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The comparison between bentonite-alginate beads and bentonite-alginate films in Cd(II) removal from aqueous solution was investigated. The experimental Cd(II) adsorption data were fitted to adsorption isotherm and kinetic models. Results showed that both bentonite-alginate film and beads were fitted better to the Langmuir isotherm model, the calculated saturation adsorption capacity for bentonite-alginate film was 59.9 mg/g as compared to 17.9 mg/g for the beads. The kinetic studies indicated that both samples followed the pseudo-second-order kinetic. The bentonite- alginate film showed higher adsorption capacity, rate constant as well as initial adsorption rate. This investigation showed that the adsorption behavior of both samples, in terms of adsorption isotherm and kinetic models, did not deviate significantly. The bentonite-alginate film has better performance in Cd(II) removal, attributed to the larger surface area which is exposed to the Cd(II) solution.
CIS based chalcopyrite absorber materials are usually substituted in the cation and anion lattice to yield mixed pentanary crystals with the general composition Cu(In,Ga)(Se,S)2 to achieve an optimised adaptation of the semiconductor bandgap to the terrestrial solar spectrum. Real-time investigations during the annealing of stacked elemental layers (SEL) of sputtered metals Cu and In and evaporated chalcogens S and Se with varying ratios were performed by angle-dispersive time-resolved XRD (X-ray diffraction) measurements. After qualitative phase analysis the measured powder diagrams were quantitatively analysed by the Rietveld method, the phases formed determined and their reaction kinetics obtained. Ternary indium and copper sulfoselenides form by the sulfoselenisation of the intermetallic alloy yielding different educts for the chalcopyrite formation with varying sulfur content. For S/(S+Se) ≥ 0.5 the formation of the chalcopyrite CuIn(S,Se)2 is similar to the crystallisation path of CuInS2. With increasing amount of selenium (S/(S+Se) = 0.25) different ternary sulfoselenides contribute to the semiconductor formation. For small amounts of sulfur, i.e. S/(S+Se) ≤ 0.1, the chalcopyrite crystallisation proceeds comparable to the one observed for sulfur-free Cu-In-Se precursors. The formation of CuIn(S,Se)2 is accelerated and proceeds mainly after the peritectic decomposition of Cu(S,Se) to Cu2(S,Se). The sulfur content determines the crystallisation temperature of the semiconductor because Cu(S,Se) decomposes at higher temperatures with increasing sulfur. Upon heating S ↔ Se exchange reactions take place in the Cu-S-Se and Cu-In-S-Se system.
The short circuit current and conversion efficiency of the poly(multi)-crystalline solar cells are increased by the passivation process using hydrogen plasma. The passivation rate apparently increases at a reverse bias voltage near 0.6V during the hydrogenation process. The effects of the bias voltage on the passivation are large at the substrate temperatures between 200C and 250C. The phenomena are likely due to the existence of positively-ionized hydrogen, H+. The H+ ions can be accelerated from the surface into the bulk by the electric field with the negative bias. The possibility of the H+ ions in the bulk silicon has been predicted in the previous reports. The increase of the incorporated hydrogen is confirmed by IR absorption measurements. The enhanced diffusion of hydrogen induced by the reverse bias is supported by the results of spectral response characteristics of the hydrogenated solar cells.
In this study, 1 μm thick polycrystalline CdTe films were deposited by magnetron sputtering using a variable argon pressure, 2.5 ≤ pAr ≤ 50 mTorr, and a fixed substrate temperature, Ts = 230°C. Real time spectroscopic ellipsometry (RTSE) was performed during deposition in order to analyze the nucleation and coalescence, as well as the evolution of the surface roughness thickness ds with bulk layer thickness db and the depth profile in the void volume fraction fv. A linear correlation was found between the final ds value measured by RTSE at the end of deposition and the root-mean-square (rms) surface roughness measured by atomic force microscopy (AFM) ex situ after deposition. A monotonic decrease in RTSE-determined roughness thickness is observed with decreasing Ar pressure from 18 to 2.5 mTorr. The lowest pressure also leads to the greatest bulk layer structural uniformity; in this case, fv increases to 0.04 with increasing CdTe thickness to 1 μm. The photovoltaic performance of CdTe films prepared with the lowest pressure of pAr = 2.5 mTorr is compared with that of previously optimized CdTe solar cells with pAr = 10 mTorr.
