glow curves showed a complex structure with a dosimetric maximum located at ~ 200 °C. TL response of roof tile samples increases as the radiation dose increases in the 25 Gy to 1.6 kGy range. One response showed a linear behaviour, with no evidence of saturation within the dose interval investigated. The entire TL glow curve exhibited a remarkable reusability during 10 consecutive irradiation-TL readout cycles. The total TL signal showed a very low fading and remained almost constant after 3 h of irradiation and the corresponding TL readout. TL dosimetry features of powdered roof tile place it as a promising material in retrospective dosimetry as well as in possible TL dating applications.
The paper presents the results of PL spectrum analysis of CdSe/ZnS QDs covered by PEG polymer with and without bioconjugation to bio-molecules .– the Osteopontin antibodies. Commercial CdSe/ZnS QDs used in the study are characterized by the color emission with the maximum at 640 nm (1.96 eV) at 300K. It is shown that PL spectra of nonconjugated QDs can be presented as a superposition of PL bands related to exciton emission in the CdSe core (1.96 eV) and some high energy PL bands (in the spectral range 2.37 .– 3.00 eV). The comparative study of PL spectrum at high (300K) and low (10K) temperatures has testified that high energy PL bands deal with electronhole emission via interface states at the CdSe/ZnS/polymer interfaces.
It is revealed that the QD bioconjugation to the anti Osteopontin antibody is accompanied by the change dramatically in PL spectra. Main features of PL spectrum transformstions deal with decreasing the PL intensity of interface related PL bands and the rise of intensity of CdSe core related PL bands. The explanation of mentioned effects has been proposed on the base of re-charging of interface related states at the bioconjugation process.
Nanorod arrays of chromium (Cr) were grown on glassy carbon (GC) electrodes by a dc magnetron sputtering glancing angle deposition (GLAD) technique. The Cr nanorods were used as low-cost, high surface area, metallic supports for a conformal layer of Pt thin film catalyst, as a potential low-loading electrocatalyst for the oxygen reduction reaction (ORR) in polymer electrolyte membrane (PEM) fuel cells. A dc magnetron sputtering small angle deposition (SAD) technique was utilized for a conformal coating of Pt on Cr nanorods. The ORR activity of SAD-Pt/GLAD-Cr electrodes was investigated using cyclic voltammetry (CV) and rotating-disk electrode (RDE) techniques in a 0.1 M HClO4 solution at room temperature. A reference sample consisting of GLAD Cr nanorods coated with a Pt thin film deposited at normal incidence (θ = 0o) was prepared and compared with the SAD-Pt/GLAD-Cr nanorods. Compared to GLAD Cr nanorods coated with Pt thin film at θ = 0o, the SAD-Pt/GLAD-Cr nanorod electrode exhibited higher ECSA and area-specific and mass-specific ORR activity. These results indicate that the growth of catalyst layer on the base-metal nanorods by the SAD technique provides a more conformal and possibly a nanostructured coating, significantly enhancing the catalyst utilization.
We show a novel, bioengineered, moldable platform for bone regeneration composed of porous bionanocomposite scaffolds made of components that are normally found in bone tissue (calcium, collagen, carbonate, sodium, and phosphorous). To accommodate high- or low-stress environments, the hardness and modulus (stiffness) of these scaffolds can be tuned in a wide range in Megapascal (MPa) to Gigapascal (GPa) regions, while maintaining the required viscoelasticity. Our approach to control the mechanical properties is based on a new formulation of mineralized bioscaffolds by incorporation of calcium carbonate in which, calcium and phosphorous are in the form of calcite, calcium polyphosphate (CPP) and hydroxyapatite (HAP). The variation in the calcium carbonate concentration allows tuning of calcite/CPP contents in the bioscaffold to tailor the degree of mineralization and mechanical and viscoelastic properties that closely match those of natural bone. Our results demonstrate an ideal framework for new bone scaffold designs for advanced bone substitute applications.
Uranyl adsorption/reduction by Fe2+ on hematite and pyrite has been studied at neutral pH under anoxic and CO2-free conditions. XPS results confirm that more U3O8 precipitates on hematite than on pyrite reacted for 24 h in 160 μM uranyl nitrate and 160 μM Fe2+ solution at initial pH 7.3. These results are explained in terms of co-adsorption energy and U atom Mulliken charge transfer by quantum mechanical calculations. Moreover, in situ fluid tapping-mode AFM experiments on hematite indicate a deceleration of the U reduction rate within 24 h due to the passivation of the surface caused by the formation of orthorhombic U3O8 crystals. In addition, crystals observed using AFM show morphologies of orthorhombic schoepite appearing on hematite after 5 h.
