Ultrathin Boundary-Less SnO2 Films with Surface-Activated Two-Dimensional Nanograins Enable Fast and Sensitive Hydrogen Gas Sensing.

Fast and reliable semiconductor hydrogen sensors are crucially important for the large-scale utilization of hydrogen energy. One major challenge that hinders their practical application is the elevated temperature required, arising from undesirable surface passivation and grain-boundary-dominated electron transportation in the conventional nanocrystalline sensing layers. To address this long-standing issue, in the present work, we report a class of highly reactive and boundary-less ultrathin SnO2 films, which are fabricated by the topochemical transformation of 2D SnO transferred from liquid Sn-Bi droplets. The ultrathin SnO2 films are purposely made to consist of well-crystallized quasi-2D nanograins with in-plane grain sizes going beyond 30 nm, whereby the hydroxyl adsorption and grain boundary side-effects are effectively suppressed, giving rise to an activated (101)-dominating dangling-bond surface and a surface-controlled electrical transportation with an exceptional electron mobility of 209 cm2 V-1 s-1. Our work provides a new cost-effective strategy to disruptively improve the gas reception and transduction of SnO2. The proposed chemiresistive sensors exhibit fast, sensitive, and selective hydrogen sensing performance at a much-reduced working temperature of 60 °C. The remarkable sensing performance as well as the simple and scalable fabrication process of the ultrathin SnO2 films render the thus-developed sensors attractive for long awaited practical applications in hydrogen-related industries.

Breaking the Mutual Constraint between Polarization and Voltage Resistance with Nanograined High-Entropy Ceramic.

Dielectric ceramics with a high energy storage capacity are key to advanced pulsed power capacitors. However, conventional materials face a mutual constraint between polarization strength and the breakdown strength bottleneck. To address this limitation, the concept of nanograined high-entropy ceramics is introduced in this work. By introducing a large number of constituent elements into the A-site of perovskite material lattice, high-entropy (Bi0.2K0.2Ba0.2Sr0.2Ca0.2)TiO3-0.2 'CuO relaxor ceramic with nanoscale grains have been successfully prepared, which breaks the mutual constraint between polarization strength and breakdown strength bottleneck and results a recoverable energy density (Wrec ∼ 6.86 J/cm3) and an efficiency (η ∼ 87.7%) at 670 kV/cm. Moreover, its excellent stability makes it potentially useful under a variety of extreme conditions, including at high temperatures and high/low frequencies. These obtained results demonstrate that this nanograined high-entropy lead-free perovskite ceramic has great potential for energy storage applications.

Superficial Grain Refinement of 316L Stainless Steel by Rolling with Rough Rolls.

This study presents a novel approach to producing superficial micro- and nanostructures using a cold rolling process with rough rolls, followed by low-temperature annealing. The proposed technique attempts to recreate the superficial deformation occurring in the sandblasting process. It allows for the generation of an inhomogeneous network, or tangle, of high-deformation zones on the material's surface that act as nucleation centers during the subsequent annealing process. However, the proposed method has a significant advantage over sandblasting: it is a continuous process with high productivity. An austenitic stainless-steel sheet, previously normalized, was used as the raw material. The samples were cold rolled using rough rolls (rhombic-based pyramids of 2.08 mm, 1.04 mm, and 1.5 mm in length, width, and height, respectively) and annealed at temperatures between 200 °C and 400 °C for one hour. An optical and electronic microstructure analysis showed the presence of small, heterogeneously distributed surface grains of 200-300 nm in diameter. Finite element analysis revealed significant deformation that was inhomogeneous and likely responsible for the uneven distribution of the recrystallized grains. Additionally, surface nanohardness results showed a 20% increase with respect to the central zone of the material. Finally, wear tests of the treated samples showed lower wear than samples rolled with conventional rolls.

Zirconia-Toughened Alumina (ZTA) Nanoceramics with a Gradient Microstructure: A Comparative Study of ZTA Ceramics with Fibrous and Granular Morphology.

