Facile Synthesis of Ni-MgO/CNT Nanocomposite for Hydrogen Evolution Reaction.

In this study, the pristine MgO, MgO/CNT and Ni-MgO/CNT nanocomposites were processed using the impregnation and chemical vapor deposition methods and analyzed for hydrogen evolution reaction (HER) using the electrochemical water splitting process. Furthermore, the effect of nickel on the deposited carbon was systematically elaborated in this study. The highly conductive carbon nanotubes (CNTs) deposited on the metal surface of the Ni-MgO nanocomposite heterostructure provides a robust stability and superior electrocatalytic activity. The optimized Ni-MgO/CNT nanocomposite exhibited hierarchical, helical-shaped carbon nanotubes adorned on the surface of the Ni-MgO flakes, forming a hybrid metal-carbon network structure. The catalytic HER was carried out in a 1M alkaline KOH electrolyte, and the optimized Ni-MgO/CNT nanocomposite achieved a low (117 mV) overpotential value (ɳ) at 10 mA cm-2 and needed a low (116 mV/dec) Tafel value, denotes the Volmer-Heyrovsky pathway. Also, the high electrochemical active surface area (ECSA) value of the Ni-MgO/CNT nanocomposite attained 515 cm2, which is favorable for the generation of abundant electroactive species, and the prepared electrocatalyst durability was also performed using a chronoamperometry test for the prolonged duration of 20 h at 10 mA cm-2 and exhibited good stability, with a 72% retention. Hence, the obtained results demonstrate that the optimized Ni-MgO/CNT nanocomposite is a highly active and cost-effective electrocatalyst for hydrogen energy production.

Effects of molybdenum on hot deformation behavior and microstructural evolution of Fe40Mn40Co10Cr10C0.5 high entropy alloys.

The remarkable properties of high-entropy alloys (HEAs) have resulted in their increased research interest and prompted the use of various strategies to enhance their mechanical properties. In this study, the effects of Mo on the hot compressive deformation behavior of carbon-containing FeMn40Co10Cr10 HEAs in the temperature range of 800-1000°C and strain rate of 0.001-0.1 s-1 was investigated. The microstructural evolutilon and phase structure were characterized by X-ray diffraction and electron backscattered diffraction. The effects of strain, strain rate, and deformation temperature on the thermally activated deformation restoration process of the Fe39.5Mn40Co10Cr10C0.5 and Fe38.3Mn40Co10Cr10C0.5Mo1.7 HEAs during hot compression were represented by the Zener-Hollomon parameter. Dynamic recrystallization was initiated at 800°C with the strain rate of 0.001-0.1 s-1. The precipitation of the M23C6 carbide along the grain boundaries and within the matrix exerted a strong pinning effect on the grain/subgrain boundaries and promoted dynamic recrystallization through the particle-stimulated nucleation of recrystallization. Moreover, the addition of Mo to the Fe39.5Mn40Co10Cr10C0.5 HEA changed the dynamic recrystallization mechanism by reducing the stacking fault energy and enhancing the reverse f c c ↔ h c p phase transformation. The heterogeneous microstructure composed of ultrafine, fine, and larger grains in the Fe38.3Mn40Co10Cr10C0.5Mo1.7 HEA could be obtained by the nucleation of new recrystallized grains at large deformed grain boundaries adjacent to the first necklace structures and shear bands.

Supporting data for strengthening and deformation behavior of as-cast CoCrCu1.5MnNi high entropy alloy with micro-/nanoscale precipitation.

The data presented here are related to the research article entitled "Strengthening and deformation behavior of as-cast CoCrCu1.5MnNi high-entropy alloy (HEA) with micro-/nanoscale precipitation [1]". Non-equimolar CoCrCu1.5MnNi was cast by the conventional induction melting under a high-purity Ar atmosphere. Scanning electron microscopy equipped with energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM) were used for micro- and nanostructure characterization. Subsize tensile specimens with two different gage length to width ratio were tested at room and cryogenic temperatures to assess the accuracy of strength and ductility data in the as-cast CoCrCu1.5MnNi HEAs. The mixing enthalpy (ΔHmix) versus lattice elastic energy (ΔHel) criterion was used to predict the stable phases. The data on the effects of microstructural and nanostructural distribution of various phases on mechani-cal properties in the as-cast HEA could be used in designing high entropy alloys with excellent as-cast mechanical performance.

