Flaw-Containing Alumina Hollow Nanostructures Have Ultrahigh Fracture Strength To Be Incorporated into High-Efficiency GaN Light-Emitting Diodes.

In the present study, we found that α-alumina hollow nanoshell structure can exhibit an ultrahigh fracture strength even though it contains a significant number of nanopores. By systematically performing in situ mechanical testing and finite element simulations, we could measure that the fracture strength of an α-alumina hollow nanoshell structure is about four times higher than that of the conventional bulk size α-alumina. The high fracture strength of the α-alumina hollow nanoshell structure can be explained in terms of conventional fracture mechanics, in that the position and size of the nanopores are the most critical factors determining the fracture strength, even at the nanoscales. More importantly, by deriving a fundamental understanding, we would be able to provide guidelines for the design of reliable ceramic nanostructures for advanced GaN light-emitting diodes (LEDs). To that end, we demonstrated how our ultrastrong α-alumina hollow nanoshell structures could be successfully incorporated into GaN LEDs, thereby greatly improving the luminous efficiency and output power of the LEDs by 2.2 times higher than that of conventional GaN LEDs.

Engineering the shape and structure of materials by fractal cut.

In this paper we discuss the transformation of a sheet of material into a wide range of desired shapes and patterns by introducing a set of simple cuts in a multilevel hierarchy with different motifs. Each choice of hierarchical cut motif and cut level allows the material to expand into a unique structure with a unique set of properties. We can reverse-engineer the desired expanded geometries to find the requisite cut pattern to produce it without changing the physical properties of the initial material. The concept was experimentally realized and applied to create an electrode that expands to >800% the original area with only very minor stretching of the underlying material. The generality of our approach greatly expands the design space for materials so that they can be tuned for diverse applications.

Easy preparation of self-assembled high-density buckypaper with enhanced mechanical properties.

A controlled assembly and alignment of carbon nanotubes (CNTs) in a high-packing density with a scalable way remains challenging. This paper focuses on the preparation of self-assembled and well-aligned CNTs with a densely packed nanostructure in the form of buckypaper via a simple filtration method. The CNT suspension concentration is strongly reflected in the alignment and assembly behavior of CNT buckypaper. We further demonstrated that the horizontally aligned CNT domain gradually increases in size when increasing the deposited CNT quantity. The resultant aligned buckypaper exhibited notably enhanced packing density, strength, modulus, and hardness compared to previously reported buckypapers.

Nanoscale liquid Al phase formation through beam heating of MgAl2O4 in TEM.

In this study, electron-beam irradiation of a MgAl2O4 single-crystalline thin-film specimen in a transmission electron microscope reveals an unexpected formation of nanoscale liquid Al droplets. Despite the comparable melting temperatures of Mg and Al, the resulting liquid phase is predominantly composed of Al. This predominant presence of Al in the liquid phase is attributed to the selective evaporation of Mg, driven by its higher vapor pressure at elevated temperatures. Our observations suggest a correlation between electron-beam irradiation and a subsequent rise in specimen temperature. In particular, the observed melting of Al defies explanation by the widely accepted mechanism that attributes specimen heating to electron-energy loss, given the negligible energy deposited as determined by the collision stopping power. Instead, we suggest that the significant specimen heating is due to Auger excitation, a process known to deposit substantial energy. This contention is supported by a quantitative heat-transfer finite element analysis.

Geometry-induced dislocations in coaxial heterostructural nanotubes.

Highly localized dislocations in GaN/ZnO hetero-nanostructures are generated from the residual strain field by lattice mismatches at two interfaces: between the substrate and hetero-nanostructures, and between the ZnO core and GaN shell. The local strain field is measured using tranmission electron microscopy, and the relationship between the nanostructure morphology and the highly localized dislocations is analyzed by a finite element method.

Statistical analysis on static recrystallization texture evolution in cold-rolled AZ31 magnesium alloy sheet.

Cast AZ31B-H24 magnesium alloy, comprising Mg with 3.27 wt% Al and 0.96 wt% Zn, was cold rolled and subsequently annealed. Global texture evolutions in the specimens were observed by X-ray diffractometry after the thermomechanical processing. Image-based microstructure and texture for the deformed, recrystallized, and grown grains were observed by electron backscattered diffractometry. Recrystallized grains could be distinguished from deformed ones by analyzing grain orientation spread. Split basal texture of ca. ±10-15° in the rolling direction was observed in the cold-rolled sample. Recrystallized grains had widely spread basal poles at nucleation stage; strong {0001} basal texture developed with grain growth during annealing.

