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The alloyed layers were produced on Mg by heating the specimens in contact with pure Al powder or Al + Zn powder mixtures. The powder material acting as the source of diffusion elements was held under pressure during heating, and this led to the formation of thick, continuous layers in a short heating time (1 h). The layer formation process took place through partial melting at the substrate/powder interface. The Al-enriched layer was characterized by a eutectic structure composed of an Mg17Al12 intermetallic phase and a solid solution of Al in Mg. The Al/Zn-enriched layers produced from Al + 20% Zn and Al + 40% Zn powder mixtures consisted of Mg17(Al,Zn)12 and Mg5Al2Zn2 and a solid solution of Al and Zn in Mg. The alloyed layers had higher hardness and better wear resistance than the Mg substrate. The results of the polarization measurements show that the Al- and the Al/Zn-enriched layers provide a certain level of protection to Mg against corrosion.
We present a novel soft-nanoimprint procedure to fabricate high-quality sub-wavelength hole arrays in optically thick films of gold on glass substrates. We fabricate 0.5 × 0.5 mm2 structures composed of a square array of 180 nm-diameter holes with a 780 nm pitch. Optical angular transmission measurements on the arrays show clear extraordinary transmission peaks corresponding to the dispersion of surface plasmon polaritons propagating on either side of the metal film. The transmission features can be strongly controlled by engineering the dielectric environment around the holes. As the nanoimprint procedure enables fabrication of nanoscale patterns over wafer-scale areas at low cost, these imprinted metal nanoparticle arrays can find applications in, e.g., optical components, photovoltaics, integrated optics, and microfluidics.
To obtain a floating and magnetically recyclable photocatalyst, nano-scaled Fe3O4 particles are first deposited on the surface of the KH-550 modified cenosphere under a hydrothermal condition. The Fe3O4 coated cenosphere is then loaded with a layer of globular-flower-like SiO2 particles by a precipitation method. The Fe3O4/SiO2 double-layer structured cenosphere is finally immobilized with TiO2 nanoparticles doped with rare earth element Eu3+ to enhance the photoactivity of TiO2 using titanium sulfate, urea, and polyvinylpyrrolidone by a hydrothermal treatment. The as-prepared cenosphere is systematically characterized by various characterization techniques. The properties of photocatalytic degradation of methylene blue dye are also investigated. Results show that after being doped with 0.1% Eu3+ ions in relation to Ti4+ ions, the photocatalytic degradation efficiency for the Fe3O4/SiO2/Eu-doped TiO2 coated cenosphere is significantly improved under both ultraviolet and visible light irradiations. The saturation magnetization of the Fe3O4/SiO2/Eu-doped TiO2 coated cenosphere increases to some degree.
Thin films of the conjugated polymer poly(3-hexylthiophene) (P3HT) of different morphological structures were fabricated using both conventional spin-casting and the matrix-assisted pulsed laser evaporation (MAPLE). Films deposited by MAPLE exhibit inhomogeneous morphologies comprised globular subfeatures with dimensions of the order of 100 nm. We show that whereas the in-plane carrier mobilities of MAPLE-deposited films (8.3 × 10−3 cm2/V/s) are comparable with those of spin-cast analogs (5.5 × 10−3 cm2/V/s), the out-of-plane mobilities are an order of magnitude lower (4.1 × 10−4 cm2/V/s versus 2.7 × 10−3 cm2/V/s). Both in- and out-of-plane carrier transport characteristics of MAPLE-deposited films indicate a broad density of states and high carrier trap concentration. Optical absorbance spectroscopy not only corroborates a high degree of energetic disorder in MAPLE-deposited films, but also suggests that the P3HT chains possess average conjugation lengths comparable with spin-cast counterparts. Our findings, rationalized in terms of the Gaussian Disorder Model, describing carrier transport in an environment characterized by both positional and energetic disorder, provide important perspectives on the extent to which disorder impacts mechanisms of charge transport in conjugated polymers.