Data supporting the hierarchically activated deformation mechanisms to form ultra-fine grain microstructure in carbon containing FeMnCoCr twinning induced plasticity high entropy alloy.

This article presents data regarding the research paper entitled "Hierarchically activated deformation mechanisms to form ultra-fine grain microstructure in carbon containing FeMnCoCr twinning induced plasticity high entropy alloy [1]". In this article we provide supporting data for describing the associated mechanisms in microstructure evolution and grain refinement of a carbon-doped TWIP high-entropy alloy (HEA) during thermomechanical processing. Microstructural characterization before and after deformation was performed using scanning electron microscope (SEM) outfitted with EBSD detector and transmission electron microscopy (TEM) were used for microstructure observation and investigation of nanostructure evolution during deformation. Inverse pole figure (IPF) map, grain boundary map and kernel average misorientation map (KAM) were used for systematic analysis of nanostructural evolution and deformed heterostructure consisting of hierarchical mechanical twinning, shear-banding, microbanding and formation of strain-induced boundaries (SIBs).

Microstructural Evolution and Mechanical Properties of Non-Equiatomic (CoNi)74.66Cr17Fe8C0.34 High-Entropy Alloy.

In this study, we manufactured a non-equiatomic (CoNi)74.66Cr17Fe8C0.34 high-entropy alloy (HEA) consisting of a single-phase face-centered-cubic structure. We applied in situ neutron diffraction coupled with electron backscattered diffraction (EBSD) and transmission electron microscopy (TEM) to investigate its tensile properties, microstructural evolution, lattice strains and texture development, and the stacking fault energy. The non-equiatomic (CoNi)74.66Cr17Fe8C0.34 HEA revealed a good combination of strength and ductility in mechanical properties compared to the equiatomic CoNiCrFe HEA, due to both stable solid solution and precipitation-strengthened effects. The non-equiatomic stoichiometry resulted in not only a lower electronegativity mismatch, indicating a more stable state of solid solution, but also a higher stacking fault energy (SFE, ~50 mJ/m2) due to the higher amount of Ni and the lower amount of Cr. This higher SFE led to a more active motion of dislocations relative to mechanical twinning, resulting in severe lattice distortion near the grain boundaries and dislocation entanglement near the twin boundaries. The abrupt increase in the strain hardening rate (SHR) at the 1~3% strain during tensile deformation might be attributed to the unusual stress triaxiality in the {200} grain family. The current findings provide new perspectives for designing non-equiatomic HEAs.

Comparative Insight into the Interfacial Phase Evolutions during Solution Treatment of Dissimilar Friction Stir Welded AA2198-AA7475 and AA2198-AA6013 Aluminum Sheets.

In the current research, dissimilar friction stir welded (FSW) sheets of AA2198-AA7475 and AA2198-AA6013 were solution treated at 460-580 °C for 1 h. Annealing at 580 °C led to complete degradation of both dissimilar weldments from the AA2198 side. According to the microstructure inspection, solution treatment triggered abnormal grain growth within the stir zone (SZ), and applying higher treatment temperatures enhanced the fraction of transformed grains. SEM analysis revealed that the pre-melting of grain boundaries (GBs) over 540 °C encouraged the diffusion of solute atoms to the GBs. The massive diffusion of Cu to the GBs led to the formation of Cu-rich eutectic phases in AA7475 and AA2198 and dense Cu-rich particles in AA6013. In the meantime, the diffusion of Mg and Zn to the GBs of AA7475 and Fe and Si to the GBs of AA6013 eventuated in the formation of coarse particles at the GBs which, in return, attenuated the bonding adhesion of the grains at SZ. The formation of remarkable Cu-rich phases in the pre-melted regions and significant contraction of the eutectic phase while cooling as well as the formation of particles at GBs resulted in intergranular failure of the joints from the AA2198 side of the SZ.