Elucidating the role of a unique step-like interfacial structure of η4 precipitates in Al-Zn-Mg alloy.

Al-Zn-Mg alloys are widely used in the transportation industry owing to their high strength-to-weight ratio. In these alloys, the main strengthening mechanism is precipitation hardening that occurs because of the formation of nano-sized precipitates. Herein, an interfacial structure of η4 precipitates, one of the main precipitates in these alloys, is revealed using aberration-corrected scanning transmission electron microscopy and first-principles calculations. These precipitates exhibit a pseudo-periodic steps and bridges. The results of this study demonstrate that the peculiar interface structure of η4/Al relieves the strain energy of η4 precipitates thus stabilizing them. The atomistic role of this interfacial structure in the nucleation and growth of the precipitates is elucidated. This study paves the way for tailoring the mechanical properties of alloys by controlling their precipitation kinetics.

Doubled strength and ductility via maraging effect and dynamic precipitate transformation in ultrastrong medium-entropy alloy.

Demands for ultrahigh strength in structural materials have been steadily increasing in response to environmental issues. Maraging alloys offer a high tensile strength and fracture toughness through a reduction of lattice defects and formation of intermetallic precipitates. The semi-coherent precipitates are crucial for exhibiting ultrahigh strength; however, they still result in limited work hardening and uniform ductility. Here, we demonstrate a strategy involving deformable semi-coherent precipitates and their dynamic phase transformation based on a narrow stability gap between two kinds of ordered phases. In a model medium-entropy alloy, the matrix precipitate acts as a dislocation barrier and also dislocation glide media; the grain-boundary precipitate further contributes to a significant work-hardening via dynamic precipitate transformation into the type of matrix precipitate. This combination results in a twofold enhancement of strength and uniform ductility, thus suggesting a promising alloy design concept for enhanced mechanical properties in developing various ultrastrong metallic materials.

Fatigue-free, electrically reliable copper electrode with nanohole array.

Design and fabrication of reliable electrodes is one of the most important challenges in flexible devices, which undergo repeated deformation. In conventional approaches, mechanical and electrical properties of continuous metal films degrade gradually because of the fatigue damage. The designed incorporation of nanoholes into Cu electrodes can enhance the reliability. In this study, the electrode shows extremely low electrical resistance change during bending fatigue because the nanoholes suppress crack initiation by preventing protrusion formation and damage propagation by crack tip blunting. This concept provides a key guideline for developing fatigue-free flexible electrodes.

Faceting-roughening transition of a Cu grain boundary under electron-beam irradiation at 300 keV.

In this study, we examined the beam-irradiation effect on the structural evolution of the grain boundary (GB) in a Cu bicrystal at room temperature using a Cs-corrected, monochromated transmission electron microscope at an acceleration voltage of 300 keV. Faceting of the GB was observed at a low current density of the electron beam. With increasing current density, the GB became defaceted. The faceting-roughening transition was shown to be reversible, as the process was reversed upon decreasing the current density. The structural transition is explained by inelastic scattering effects by electron-beam irradiation.

Suppressing High-Current-Induced Phase Separation in Ni-Rich Layered Oxides by Electrochemically Manipulating Dynamic Lithium Distribution.

Understanding the cycling rate-dependent kinetics is crucial for managing the performance of batteries in high-power applications. Although high cycling rates may induce reaction heterogeneity and affect battery lifetime and capacity utilization, such phase transformation dynamics are poorly understood and uncontrollable. In this study, synchrotron-based operando X-ray diffraction is performed to monitor the high-current-induced phase transformation kinetics of LiNi0.6 Co0.2 Mn0.2 O2 . The sluggish Li diffusion at high Li content induces different phase transformations during charging and discharging, with strong phase separation and homogeneous phase transformation during charging and discharging, respectively. Moreover, by exploiting the dependence of Li diffusivity on the Li content and electrochemically tuning the initial Li content and distribution, phase separation pathway can be redirected to solid solution kinetics at a high charging rate of 7 C. Finite element analysis further elucidates the effect of the Li-content-dependent diffusion kinetics on the phase transformation pathway. The findings suggest a new direction for optimizing fast-cycling protocols based on the intrinsic properties of the materials.