Developing high energy density supercapacitors is of great importance to the transportation, consumer electronics, and micro-grid energy storage sectors. Recently, the development of high voltage organic electrolyte based supercapacitor devices has been gaining much attention. Among them, there is an on-going intense interest in investigating high capacity lithium ion storage anode materials in hybrid supercapacitors. However, developing high capacity cathode materials for high voltage organic electrolyte supercapacitor devices is rarely investigated. The low electrical double layer capacitances of carbon cathode electrodes, which are widely used in current supercapacitor devices, are often the limiting bottleneck. In this contribution, we investigated the electrochemical energy storage behavior of a polyaniline (PANI)-single wall carbon nanotube (SWCNT) composite material in an organic electrolyte as a supercapacitor cathode. The PANI-SWCNT composite exhibits a high specific capacitance of 503 F/g, of which 58.8% of the total capacitance is attributed to the pseudocapacitive and electrical double layer energy storage. The cycling stability of the PANI-SWCNT composite could be further improved by polydopamine (PDA) modification. The PDA with strong adhesion properties is able to prevent mechanical degradation. The PDA modified PANI-SWCNT shows excellent stability with only 5% degradation after 2000 cycles.
This article features the importance of nanomaterial–protein interfaces, with a special interest on two-dimensional (2D) nanomaterials, for next generation sensors and electronics. Graphene, the first isolated and studied 2D nanomaterial, is taken as the material of most interest and then focused on its engineering by heteroatom doping. The success of graphene engineering for sensors widened the search for better and efficient biosensor platforms of other layered materials such as boron nitride and transition metal dichalcogenides. But functionalization of 2D backbones with biomolecules often ends up with the disruption of the biological activities due to various reasons. This has to be fundamentally studied and corrected for the clinical implementation of these materials based novel sensing platforms in point-of-care devices and micro-fluidic chips. At the end, importance of various 2D materials–biomolecule interfaces is discussed, and MoS2 based label-free biosensor is highlighted. A method for the modification of MoS2–biomolecule interaction via covalent functionalization of oxygen functionalities in MoS2 is also proposed.
The present report presents results from the fabrication, structural, and optical characteristics of sub-100 nm thermal chemical vapor deposition-grown silicon-oxycarbide (SiCxOy) nanowire (NW) arrays fabricated by e-beam lithography and reactive-ion-etching. The composition of SiCxOy materials follows closely the silicon-oxycarbide stoichiometry [SiCxO2(1−x), (0 < x < 1)] as observed by compositional and structural analysis. The corresponding structural and bonding evolution of SiCxOy are well-correlated with changes in their optical properties, as demonstrated by the linear dependence of their optical gap and refractive index with [Si–C]/[Si–O] bond–area ratio. By virtue of these advantages, properly tailored SiCxOy NWs were fabricated, exhibiting strong room-temperature visible photoluminescence (PL) through engineering of [Si–C]/[Si–O] bonds. The current studies focused on the thermal-oxidation and excitation intensity behavior of SiCxOy NWs revealed their very good stability, as their luminescence characteristics remain unchanged upon annealing in oxygen ambient (250 °C), while the PL intensity dependence on the excitation power-density exhibited a linear increase up to ∼800 W/cm2.
Crack propagation behaviors in a precracked single crystal Ag under mode I loading at different temperatures are studied by molecular dynamics simulation. The simulation results show that the crack propagation behaviors are sensitive to external temperature. At 0 K, the crack propagates in a brittle manner. Crack tip blunting and void generation are first observed followed by void growth and linkage with the main crack, which lead to the propagation of the main crack and brittle failure immediately without any microstructure evolution. As the temperature gets higher, more void nucleations and dislocation emissions occur in the crack propagation process. The deformation of the single crystal Ag can be considered as plastic deformation due to dislocation emissions. The crack propagation dynamics characterizing the microstructure evolution of atoms around the crack tip is also shown. Finally, it is shown that the stress of the single crystal Ag changes with the crack length synchronously.