ZrO2-toughened Al2O3 (ZTA) ceramic composites with a porosity gradient and with improved mechanical properties have a wide range of possible applications. We fabricated nanofibrous and nanogranular Y-ZTA and Ce-ZTA composites with a gradient microstructure by creating a temperature gradient during SPS sintering, with the use of asymmetric graphite tool arrangement (ASY). In this study, we examined the morphology effect of the starting materials on the sintering process and on the final microstructure, as well as the mechanical properties of the composites. A large temperature difference was established for both the granular and fibrous samples fabricated in the ASY configuration, which resulted in gradient porosity along the ceramics bodies: the upper part of the ceramics showed a highly porous fine microstructure, while the opposite side was highly densified. The final microstructure of the composites can be tailored by varying the morphology of the starting ceramics or the graphite configuration. A highly porous skeleton-like structure was formed by sintering fibres in the ASY configuration, whereas the granular precursors resulted in a much less porous composite. The microstructure affected the mechanical properties of the composite. Improved hardness and more than 50% higher compression strength were obtained for the granular Ce-ZTA samples as compared to the fibrous sample. Gradient porosity with fibrous or granular morphology promotes the penetration of bioactive nanosized hydroxyapatite (HAp) into the pore structure. Fibrous ZTA absorbs HAp more effectively due to its higher porosity as well as its bimodal pore structure.

Giant Energy Density via Mechanically Tailored Relaxor Ferroelectric Behavior of PZT Thick Film.

Relaxor ferroelectrics (RFEs) are being actively investigated for energy-storage applications due to their large electric-field-induced polarization with slim hysteresis and fast energy charging-discharging capability. Here, a novel nanograin engineering approach based upon high kinetic energy deposition is reported, for mechanically inducing the RFE behavior in a normal ferroelectric Pb(Zr0.52 Ti0.48 )O3 (PZT), which results in simultaneous enhancement in the dielectric breakdown strength (EDBS ) and polarization. Mechanically transformed relaxor thick films with 4 µm thickness exhibit an exceptional EDBS of 540 MV m-1 and reduced hysteresis with large unsaturated polarization (103.6 µC cm-2 ), resulting in a record high energy-storage density of 124.1 J cm-3 and a power density of 64.5 MW cm-3 . This fundamental advancement is correlated with the generalized nanostructure design that comprises nanocrystalline phases embedded within the amorphous matrix. Microstructure-tailored ferroelectric behavior overcomes the limitations imposed by traditional compositional design methods and provides a feasible pathway for realization of high-performance energy-storage materials.

High-Strength ß-Phase Magnesium-Lithium Alloy Prepared by Multidirectional Rolling.

Magnesium-lithium alloys are popular in the lightweight application industry for their very low density. However, as the lithium content increases, the strength of the alloy is sacrificed. Improving the strength of ß-phase Mg-Li alloys is urgently needed. The as-rolled Mg-16Li-4Zn-1Er alloy was multidirectionally rolled at various temperatures in comparison to conventional rolling. The results of the finite element simulations showed that multidirectional rolling, as opposed to conventional rolling, resulted in the alloy effectively absorbing the input stress, leading to reasonable management of stress distribution and metal flow. As a result, the alloy's mechanical qualities were improved. By modifying the dynamic recrystallization and dislocation movement, both high-temperature (200 °C) and low-temperature (-196 °C) rolling greatly increased the strength of the alloy. During the multidirectional rolling process at -196 °C, a large number of nanograins with a diameter of 56 nm were produced and a strength of 331 MPa was obtained.

Nanoscale Ultrafine Zinc Metal Anodes for High Stability Aqueous Zinc Ion Batteries.