A powerful fabrication platform for a wide range of biomimetic, high-aspect-ratio nanostructured surfaces is introduced. The principles of soft lithography are extended into a double-mold replication process, whereby a master topography is mapped onto an elastomeric inverse mold and replicated in arbitrary multiple material and stiffness gradients, and an array of modified geometries. Control of geometry via deformation of the inverse mold and control of stiffness via prepolymer mixing are discussed. New capabilities enabled by our approach include biomimetic actuation/sensor arrays with programmable biases, precisely tunable mechanical and geometric properties for optical or wetting applications, and flexible curved substrates. Indeed, flexibly anchored ciliary high-aspect-ratio nanostructures are now possible, and a proof-of-principle is described.
Nanoporous devices constitute emerging platforms for selective molecule separation and sensing, with great potential for high throughput and economy in manufacturing and operation. Acting as mass transfer diodes similar to a solid-state device based on electron conduction, conical pores are shown to have superior performance characteristics compared to traditional cylindrical pores. Such phenomena, however, remain to be exploited for molecular separation. Here we present performance results from silicon membranes created by a new synthesis technique based on interferometric lithography. This method creates millimeter sized planar arrays of uniformly tapered nanopores in silicon with pore diameter 100 nm or smaller, ideally-suited for integration into a multi-scale microfluidic processing system. Molecular transport properties of these devices are compared against state-of-the-art polycarbonate track etched (PCTE) membranes. Mass transfer rates of up to fifteen-fold greater than commercial sieve technology are obtained. Complementary results from molecular dynamics simulations on molecular transport are reported.
Current biomaterials as a scaffold for bone regeneration are limited by the extent of degradation concurrent with bone formation, mechanical strength, and the extent of osteogenic differentiation of marrow stromal cells migrating from the surrounding tissues. In this project, a novel laminated nanocomposite scaffold is fabricated, consisting of poly (L-lactide ethylene oxide fumarate) (PLEOF) hydrogel reinforced with poly (L-lactide acid) (PLLA) electrospun nanofibers and hydroxyapatite (HA) nanoparticles. The laminated nanocomposites were fabricated by dry-hand lay up technique followed by compression molding and thermal crosslinking. The laminated nanocomposites were evaluated with respect to mechanical strength and osteogenic differentiation of marrow stromal (BMS) cells. Laminates showed modulus values much higher than that of hydrogel or fiber. The effect of laminated nanocomposites on osteogenic differentiation of BMS cells was determined in terms of ALPase activity and calcium content. Our results demonstrate that grafting RGD peptide to a PLEOF/HA hydrogel reinforced with PLLA nanofibers synergistically enhances osteogenic differentiation of BMS cells.
Coffinite (USiO4, I41/amd, Z=4) is the major alteration phase of uraninite, UO2+x, under reducing conditions in natural uranium deposits. Thus, it is important to understand the radiation response of coffinite because it is an expected alteration product of the UO2 in spent nuclear fuel. In the present study, we conducted in-situ transmission electron microscopy (TEM) investigation of synthetic coffinite under 1 MeV-Kr2+ ion beam irradiation. The radiation-induced crystalline-to-amorphous transformation was observed in the synthetic nanocrystalline USiO4, with a critical dose of ∼ 0.27 displacements per atoms (dpa) for which full amorphization occurred at room temperature. The critical dose increases as rising irradiation temperature, and above the critical temperature (Tc), ∼ 608 K, coffinite cannot be amorphized. These results are compared with previous studies on the isostructural zircon (ZrSiO4, Tc=1000K) and thorite (ThSiO4, Tc>1100K), which indicates that synthetic coffinite is more stable to ion beam irradiation at elevated temperature.