For the first time, we have used a metal oxide-coated quartz crystal microbalance (QCM) to measure Cs+ adsorption onto illuminated and un-illuminated mesoporous TiO2 (m-TiO2) films by microgravimetric means in-situ. In the simplest case, such experiments yield two parameters of interest: K, the Langmuir adsorption coefficient and mmax the maximum mass of adsorbate to form a complete monolayer at the m-TiO2-coated quartz crystal piezoelectric surface. Importantly, we have found that illumination of the m-TiO2 film with ultra bandgap light results in an increase in mmax i.e. illumination allows for greater adsorption of substrate to occur than in the dark. Our studies also show that under illumination, K also increases indicating a higher affinity for surface adsorption. The photoinduced change in mmax and K are thought to be due to an increase in surface bound titanol groups, thus increasing the number of available adsorption sites – and so providing evidence to support the notion of photoinduced adsorption processes in photocatalytic systems. These findings have implications for the development of a reversible adsorption based microgravimetric sensor for Cs+.
Macrosegregation is harmful to the material properties (strength, corrosion resistance, etc.) and it must be avoided or eliminated from castings. In this work, macrosegregation behavior is evaluated in terms of silicon concentration in cast ingots of steels with 0.5, 1.5 and 3 wt% Si. The dimensions of the castings are 25x30x12.5 cm. The Si segregation profiles are evaluated in three zones: upper, middle and bottom of each ingot. The characterization is carried out by energy dispersive spectrometry in at least 10 positions of each zone of the ingot. Silicon analysis is evaluated from the surface to the centre of each ingot. The experimental results are compared with predictions using an Experimental Segregation Index (ESI) and the Scheil Segregation Index (SSI). The experimental results show a strong deviation from the profiles predicted by the Scheil model. The evaluation of the degree of segregation by "ESI" indicates little variation of silicon from the surface to the center of the ingot showing a uniform distribution across the ingot analyzed.
We present the fabrication and characterization of transparent thin film heaters (TTFHs) based on silver nanowires. The goal is to develop a simple process for the production of transparent heating elements by large area printing techniques. The TTFHs are based on recently developed random networks of silver nanowires. Thanks to the very low sheet resistance achievable with silver nanowires, we show that it is possible to obtain high heating rates and good steady state temperatures at low voltages, typically below 12 V.
Increasing concentrations of selenium oxoanions in the environment are placing many animals at risk for reproduction failure and deformities. The understanding of binding mechanisms of selenium oxoanions to iron and manganese based oxide minerals could lead to enhanced understanding of selenium mobility in the environment. In this study, the binding mechanisms of selenium oxoanions, selenite and selenate, to non microwave-assisted and microwave-assisted synthetic Fe3O4, Mn3O4, and MnFe2O4 nanomaterials were investigated through the use of X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) spectroscopy studies revealed the oxidation state of selenite and selenate remains the same after binding occurs to all nanomaterials in pH 2, 4, or 6 environments. The binding modes of selenite and selenate were determined to be bidentate binuclear through use of Extended x-ray absorption fine structure (EXAFS) and were independent of nanomaterials, synthetic technique, and pH.
Poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes are prepared by a novel ultrashort galvanic pulse electropolymerization technique for application in solid-state supercapacitors. Microstructure studies using scanning electron microscopy (SEM) show that PEDOT electrodes deposited by pulse polymerization are highly porous as compared to the conventional potentiostatic polymerization. In addition, as revealed by the X-ray photoelectron spectroscopy (XPS) studies in the PEDOT films formed by pulse polymerization, the polymer chains are fully conjugated with the dopant ClO4- ions. Solid-state supercapacitor cells using pulse polymerized PEDOT electrodes and ionic liquid gel polymer electrolyte were fabricated and characterized. The impedance spectroscopy studies show that the pulse polymerized PEDOT electrode have specific capacitance value of ∼ 65 F g-1 as compared to ∼52 F g-1for potentiostatically polymerized PEDOT and significantly lower interfacial and charge transfer resistance. Cyclic voltammetry (CV) and galvanostatic charge-discharge characterization show highly capacitive behavior of the supercapacitor cells in the solid-state configuration.
Two technological processes of synthesis of nanopowders containing Al2O3, AlN, and AlON have been investigated. It has been established that AlN nanoparticles formed on the base of ablation products (Al and N2) during laser irradiation of AlN targets are coated with AlON films of different composition and have a complex surface defective structure. In composite powders obtained by carbothermal reduction of Al2O3, along with AlN and AlON, initial oxide Al2O3 is present, which indicates the incompleteness of the process.