Evidence of Stress Development as a Source of Driving Force for Grain-Boundary Migration in a Ni Bicrystalline TEM Specimen.

In a previous study, using high-resolution transmission electron microscopy (HRTEM), we examined grain-boundary migration behavior in a Ni bicrystal. A specimen for transmission electron microscopy (TEM) was prepared using focused ion beam. The Ni lamella in the specimen was composed of two grains with surface normal directions of [1 0 0] and [1 1 0]. As the lamella was heated to 600 °C in a TEM, it was subjected to compressive stresses. The stress state of the Ni lamella approximated to the isostress condition, which was confirmed by a finite element method. However, the stress development was not experimentally confirmed in the previous study. In the present study, we present an observation of stacking faults with a length of 40-70 nm at the grain boundary as direct evidence of the stress development.

A new class of lightweight, stainless steels with ultra-high strength and large ductility.

Steel is the global backbone material of industrialized societies, with more than 1.8 billion tons produced per year. However, steel-containing structures decay due to corrosion, destroying annually 3.4% (2.5 trillion US$) of the global gross domestic product. Besides this huge loss in value, a solution to the corrosion problem at minimum environmental impact would also leverage enhanced product longevity, providing an immense contribution to sustainability. Here, we report a leap forward toward this aim through the development of a new family of low-density stainless steels with ultra-high strength (> 1 GPa) and high ductility (> 35%). The alloys are based on the Fe-(20-30)Mn-(11.5-12.0)Al-1.5C-5Cr (wt%) system and are strengthened by dispersions of nano-sized Fe3AlC-type κ-carbide. The alloying with Cr enhances the ductility without sacrificing strength, by suppressing the precipitation of κ-carbide and thus stabilizing the austenite matrix. The formation of a protective Al-rich oxide film on the surface lends the alloys outstanding resistance to pitting corrosion similar to ferritic stainless steels. The new alloy class has thus the potential to replace commercial stainless steels as it has much higher strength at similar formability, 17% lower mass density and lower environmental impact, qualifying it for demanding lightweight, corrosion resistant, high-strength structural parts.

Analyzing the microstructure and related properties of 2D materials by transmission electron microscopy.

Two-dimensional materials such as transition metal dichalcogenide and graphene are of great interest due to their intriguing electronic and optical properties such as metal-insulator transition based on structural variation. Accordingly, detailed analyses of structural tunability with transmission electron microscopy have become increasingly important for understanding atomic configurations. This review presents a few analyses that can be applied to two-dimensional materials using transmission electron microscopy.

Selective crack suppression during deformation in metal films on polymer substrates using electron beam irradiation.

While cracks are usually considered detrimental, crack generation can be harnessed for various applications, for example in ceramic materials, via directing crack propagation and crack opening. Here, we find that electron beam irradiation prompts a crack suppression phenomenon in a copper (Cu) thin film on a polyimide substrate, allowing for the control of crack formation in terms of both location and shape. Under tensile strain, cracks form on the unirradiated region of the Cu film whereas cracks are prevented on the irradiated region. We attribute this to the enhancement of the adhesion at the Cu-polyimide interface by electrons transmitted through the Cu film. Finally, we selectively form conductive regions in a Cu film on a polyimide substrate under tension and fabricate a strain-responsive organic light-emitting device.

Microstructure and Solidification Crack Susceptibility of Al 6014 Molten Alloy Subjected to a Spatially Oscillated Laser Beam.

Oscillating laser beam welding for Al 6014 alloy was performed using a single mode fiber laser and two-axis scanner system. Its effect on the microstructural evolution of the fusion zone was investigated. To evaluate the influence of oscillation parameters, self-restraint test specimens were fabricated with different beam patterns, widths, and frequencies. The behavior of hot cracking propagation was analyzed by high-speed camera and electron backscatter diffraction. The behavior of crack propagation was observed to be highly correlated with the microstructural evolution of the fusion zone. For most oscillation conditions, the microstructure resembled that of linear welds. A columnar structure was formed near the fusion line and an equiaxed structure was generated at its center. The wide equiaxed zone of oscillation welding increased solidification crack susceptibility. For an oscillation with an infinite-shaped scanning pattern at 100 Hz and 3.5 m/min welding speed, the bead width, solidification microstructure, and the width of the equiaxed zone at the center of fusion fluctuated. Furthermore, the equiaxed and columnar regions alternated periodically, which could reduce solidification cracking susceptibility.