Cadmium telluride (CdTe) is a leading thin film photovoltaic (PV) material due to its near ideal band gap of 1.45 eV, its high optical absorption coefficient and availability of various device fabrication methods. Superstrate CdTe solar cells fabricated on glass have to-date exhibited efficiencies of 16.5%. Work on substrate devices has been limited due to difficulties associated with the formation of an ohmic contact with CdTe. Foil substrate curvature, flaking, delamination and adhesion as a result of compressive strain due to the coefficient of thermal expansion (CTE) mismatch between the flexible foil substrate and the solar cell films has been studied. Thin films have been characterized by AFM, XRD, SEM, ASTM D3359-08 tape test, and solar cells have been characterized using J-V and spectral measurements. Adhesion improves by minimizing the mismatch of the CTE . A CdCl2 treatment is important for high efficiency solar cells. The treatment influences the microstructure and interface properties of the layers. The effect of the current CdCl2 chemical treatment increases flaking and has to be optimized for the CdTe substrate cell on foil. We have also fabricated solar cells on tantalum, molybdenum and tungsten foils, all with lower CTEs than SS430. We are currently producing solar cells with a VOC of 630mV, a 50% fill factor and over 6.0% efficiency.
Optically pumped terahertz silicon lasers utilize transitions between shallow donor states at low lattice temperatures. Population inversion in these lasers is built-up due to selective relaxation routes of optically excited electrons into impurity ground state. Each relaxation step of the electron occurs under assistance of intervalley and intravalley phonons with energies approaching the particular energy gaps between interacting excited donor states. These impurity phonon interactions determine, at the end, the lifetimes of the laser levels, and, therefore, efficiency of intracenter silicon lasers. Deformation of silicon crystal is a classical example of controllable influence on energy spectrum of shallow donor levels due to specific splitting and shifts of conduction band valleys. Using moderate (up to 400 MPa) external uniaxial deformation of a crystal, one can radically modify the impurity spectra while the phononic spectra remain almost unchanged. We have demonstrated significant improvement of efficiency for intracenter silicon lasers followed by changes of lifetime for the upper and the lower laser levels due to moving the impurity levels either into or out of resonance with corresponding intervalley phonon frequencies.
In this paper, we report the development of AlGaN-based deep ultraviolet LEDs by rf plasma-assisted molecular beam epitaxy (MBE) emitting between 277 and 300 nm. Some of these devices were evaluated after fabrication at bare-die and some at wafer-level configurations. Devices with total optical output of 1.3 mW at injection current of 200 mA were produced, with maximum external quantum efficiency (EQE) of 0.16%. These performance values are equivalent to those reported for deep UV-LEDs grown by the Metalorganic chemical vapor deposition (MOCVD) method and measured at bare-die configuration. In parallel, we have evaluated the internal quantum efficiency (IQE) of AlGaN quantum wells, and found that such wells emitting at 250 nm have an IQE of 50%. From the analysis of these data, we concluded that the efficiency of deep UV LEDs is not limited by the IQE but by the light extraction efficiency, injection efficiency or a combination of both.
Hydrogen storage in advanced solid state materials has been an intense area of research due to many drawbacks in conventional high pressure or cryogenic liquid hydrogen storage methods. A practical hydrogen storing material is required to have high storage capacity and fast dehydrogenation kinetics. Among many solid state materials for hydrogen storage, magnesium hydride (MgH2) combines a hydrogen capacity of 7.6 wt % with the benefit of the low cost of production and abundance. The main difficulties for implementing MgH2 are slow absorption/desorption kinetics and high reactivity towards air and oxygen, which are also common issues in most lightweight metal hydrides. Previously, improvements in hydrogen storage and release properties have been reported by using nanostructured magnesium that can be obtained through various fabrication methods including ball-milling, mechanical alloying, and vapor transport. In this study, we investigate the hydrogen absorption and desorption properties of magnesium “nanotrees” fabricated by glancing angle deposition (GLAD) technique, and also conventional Mg thin films deposited at normal incidence. Mg nanotrees are about 15 μm long, 10 μm wide, and incorporate “nanoleaves” of about 20 nm in thickness and 1,2 μm in lateral width. A quartz crystal microbalance (QCM) gas absorption/desorption measurement system has been used for our hydrogen storage studies. Nanostructured and thin film Mg have been deposited directly on the surface of the gold coated unpolished quartz crystal samples. QCM hydrogen storage experiments have been performed at temperatures ranging between 100-300 °C, and at H2 pressures of 10 and 30 bars. Our QCM measurements revealed that Mg nanotrees can absorb hydrogen at lower temperatures and also at a faster rate compared to Mg thin film. In addition, Mg nanotrees can reach hydrogen storage values of about 4.80 wt% at 100 °C, and up to about 6.71 wt% (which is close to the theoretical maximum storage value of Mg) at temperatures lower than 150 °C. The significant enhancement in hydrogen absorption properties of our Mg nanotrees is believed to originate from novel physical properties of their nanoleaves. These nanoleaves are very thin (∼20 nm) and both surfaces are exposed to hydrogen enhancing the diffusion rate of hydrogen together with a decreased diffusion length. Based on X-ray diffraction measurements, individual nanoleaves have non-close-packed crystal planes that can further enhance the hydrogen absorption kinetics. In addition, our nanostructured Mg have been observed to quite resistant to surface oxidation, which is believed to due to the single crystal property of the Mg nanoleaves, which further improves the absorption kinetics of hydrogen.