Aqueous Zn batteries (AZBs) are a promising energy storage technology, due to their high theoretical capacity, low redox potential, and safety. However, dendrite growth and parasitic reactions occurring at the surface of metallic Zn result in severe instability. Here we report a new method to achieve ultrafine Zn nanograin anodes by using ethylene glycol monomethyl ether (EGME) molecules to manipulate zinc nucleation and growth processes. It is demonstrated that EGME complexes with Zn2+ to moderately increase the driving force for nucleation, as well as adsorbs on the Zn surface to prevent H-corrosion and dendritic protuberances by refining the grains. As a result, the nanoscale anode delivers high Coulombic efficiency (ca. 99.5%), long-term cycle life (over 366 days and 8800 cycles), and outstanding compatibility with state-of-the-art cathodes (ZnVO and AC) in full cells. This work offers a new route for interfacial engineering in aqueous metal-ion batteries, with significant implications for the commercial future of AZBs.

Effect of Ultrasonic Surface Mechanical Attrition Treatment-Induced Nanograins on the Mechanical Properties and Biocompatibility of Pure Titanium.

Commercially pure titanium (Ti) is widely used in bio-implants due to its high corrosion resistance. However, Ti exhibits marginally low mechanical and tribological properties, which limit its applications in some orthopedic implants. In this work, the Ti samples were subjected to ultrasonic surface mechanical attrition treatment (SMAT) for various durations to improve their surface properties such as hardness, strength and surface energy. SMAT-induced grain refinement was analyzed using optical, scanning electron and atomic force microscopy techniques. A Vickers hardness test was performed to determine the through-thickness hardness. Mechanical testing was carried out to measure the yield strength, ultimate tensile strength and ductility of the specimens. Corrosion tests were performed on a Gamry Potentiostat. The surface energy of SMAT-modified samples was calculated using the Owens-Wendt method. It was observed that SMAT reduced the average grain size from 50 µm to as low as 100 nm. The grain refinement and the corresponding grain boundary density led to a significant improvement in mechanical properties and biocompatibility in terms of increased hardness, yield and tensile strengths, surface energy, corrosion rate and hydrophilicity.

Supercritical Relaxor Nanograined Ferroelectrics for Ultrahigh-Energy-Storage Capacitors.

Supercritical relaxor nanograined ferroelectrics are demonstrated for high-performance dielectric capacitors, showing record-high overall properties of energy density ≈13.1 J cm-3 and field-insensitive efficiency ≈90% at ≈74 kV mm-1 and superior charge-discharge performances of high power density ≈700 MW cm-3 , high discharge energy density ≈6.67 J cm-3 , and ultrashort discharge time <40 ns at 55 kV mm-1 . Ex/in situ transmission electron microscopy, Raman spectroscopy, and synchrotron X-ray diffraction provide clear evidence of the supercritical behavior in (Na,K)(Sb,Nb)O3 -SrZrO3 -(Bi0.5 Na0.5 )ZrO3 ceramics, being achieved by engineering the coexistence of multiple local symmetries within the ergodic relaxor zone. The vanished difference between the ground relaxor state and the high-field supercritical state eliminates polarization hysteresis. The supercritical evolution with electric field enables a highly delayed polarization saturation with continuously increased polarization magnitudes. The results demonstrate that such a design strategy of compositionally induced and field-manipulated supercritical behavior can be generalizable for developing desirable energy-storage dielectrics for applications in ceramic/film capacitors.

Realizing Interfacial Electron/Hole Redistribution and Superhydrophilic Surface through Building Heterostructural 2 nm Co0.85 Se-NiSe Nanograins for Efficient Overall Water Splittings.