Data on the microstructure and deformation of Fe50Mn25Cr15Co10Nx (x=0∼1.6) supporting the modifications of partial-dislocation-induced defects (PDIDs) and strength/ductility enhancement in metastable high entropy alloys.

The data presented in this article are related to a research paper on the modification of deformed nanostructure and mechanical performance of metastable high entropy alloys (HEAs) [1]. Fe50Mn25Cr15Co10 alloys with and without nitrogen were synthesized in a vacuum induction furnace using pure metals of 99.99% purity and FeCrN2 as nitrogen source. The nitrogen content was determined by Leco O/N-836 determinator for nitrogen-doped alloys. Transmission electron microscopy (TEM) were carried at 200 kV equipped with energy dispersive spectroscopy (EDS). Tensile testing was performed at room temperature. The strain rate jump tests were conducted by changing the strain rate between 10-3 and 10-2 s-1 to measure the strain rate sensitivity. The nanostructural evolutions by deformation including extended stacking faults (ESFs), ε-martensite and twins were examined using EBSD and TEM for the annealed samples and those strained to different strain levels. The role of partial dislocations on the formation of various PDIDs were analysed and the energies stored as deformed nanostructure (ESDN) after the PDID band formation were used to predict the evolution of various nanostructure with strain. The data and approach would provide a useful insight into the nanostructural evolution in metastable high entropy alloys.

Bi2WO6 and FeWO4 Nanocatalysts for the Electrochemical Water Oxidation Process.

Polyvinylpyrrolidone (PVP)-assisted nanocatalyst preparation was succeeded by employing a controlled solvothermal route to produce efficient electrodes for electrochemical water-splitting applications. Bi2WO6 and FeWO4 nanocatalysts have been confirmed through the strong signature of (113) and (111) crystal planes, respectively. The binding natures of Bi-W-O and Fe-W-O have been thoroughly discussed by employing X-ray photoelectron spectroscopy which confirmed the formation of Bi2WO6 and FeWO4. The freestanding nanoplate array morphology of Bi2WO6 and the fine nanosphere particle morphology of FeWO4 nanocatalysts were revealed by scanning electron microscopy images. With these confirmations, the fabrication of durable, long-term electrodes for electrochemical water splitting has been subjected to efficient oxidation of water, confirmed by obtaining 2.79 and 1.96 mA/g for 0.5 g PVP-assisted Bi2WO6 and FeWO4 nanocatalysts, respectively. The water oxidation mechanism of both nanocatalysts has been revealed with the support of 24 h stability test over continuous water oxidation and faster charge transfer achieved by the smaller Tafel slope values of 75 and 78 mV/dec, respectively. Generally, these nanocatalysts are utilized for photocatalytic applications. The present study revealed the PVP-assisted synthesis to produce electrocatalytically active nanocatalysts and their electrochemical water-splitting mechanism which will offer a pathway for research interests with regard to the production of multifunctional nanocatalysts for both electro- and photocatalytic applications in the near future.

Electrochemical Performance of ß-Nis@Ni(OH)2 Nanocomposite for Water Splitting Applications.

Investigation on the formation mechanism of the ß-NiS@Ni(OH)2 nanocomposite electrode for electrochemical water splitting application was attempted with the use of the hydrothermal processing technique. Formation of single-phase ß-NiS, Ni(OH)2 and composite-phase ß-NiS@Ni(OH)2 has been thoroughly analyzed by X-ray diffractometer (XRD) spectra. Three different kinds of morphologies such as rock-like agglomerated nanoparticles, uniformly stacked nanogills, and uniform nanoplates for ß-NiS, Ni(OH)2, and ß-NiS@Ni(OH)2 materials, respectively, were confirmed by SEM images. The characteristic vibration modes of ß-NiS, Ni(OH)2, and ß-NiS@Ni(OH)2 nanocomposites were confirmed from Raman and Fourier transform infrared spectra. Near band edge emission and intrinsic vacancies present in the nanocomposites were retrieved by photoluminescence spectra. The optical band gaps of the synthesized nanocomposites were calculated as 2.1, 2.5, and 2.2 eV for ß-NiS, Ni(OH)2, and ß-NiS@Ni(OH)2 products, respectively. The high-performance electrochemical water splitting was achieved for the ß-NiS@Ni(OH)2 nanocomposite as 240 mA/g at 10 mV/s from a linear sweep voltammogram study. The faster charge mobile mechanism of the same electrode was confirmed by electrochemical impedance spectra and a Tafel slope value of 53 mV/dec. The 18 h of stability was achieved with 95% retention, which was also reported for the NiS@Ni(OH)2 nanocomposite for continuous electrochemical water splitting applications.