The search for alternative earth abundant semiconducting nanocrystals for sustainable energy applications has brought forth the need for nanoscale syntheses beyond bulk synthesis routes. Of particular interest are metal phosphides and derivative I–V–VI chalcogenides including copper phosphide (Cu3P) and copper thiophosphate (Cu3PS4). Herein, we report a one-pot, solution-based synthesis of Cu3P nanocrystals utilizing an in situ phosphorus source: phosphorus pentasulfide (P2S5) in trioctylphosphine. By injecting this phosphorus source into a copper solution in oleylamine, uniform and size controlled Cu3P nanocrystals with a phosphorous-rich surface are synthesized. The subsequent reaction of the Cu3P nanocrystals with decomposing thiourea forms nanoscale Cu3PS4 particles having p-type conductivity and an effective optical band gap of 2.36 eV. The synthesized Cu3PS4 produces a cathodic photocurrent during photoelectrochemical measurements, demonstrating its application as a light-absorbing material. Our process creates opportunities to explore other solution-based metal-phosphorus systems and their subsequent sulfurization for earth abundant, alternative energy materials.
Hot compression tests were carried out on the duplex α + β leaded brass CuZn39Pb3 in temperature range of 600–800 °C and at strain rates of 0.001–1 s−1. A self-consistent model was used to analyze the flow behavior of the constituents and the material. A linear viscoplastic model was used to relate the flow stress of β and α + β composite to strain rate and the corresponding viscosity parameters were calculated at various deformation conditions. Using the viscosity parameters of β and α + β and the volume fractions of the constituents, the viscosity parameter of α was calculated. The values of the viscosity-like parameters and strain rate sensitivity for β and α + β composite were calculated using the nonlinear powerlaw viscoplastic equation. The results showed that the flow stress of α calculated using the self-consistent model was considerably higher than that of β. The difference could be attributed to the lower Zn content in α. The flow stress of α + β composite was calculated using the law of mixture rule. The law of mixture modeling of α + β composite for the iso-strain condition resulted to the overestimation of flow stress. The difference between the experimental and predicted results was attribute to the strain partitioning between α and β.
(1 − x) (Bi1/2Na1/2)TiO3–xBiFeO3 (x = 0–0.9) ceramics were prepared and the ferroelectric and piezoelectric properties along with the crystal structure were investigated. The crystal system of the ceramics was rhombohedral with the R3c symmetry throughout the compositions. The rhombohedral distortion (90° − α), where α was the rhombohedral angle based on a pseudocubic perovskite cell, was minimized at x = 0.1, while the lattice constant increased linearly with x. Saturated ferroelectric polarization-electric field hysteresis loops were observed at x = 0–0.6. The coercive field was reduced at x = 0.05–0.2 and the high remanent polarization of 30–35 µC/cm2 was obtained at x = 0–0.4. The piezoelectric constants d33 and d33* (which was calculated from a unipolar strain–electric field curve) were maximized to 93 pC/N at x = 0.1 and 183 pm/V at x = 0.05, respectively. These results suggested that the increase in the piezoelectric properties was associated with the reduction in the rhombohedral distortion, which could be useful in development of high performance lead-free piezoelectric materials.
Flexible touch sensors with high sensitivity show promise in biomedical diagnostics and for artificial “electronic skin” for robotics or prosthetic devices. For “electronic skin” applications, there exists a need for low-cost, scalable methods for producing pixels that sense both medium (10–100 kPa) and low pressures (<10 kPa). Here, the “breath figures” (BFs) method, a simple, self-assembly-based method for producing honeycomb-structured porous polymer films, was used to prepare pattern compressible, and microstructured dielectric layers for capacitive pressure sensors. Porous polystyrene BFs films served as molds for structuring polydimethylsiloxane dielectrics. Pressure sensing devices containing the BFs-molded dielectrics consistently gave pressure response with little hysteresis, high sensitivities at lower applied pressures, and improved sensitivity at higher pressures. Analysis of microstructure geometries and pressure sensor performance suggests that structures with higher aspect ratios (height-to-width) produce less hysteresis, and that less uniform, more polydisperse structures yield a more linear pressure response.