Our experience with shape memory polymers (SMP) began with a project to develop an embolic coil release actuator in 1996. This was the first known SMP device to enter human trials. Recent progress with the SMP devices include multiple device applications (stroke treatments, stents, other interventional devices), functional animal studies, synthesis and characterization of new SMP materials, in vivo and in vitro biocompatibility studies and device-tissue interactions for the laser, resistive, or magnetic-field activated actuators. We describe several of our applied SMP devices.
Asymmetric superlattices (SLs) with ferromagnetic La0.7Sr0.3MnO3 (LSMO) and ferroelectric Ba0.7Sr0.3TiO3 (BST) as constitutive layers were fabricated on conducting LaNiO3 (LNO) coated (001) oriented MgO substrates using pulsed laser deposition (PLD). The crystallinity, ferroelectric and magnetic properties of the SLs were studied over a wide range of temperatures and frequencies. The structure exhibited ferromagnetic behavior at 300K, and ferroelectric behavior over a range of temperatures between 100K and 300K. The dielectric response as a function of frequency obeys normal behavior below 300 K, whereas it follows Maxwell–Wagner model at elevated temperatures. The effect of ferromagnetic LSMO layers on ferroelectric properties of the SL indicated strong influence of the interfaces. The asymmetric behavior of ferroelectric loop and the capacitance-voltage relationship suggest development of a built field in the SLs due to high strain across the interfaces.
Nanocrystalline Ni0.5Zn0.5Fe2O4 thin films have been synthesized with various grain sizes by sol–gel method on polycrystalline silicon substrates. The morphology and microwave absorption properties of the films calcined in the 673–1073 K range were studied by using XRD, AFM, near–field evanescent microwave microscopy, coplanar waveguide and direct microwave heating measurements. All films were uniform without microcracks. The increase of the calcination temperature from 873 to 1073 K and time from 1 to 3h resulted in an increase of the grain size from 12 to 27 nm. The complex permittivity of the Ni-Zn ferrite films was measured in the frequency range of 2–15 GHz. The heating behavior was studied in a multimode microwave cavity at 2.4 GHz. The highest microwave heating rate in the temperature range of 315–355 K was observed in the film close to the critical grain size of 21 nm in diameter marked by the transition from single– to multi–domain structure of nanocrystals in Ni0.5Zn0.5Fe2O4 film and by a maximum in its coercivity.
Implementation of full thermodynamic models in performance assessment (PA) calculations (large domain and very large timescales) is practically unfeasible due to excessive computational times. The complex competitive sorption processes of radionuclides are often simplified.
In this paper, such simple sorption models (i.e. linear Kd and Langmuir isotherms) were compared with more complex thermodynamic models for a reduced geometry and relatively short timescales (compared to traditional PA calculations).
Within the context of a safety case the value of this study is twofold. Primarily, it provides support information on how to choose adequate parameter values in a consistent simplified analysis for compliance with safety criteria. For the cases studied in this paper it became clear that a linear model is sufficient to represent sorption, but a proper choice of the Kd values is critical. Secondly, the comparison of results from these compliance calculations with more realistic analyses demonstrates quantitatively the safety margin implicitly present in PA calculations through model abstraction.