Macroparticles Reduction Using Filter Free Cathodic Vacuum Arc Deposition Method in ZnO Thin Films.

We report a new method to reduce macroparticles in ZnO thin films using filter free cathodic vacuum arc deposition without using any cooling arrangements operated at low arc current. The detailed mechanism has been proposed to reduce macroparticles during thin film deposition. The successful reduction of macroparticles was confirmed employing FESEM-EDX studies. FESEM images of ZnO thin films deposited with cathode spot to substrate distance from 10 to 20 cm revealed that the population of the macroparticles were reduced with the increase of cathode spot to substrate distances at low arc current. The prepared ZnO films were characterised and showed good structural and optical properties.

Facile and novel synthetic method to prepare nano molybdenum and its catalytic activity.

This study reports on a facile and economical synthetic method to prepare nano molybdenum by solid-state reaction technique. Metallic nano molybdenum was synthesised from molybdenum trioxide, molybdenum IV oxide and molybdenum VI oxide through thermal decomposition technique. Metallic nano molybdenum prepared from molybdenum IV oxide was used to study the catalytic effect of molybdenum nanoparticles on the growth of Anabaena sp. The increase in concentration of nano molybdenum from 0.1 to 100% in BG11 (N⁻ Mo⁻ + nano Mo) medium increases heterocyst frequency. The chlorophyll and protein content in Anabaena sp. was found to improve when compared with bulk molybdenum particles and showed a positive influence to be used as a nano nutrient for Anabaena sp.

Structural, compositional and textural properties of monoclinic α-Bi2O3 nanocrystals.

Perfect α-Bi2O3 nanocrystals were successfully synthesized via green synthesis method. X-ray diffraction studies clearly revealed a single phase α-Bi2O3 nanocrystal without any secondary phase. The strong XPS peaks observed at 160 and 165 eV were assigned to Bi4f5/2 and Bi4f7/2 and clearly revealed Bi(3+) valence states of bismuth ions. Photoluminescence spectra revealed the perfect α-Bi2O3 crystal nature without having inter band transitions between defects, impurity and different valence states of bismuth ions. Out of thirty expected modes, the symmetry assignments of Raman bands correlated to Bg(4), Ag(5), Bg(5), Bg(6), Ag(7), Ag(8), Ag(9), Ag(10), Ag(12) and Ag(14) modes revealed perfect α-Bi2O3 nanocrystals. Transmission electron microscopy studies combined with a selected area electron diffraction pattern recorded on α-Bi2O3 nanocrystals show monoclinic structure preferential orientation with sizes approximately 200 nm in diameters and 500 nm in length.

Rambutan peels promoted biomimetic synthesis of bioinspired zinc oxide nanochains for biomedical applications.

A naturally occurring rambutan peel waste was employed to synthesis bioinspired zinc oxide nanochains. Rambutan peels has the ability of ligating zinc ions as a natural ligation agent resulting in zinc oxide nanochains formation due to its extended polyphenolic system over incubation period. Successful formation of zinc oxide nanochains was confirmed employing transmission electron microscopy studies. About 60% and ∼40% cell viability was lost and 50% and 10% morphological change was observed in 7 and 4 days incubated ZnO treated cells compared with control. Moreover, 50% and 55% of cell death was observed at 24 and 48 h incubation with 7 days treated ZnO cells and hence alters and disturbs the growth of cancer cells and could be used for liver cancer cell treatment.

Novel zirconium nitride and hydroxyapatite nanocomposite coating: detailed analysis and functional properties.