Electrochemical overall water splitting using renewable energy input is highly desirable for large-scale green hydrogen generation, but it is still challenged due to the lack of low-cost, durable, and highly efficient electrocatalysts. Herein, 1D nanowires composed of numerous 2 nm Co0.85 Se-NiSe nanograin heterojunctions as efficient precious metal-free bifunctional electrocatalyst are reported for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution with the merits of high activity, durability, and low cost. The abundant microinterface among the ultrafine nanograins and the presence of lattice distortion around nanograin interface is found to create a superhydrophilic surface of the electrocatalyst, which significantly facilitate the fast diffusion of electrolytes and the release of the formed H2 and O2 from the catalyst surface. Furthermore, synergic effect between Co0.85 Se and NiSe grain on adjusting the electronic structure is revealed, which enhances electron mobility for fast electron transport during the HER/OER process. Owing to these merits, the rationally designed Co0.85 Se-NiSe heterostructures display efficient overall water splitting behavior with a low voltage of 1.54 V at 10 mA cm-2 and remarkable long-term durability for the investigated period of 50 h.

Higher Damping Capacities in Gradient Nanograined Metals.

The capability of damping mechanical energy in polycrystalline metals depends on the activities of defects such as dislocation and grain boundary (GB). However, operating defects has the opposite effect on strength and damping capacity. In the quest for high damping metals, maintaining the level of strength is desirable in practice. In this work, gradient nanograined structure is considered as a candidate for high-damping metals. The atomistic simulations show that the gradient nanograined models exhibit enhanced damping capacities compared with the homogeneous counterparts. The property can be attributed to the long-range order of GB orientations in gradient grains, where shear stresses facilitate GB sliding. Combined with the extraordinary mechanical properties, the gradient structure achieves a strength-ductility-damping synergy. The results provide promising solutions to the conflicts between mechanical properties and damping capacity in polycrystalline metals.

Achieving a Record-High Capacitive Energy Density on Si with Columnar Nanograined Ferroelectric Films.

High energy density dielectric film capacitors are desirable in modern electronic devices. Their miniaturization and integration into Si-based microsystems create opportunities for in-circuit energy supply, buffering, and conditioning. Here, we present a CMOS (complementary metal oxide semiconductor)-compatible route for the fabrication of BaTiO3 film capacitors on Si with a record-high recoverable energy density and good efficiency (∼242 J/cm3 and ∼76% at 8.75 MV/cm). These BaTiO3 films were sputter-deposited at 350 °C and consisted of slightly compressed superfine columnar nanograins with a (001) texture. Such a nanostructure was endowed with a high breakdown strength, a reduced remnant polarization, and an enhanced maximum polarization, which are accountable for their excellent energy storage performance. Moreover, these BaTiO3 film capacitors displayed a high electrical fatigue resistance, a wide range of operating temperatures, and an excellent frequency stability. With an engineered nanostructure, the prototype perovskite of BaTiO3 has shown great promise for capacitive energy storage applications.

Room Temperature Detection of Hydrogen Peroxide Vapor by Fe2O3:ZnO Nanograins.

In this report, a Fe2O3:ZnO sputtering target and a nanograins-based sensor were developed for the room temperature (RT) detection of hydrogen peroxide vapor (HPV) using the solid-state reaction method and the radio frequency (RF) magnetron sputtering technique, respectively. The characterization of the synthesized sputtering target and the obtained nanostructured film was carried out by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray (EDX) analyses. The SEM and TEM images of the film revealed its homogeneous granular structure, with a grain size of 10-30 nm and an interplanar spacing of Fe2O3 and ZnO, respectively. EDX spectroscopy presented the real concentrations of Zn in the target material and in the film (21.2 wt.% and 19.4 wt.%, respectively), with a uniform distribution of O, Al, Zn, and Fe elements in the e-mapped images of the Fe2O3:ZnO film. The gas sensing behavior was investigated in the temperature range of 25-250 °C with regards to the 1.5-56 ppm HPV concentrations, with and without ultraviolet (UV) irradiation. The presence of UV light on the Fe2O3:ZnO surface at RT reduced a low detection limit from 3 ppm to 1.5 ppm, which corresponded to a response value of 12, with the sensor's response and recovery times of 91 s and 482 s, respectively. The obtained promising results are attributed to the improved characteristics of the Fe2O3:ZnO composite material, which will enable its use in multifunctional sensor systems and medical diagnostic devices.