Stabilization of a Ga-adlayer structure with the zincblende stacking sequence in the GaN(0 0 0 -1) surface at the nanoscale.

Profile imaging by in situ high-resolution transmission electron microscopy is used to elucidate reconstructions of the GaN(0 0 0 -1) surface during annealing in the TEM. We have successfully captured a detailed process of a change from the stacking sequence of the wurtzite to that of the zincblende structure in the topmost three Ga layers for the surface with nanoscale hill-and-valley structures. For ab initio calculations of the change in the sequence, a model structure is approximated by the addition of a 1 × 1 Ga layer on the GaN(0 0 0 -1) surface (i.e., 1 × 1 Ga-adlayer structure). The ab initio calculations predict that, as the surface size decreases, the 1 × 1 Ga-adlayer structure with the wurtzite stacking sequence in the topmost three Ga layers becomes destabilized against the adlayer with the zincblende stacking sequence in the surface layers, which well elucidates the experimental observation.

Wall-thickness-dependent strength of nanotubular ZnO.

We fabricate nanotubular ZnO with wall thickness of 45, 92, 123 nm using nanoporous gold (np-Au) with ligament diameter at necks of 1.43 µm as sacrificial template. Through micro-tensile and micro-compressive testing of nanotubular ZnO structures, we find that the exponent m in [Formula: see text], where [Formula: see text] is the relative strength and [Formula: see text] is the relative density, for tension is 1.09 and for compression is 0.63. Both exponents are lower than the value of 1.5 in the Gibson-Ashby model that describes the relation between relative strength and relative density where the strength of constituent material is independent of external size, which indicates that strength of constituent ZnO increases as wall thickness decreases. We find, based on hole-nanoindentation and glazing incidence X-ray diffraction, that this wall-thickness-dependent strength of nanotubular ZnO is not caused by strengthening of constituent ZnO by size reduction at the nanoscale. Finite element analysis suggests that the wall-thickness-dependent strength of nanotubular ZnO originates from nanotubular structures formed on ligaments of np-Au.

Migration mechanism of a GaN bicrystalline grain boundary as a model system.

Using in situ high-resolution transmission electron microscopy, we have explored migration mechanism of a grain boundary in a GaN bicrystal as a model system. During annealing at 500 °C, the grain-boundary region underwent a decrease in thickness, which occurred by decomposition or sublimation of GaN during annealing at 500 °C coupled with electron-beam sputtering. The decrease in thickness corresponds to an increase in the driving force for migration, because the migration of the grain boundary was driven by the surface energy difference. As the driving force increased with annealing time, the grain-boundary morphology turned from atomically smooth to rough, which is characterized by kinetic roughening. The observations indicate that a grain boundary exhibits a nonlinear relationship between driving force for migration and migration velocity, in discord with the general presumption that a grain boundary follows a linear relationship.

In Vitro and In Vivo Evaluation of Whitlockite Biocompatibility: Comparative Study with Hydroxyapatite and ß-Tricalcium Phosphate.

Biomimicking ceramics have been developed to induce efficient recovery of damaged hard tissues. Among them, calcium phosphate-based bioceramics have been the most widely used because of their similar composition with human hard tissue and excellent biocompatibilities. However, the incomplete understanding of entire inorganic phases in natural bone has limited the recreation of complete bone compositions. In this work, broad biomedical evaluation of whitlockite (WH: Ca18Mg2(HPO4)2(PO4)12), which is the secondary inorganic phase in bone, is conducted to better understand human hard tissue and to seek potential application as a biomaterial. Based on the recently developed gram-scale method for synthesizing WH nanoparticles, the properties of WH as a material for cellular scaffolding and bone implants are assessed and compared to those of hydroxyapatite (HAP: Ca10(PO4)6(OH)2) and ß-tricalcium phosphate (ß-TCP: ß-Ca3(PO4)2). WH-reinforced composite scaffolds facilitate bone-specific differentiation compared to HAP-reinforced composite scaffolds. Additionally, WH implants induce similar or better bone regeneration in calvarial defects in a rat model compared to HAP and ß-TCP implants, with intermediate resorbability. New findings of the properties of WH that distinguish it from HAP and ß-TCP are significant in understanding human hard tissue, mimicking bone tissue at the nanoscale and designing functional bioceramics.