In this work, we employed three different methods to fabricate solar cell structures on indium tin oxide (ITO) substrates. For the first method, multi-layered structures were prepared by using single walled carbon nanotubes (SWCNTs) and tin oxide (SnO2). First, a SWCNT layer was deposited on the ITO substrate; and photoactive material was then coated on the top of the SWCNT layer. For the second method, photoactive particles were added to a solution of SWCNTs. The SWCNT/SnO2 solution was mechanically stirred and then deposited on the ITO substrate. For the third method, we synthesized photoactive particles on SWCNTs through a chemical-solution routine using SnCl4 as a precursor. We characterized the morphology and structure of the SWCNTs coated with SnO2 nanoparticles prepared with the three different methods by using a field emission scanning electron microscope equipped with an X-ray energy dispersive spectrometer. We characterized the photoelectrochemical properties of all electrodes by using an electrochemical station; mainly, we examined the photocurrent generated under periodic illumination. Our results indicate that there are significant differences in the photocurrent in the presence of SWCNTs. We propose the following hypothetical mechanism: without carbon nanotubes, generated electrons (when light is absorbed by SnO2 particles) must cross the particle network to reach an electrode. Many electrons never escape this network to generate an electrical current. The carbon nanotubes “collect” the electrons and provide, therefore, a more direct route to the electrode, thus improving the efficiency of the solar cells.
Low-cost, high-performance gamma-ray spectrometers are urgently needed for nonproliferation and homeland security applications. Available scintillation materials fall short of the requirements for energy resolution and sensitivity at room temperature. The emerging lanthanide halide based materials, while having the desired luminosity and proportionality, have proven difficult to produce in the large sizes and low cost required due to highly anisotropic properties caused by the non-cubic crystal structure. New cubic materials, such as the recently discovered elpasolite family (A2BLnX6; Ln-lanthanide and X-halogen), hold promise for scintillator materials due to their high light output, proportionality, and toughness. The isotropic nature of the cubic elpasolites leads to minimal thermomechanical stresses during single-crystal solidification, and eliminates the problematic light scattering at the grain boundaries. Therefore, it may be possible to produce these materials in large sizes as either single crystals or transparent ceramics with high production yield and reduced costs. In this study, we investigated the “cubic” elpasolite halide synthesis and studied the structural variations of four different compounds, including Cs2NaLaBr6, Cs2LiLaBr6, Cs2NaLaI6, and Cs2LiLaI6. Attempts to produce a large-area detector by a hot forging technique were explored.
We report the magnetoresistance (MR) measurements in a nanoconstriction fabricated by focused-ion-beam (FIB) in the tunneling regime of conductance. The resistance of the contact was controlled during the fabrication process, being stable in the metallic regime, near the conductance quantum, and under high vacuum conditions. The metallic contact was deteriorated when exposed to atmosphere, resulting in a conduction mechanism by tunneling. The TMR was found to be of 3% at 24 K. The anisotropic tunneling magnetoresistance (TAMR) was around 2% for low temperatures, with a field angle dependence more abrupt than in bulk Fe. This preliminary result is promising for the application of this technique to fabricate stable ferromagnetic constrictions near the atomic regime of conductance, where high MR values are expected.
The crystallization behavior of Ge-Sb phase change materials with variable Ge:Sb ratio X between 0.079 and 4.3 was studied using time-resolved x-ray diffraction, differential scanning calorimetry, x-ray reflectivity, optical reflectivity and resistivity vs. temperature measurements. It was found that the crystallization temperature increases with Ge content from about 130 °C for X = 0.079 to about 450 °C for X = 4.3. For low X, Sb x-ray diffraction peaks occurred during a heating ramp at lower temperature than Ge diffraction peaks. For X = 1.44 and higher, Sb and Ge peaks occurred at the same temperature. Mass density change upon crystallization and optical and electrical contrast between the phases show a maximum for the eutectic alloy with X = 0.17. The large change in materials properties with composition allows tailoring of the crystallization properties for specific application requirements.