The microstructural evolution of type 347H heat-resistant austenitic steel during long-term aging at 700–900 °C was investigated by using a transmission microscope, a scanning electron microscope, and electron energy spectrum technology. The microstructural examination showed the typical micrographs of MX carbonitrides and M23C6 carbides after aging. The existence of the Z phase (NbCrN) at the grain boundaries during aging was identified. Meanwhile, the possible precipitation sequence of these particles was also confirmed. In the beginning of aging, fine Nb(C,N) precipitates first, then, M23C6 carbides precipitate along the grain boundaries. Finally, the Z phase is also observed at the grain boundaries. Moreover, the influence of isothermal holding temperature on the precipitation of MX carbonitrides and M23C6 carbides was discussed. The various microstructural characterizations showed that the M23C6 carbides and MX carbonitrides precipitate more easily with the increase of aging temperature. Furthermore, the number and the size of MX particles and M23C6 carbides increase when the isothermal holding time is prolonged.
Selective area growth of thin films reduces the number of steps in microfabrication processing and enables novel device structures. Here, we report, for the first time, selective area epitaxy of an oxide material on a GaN surface. Chlorination of the GaN surface via wet chemical processing is found effective to disrupt Mg adsorption and selectively prevent molecular beam epitaxy growth of MgO. MgO films grown on neighboring, nonchlorinated surfaces are epitaxial with a (111) MgO||(0001) GaN crystallographic relationship. Better than 3 μm lateral resolution for the selective area growth of MgO on GaN is demonstrated.
Al–12Si (80 vol%)–Ti52.4Al42.2Nb4.4Mo0.9B0.06 (at.%) (TNM) composites were successfully produced by the selective laser melting (SLM). Detailed structural and microstructural analysis shows the formation of the Al6MoTi intermetallic phase due to the reaction of the TNM reinforcement with the Al–12Si matrix during SLM. Compression tests reveal that the composites exhibit significantly improved properties (∼140 and ∼160 MPa higher yield and ultimate compressive strengths, respectively) compared with the Al–12Si matrix. However, the samples break at ∼6% total strain under compression, thus showing a reduced plasticity of the composites. Sliding wear tests were carried out for both the Al–12Si matrix and the Al–12Si–TNM composites. The composites perform better under sliding wear conditions and the wear rate increases with increasing loads. At high loads, the wear takes place at three different rates and the wear rate decreases with increasing experiment duration.
A method is presented to examine consecutive in-situ X-ray diffraction (XRD) diffractograms using exploratory factor analysis. Systematic changes in the diffractograms are described numerically by score values that could be used to correlate diffraction data with other non-stationary sample properties. Phase and structure evolution in a reacting material can be studied by in-situ XRD. The consecutively collected data can be considered a time series of datasets. Time series are non-stationary data. Such non-stationary data are often hard to examine fully by conventional evaluation methods including applications of the Rietveld method. Here a method is presented to avoid shortcomings of conventional evaluation methods. The new method helps to identify and describe significant systematic changes in in-situ XRD datasets by numerical values. These systematic changes can represent structural changes as well as changes in phase composition. The method can be used to describe the development of the complex processes of compositional and structural changes. The method is demonstrated using the example of a hydrating Portland cement mortar. This hydration process involves at least 11 phases including non-crystalline phases. In the presented example factor analysis of in-situ XRD data results in three variables (factors) describing the observed changes numerically.
The crystal structure of sitagliptin dihydrogen phosphate monohydrate (sometimes referred to as sitagliptin phosphate monohydrate) has been solved and refined using synchrotron X-ray powder diffraction data, and optimized using density functional techniques. Sitagliptin dihydrogen phosphate monohydrate crystallizes in space group P212121 (#19) with a = 6.137 108(12), b = 9.304 018(14), c = 38.307 67(10) Å, V = 2187.359(8) Å3, and Z = 4. The sitagliptin cation folds so that the two planar portions are roughly parallel. The ammonium group of the sitagliptin cation, the phosphate anion, and the water molecule form a network of strong hydrogen bonds. The result is a two-dimensional network, parallel to the ab plane. Halfway between these hydrogen bond planes, there are planes of high fluorine density. The powder pattern is included in the Powder Diffraction File™ as entry 00-064-1500.