A new type of high-quality zirconium nitride (ZrN) and hydroxyapatite (HA) bionanocomposite was prepared by radio-frequency (RF) magnetron sputtering for biomedical applications. Detailed analysis of this composite coating revealed that a higher substrate temperature (ST) (>300 °C) increased its crystallinity, uniformity, and functional properties. This nanocomposite showed some encouraging functional properties. Mechanical analyses of the nanocomposite showed improved hardness, modulus, and wear resistance, which were found to be due to the increasing volume fraction of ZrN at higher ST. Biomineralization and in vitro cell analysis revealed increased weight gain and enhanced cell activity with increased substrate temperature. Overall, the results of the present study indicate that this nanocomposite coating could become a promising alternative for biomedical applications.

Nanostructural analysis of trabecular bone.

The mechanical properties of bone are dictated by the size, shape and organization of the mineral and matrix phases at multiple levels of hierarchy. While much is known about structure-function relations at the macroscopic level, less is known at the nanoscale, especially for trabecular bone. In this study, high resolution transmission electron microscopy (HRTEM) was carried out to analyze shape and orientation of apatite crystals in murine femoral trabecular bone. The distribution and orientation of mineral apatites in trabecular bone were different from lamellar bone and the c-axis of the tablet-like mineral apatite crystals in trabecular bone was arranged with no preferred orientation. The difference in the orientation distribution of apatite crystals of trabecular bone in the present study compared with that of lamellar bone found in the literature can be attributed to the more complex local stress state in trabecular bone. Apatite crystals were also found to be multi-crystalline, not single crystalline, from dark field image analysis. From the observations of this study, it is suggested that Wolff's law can be applicable to the nanostructural orientation and distribution of apatite crystals in trabecular bone. It was also found that small round crystalline particles observed adjacent to collagen fibrils were similar in size and shape to the apatite crystals in biomimetically nucleated synthetic amorphous calcium phosphate, which suggests that they are bone mineral apatite nuclei.

Spatial control of protein within biomimetically nucleated mineral.

An ideal approach for bone tissue engineering allows for osteoconductivity, osteoinductivity, and cell transplantation. In this study, we examined coprecipitation and surface adsorption schemes with respect to their abilities to control the spatial quantity and localization of a model protein, bovine serum albumin (BSA), that is incorporated into a biomimetic apatite layer nucleated onto polylactic-co-glycolic acid (PLGA) films. Protein incorporation was characterized by determining protein: presence, quantity loaded, retention, effects on mineral morphology, and localization. FT-IR confirmed the presence of protein in all coprecipitation samples with stronger peaks in the coprecipitated samples compared to the surface adsorbed samples. Coprecipitation resulted in higher loading capacities and higher protein retention versus adsorption. Protein incorporation via coprecipitation changed the mineral morphology from sharp plate-like structures to more rounded structures, whereas, surface adsorption did not change mineral structure. By using confocal microscopy to examine the incorporation of fluorescently labeled proteins, spatial control over protein localization was exhibited. By controlling the loading quantity and localization of the model protein through the mineral thickness, a desired release profile can be achieved. A desired and effective delivery system of biological agents utilizing coprecipitation for bone regeneration can therefore be designed.

Micro- and nano-structural analyses of damage in bone.

Skeletal fractures represent a significant medical and economic burden for our society. In the US alone, age-related hip, spine, and wrist fractures accounted for more than $17 billion in direct health care costs in 2001. Moreover, skeletal fractures are not limited to the elderly; stress fractures and impact/trauma-related fractures are a significant problem in younger people also. Gaining insight into the mechanisms of fracture and how these mechanisms are modulated by intrinsic as well as extrinsic factors may improve the ability to define fracture risk and develop and assess preventative therapies for skeletal fractures. Insight into failure mechanisms of bone, particularly at the ultrastructural-level, is facilitated by the development of improved means of defining and measuring tissue quality. Included in these means are microscopic and spectroscopic techniques for the direct observation of crack initiation, crack propagation, and fracture behavior. In this review, we discuss microscopic and spectroscopic techniques, including laser scanning confocal microscopy (LSCM), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman spectroscopic imaging for visually observing microdamage in bone, and the current understanding of damage mechanisms derived from these techniques.