Deformation Twinning Induced High Tensile Ductility of a Gradient Nanograined Cu-Based Alloy.

We investigated the tensile properties of gradient nanograined Cu and CuAl samples prepared by plastic deformation. Tensile tests showed that the gradient nanograined Cu-4.5Al sample exhibits a uniform elongation of ~22% without any cracks, while the uniform elongation of the gradient nanograined Cu sample is only ~18%. Numerous mechanical twinning retards the softening of the nanograins and accommodates a high tensile ductility in the gradient nanograined Cu-4.5Al sample. This work indicates that mechanical twinning is a potential deformation mechanism to achieve high tensile ductility of nanograined materials.

Highly Efficient Halide Perovskite Light-Emitting Diodes via Molecular Passivation.

Metal halide perovskites are promising for applications in light-emitting diodes (LEDs), but still suffer from defects-mediated nonradiative losses, which represent a major efficiency-limiting factor in perovskite-based LEDs (PeLEDs). Reported here is a strategy to synthesize molecular passivators with different anchoring groups for defects passivation. The passivated perovskite thin films exhibit improved optoelectronic properties as well as reduced grain size and surface roughness, thus enable highly efficient PeLEDs with an external quantum efficiency of 15.6 % using an imidazolium terminated passivator. Further demonstrated is that the in situ formation of low-dimensional perovskite phase on the surface of three-dimensional perovskite nanograins is responsible for surface defects passivation, which leads to significantly enhanced device performance. Our results provide new fundamental insights into the role of organic molecular passivators in boosting the performance of PeLEDs.

The Effects of Grain Size and Twins Density on High Temperature Oxidation Behavior of Nickel-Based Superalloy GH738.

In the present study, surface treatment techniques such as room temperature machining (RTM) and low temperature burnishing (LTB) processing have been used to improve the microstructure of GH738 superalloy. Nano-grains and nano-twins are obtained on the top surface of RTM and LTB specimens. It is found that although the grain size of RTM and LTB specimens is almost the same, different types of nano-twins have been produced. Moreover, the effect of RTM and LTB processing on high temperature oxidation behavior of nickel-based superalloy GH738 at 700 °C is investigated. The result shows that LTB specimen has the best high temperature oxidation resistance owing to the formation of nano-grains and higher twins density, which induce to form a continuous protective Al2O3 layer at the interface between outer oxide layer and matrix. It is observed that this layer inhibits the inward diffusion of O and outward diffusion of Ti and significantly improves oxidation resistance of LTB specimen. Furthermore, the effects of nano-grains and crystal defects on the diffusion mechanism of elements are clarified during the high temperature oxidation test.

Investigation of WO3 Electrodeposition Leading to Nanostructured Thin Films.

Nanostructured WO3 represents a promising material for electrochromic and sensing devices. In this scenario, electrodeposition is a promising low-cost approach for careful production. The electrodeposition of tungsten oxide film from a peroxo-tungstic-acid (PTA) solution is investigated. WO3 is synthetized onto Indium doped Tin Oxide (ITO) substrates, in a variety of shapes, from a fragmentary, thin layer up to a thick continuous film. Samples were investigated by scanning electron (SEM) and atomic force microscopy (AFM), Rutherford backscattering spectrometry (RBS), X-ray Diffraction analysis (XRD), energy gap measurement. Electrodeposition current curves are compared with characterization results to model the growth process. Early stages of electrodeposition are characterized by a transient cathodic current revealing an instantaneous nucleation followed by a diffusion limited process. A quantitative analysis of W deposition rate and current at working electrode validates a microscopic model for WO3 electrodeposition driving the process towards nanostructured versus continuous WO3 film.

The Effect of Heat Treatment on the Microstructure and Mechanical Properties of 2D Nanostructured Au/NiFe System.

Nanostructured NiFe film was obtained on silicon with a thin gold sublayer via pulsed electrodeposition and annealed at a temperature from 100 to 400 °C in order to study the effect of heat treatment on the surface microstructure and mechanical properties. High-resolution atomic force microscopy made it possible to trace stepwise evolving microstructure under the influence of heat treatment. It was found that NiFe film grains undergo coalescence twice-at ~100 and ~300 °C-in the process of a gradual increase in grain size. The mechanical properties of the Au/NiFe nanostructured system have been investigated by nanoindentation at two various indentation depths, 10 and 50 nm. The results showed the opposite effect of heat treatment on the mechanical properties in the near-surface layer and in the material volume. Surface homogenization in combination with oxidation activation leads to abnormal strengthening and hardening-up of the near-surface layer. At the same time, a nonlinear decrease in hardness and Young's modulus with increasing temperature of heat treatment characterizes the internal volume of nanostructured NiFe. An explanation of this phenomenon was found in the complex effect of changing the ratio of grain volume/grain boundaries and increasing the concentration of thermally activated diffuse gold atoms from the sublayer to the NiFe film.

A High-Kinetics Sulfur Cathode with a Highly Efficient Mechanism for Superior Room-Temperature Na-S Batteries.

Applications of room-temperature-sodium sulfur (RT-Na/S) batteries are currently impeded by the insulating nature of sulfur, the slow redox kinetics of sulfur with sodium, and the dissolution and migration of sodium polysulfides. Herein, a novel micrometer-sized hierarchical S cathode supported by FeS2 electrocatalyst, which is grown in situ in well-confined carbon nanocage assemblies, is presented. The hierarchical carbon matrix can provide multiple physical entrapment to polysulfides, and the FeS2 nanograins exhibit a low Na-ion diffusion barrier, strong binding energy, and high affinity for sodium polysulfides. Their combination makes it an ideal sulfur host to immobilize the polysulfides and achieve reversible conversion of polysulfides toward Na2 S. Importantly, the hierarchical S cathode is suitable for large-scale production via the inexpensive and green spray-drying method. The porous hierarchical S cathode offers a high sulfur content of 65.5 wt%, and can deliver high reversible capacity (524 mAh g-1 over 300 cycles at 0.1 A g-1 ) and outstanding rate capability (395 mAh g-1 at 1 A g-1 for 850 cycles), holding great promise for both scientific research and real application.

Enhanced Gene Delivery in Bacterial and Mammalian Cells Using PEGylated Calcium Doped Magnetic Nanograin.

BACKGROUND: Beyond viral carriers which have been widely used in gene delivery, non-viral carriers can further improve the delivery process. However, the high cytotoxicity and low efficiency impedes the clinical application of non-viral systems. Therefore, in this work, we fabricated polyethylene glycol (PEG) coated, calcium doped magnetic nanograin (PEG/Ca(II)/Fe3O4) as a genome expression enhancer. METHODS: Monodisperse magnetic nanograins (MNGs) with tunable size were synthesized by a solvothermal method. The citrate anions on the spherical surface of MNGs capture Ca2+ ions by an ion exchange process, which was followed by surface capping with PEG. The synthesized PEG/Ca(II)/Fe3O4 was characterized using Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) spectra, vibrating sample magnetometer (VSM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). MTT test was utilized to assess the toxicity of PEG/Ca(II)/Fe3O4. Real time qPCR was applied for quantification of gene expression. RESULTS: DLS spectra and TEM images confirmed a thin layer of PEG on the nanocarrier surface. Shifting the zeta potential in the biological pH window from -23.9 mV (for Fe3O4) to ≈ +11 mV (for PEG/Ca(II)/Fe3O4) confirms the MNGs surface protonation. Cytotoxicity results show that cell viability and proliferation were not hindered in a wide range of nanocarrier concentrations and different incubation times. CONCLUSION: PEGylated calcium doped magnetic nanograin enhanced PUC19 plasmid expression into E. Coli and GFP protein expression in HEK-293 T cells compared to control. A polymerase chain reaction of the NeoR test shows that the transformed plasmids are of high quality.