Mechanically Robust Self-Organized Crack-Free Nanocellular Graphene with Outstanding Electrochemical Properties in Sodium Ion Battery.

Crack-free nanocellular graphenes are attractive materials with extraordinary mechanical and electrochemical properties, but their homogeneous synthesis on the centimeter scale is challenging. Here, a strong nanocellular graphene film achieved by the self-organization of carbon atoms using liquid metal dealloying and employing a defect-free amorphous precursor is reported. This study demonstrates that a Bi melt strongly catalyzes the self-structuring of graphene layers at low processing temperatures. The robust nanoarchitectured graphene displays a high-genus seamless framework and exhibits remarkable tensile strength (34.8 MPa) and high electrical conductivity (1.6 × 104 S m-1). This unique material has excellent potential for flexible and high-rate sodium-ion battery applications.

Work hardening behavior of hot-rolled metastable Fe50Co25Ni10Al5Ti5Mo5 medium-entropy alloy: in situ neutron diffraction analysis.

Metastability engineering is a strategy to enhance the strength and ductility of alloys via deliberately lowering phase stability and prompting deformation-induced martensitic transformation. The advantages of the strategy are widely exploited by ferrous medium-entropy alloys (MEAs) that exhibit phase transformation from metastable face-centered cubic (FCC) to hexagonal close-packed (HCP) or body-centered cubic (BCC) martensite and a significant increase in work hardening. Fe50Co25Ni10Al5Ti5Mo5 (at%) MEA is an example of such materials, which shows ~1.5 GPa of tensile strength assisted by exceptional work hardening from the deformation-induced BCC martensitic transformation. In this work, the martensitic transformation and its effect on the mechanical response of the MEA were studied by in situ neutron diffraction under tensile loading. Strain-induced BCC martensite started forming rapidly from the beginning of plastic deformation, reaching a phase fraction of ~100% when deformed to ~10% of true strain. Lattice strain and phase stress evolution indicate that stress was dynamically partitioned onto the newly formed BCC martensite, which is responsible for the work hardening response and high flow stress of the MEA. This work shows how great a role FCC to BCC martensitic transformation can play in enhancing the mechanical properties of ferrous MEAs.

Ultrafine nanoporous intermetallic catalysts by high-temperature liquid metal dealloying for electrochemical hydrogen production.

Intermetallic compounds formed from non-precious transition metals are promising cost-effective and robust catalysts for electrochemical hydrogen production. However, the development of monolithic nanoporous intermetallics, with ample active sites and sufficient electrocatalytic activity, remains a challenge. Here we report the fabrication of nanoporous Co7Mo6 and Fe7Mo6 intermetallic compounds via liquid metal dealloying. Along with the development of three-dimensional bicontinuous open porosity, high-temperature dealloying overcomes the kinetic energy barrier, enabling the direct formation of chemically ordered intermetallic phases. Unprecedented small characteristic lengths are observed for the nanoporous intermetallic compounds, resulting from an intermetallic effect whereby the chemical ordering during nanopore formation lowers surface diffusivity and significantly suppresses the thermal coarsening of dealloyed nanostructure. The resulting ultrafine nanoporous Co7Mo6 exhibits high catalytic activity and durability in electrochemical hydrogen evolution reactions. This study sheds light on the previously unexplored intermetallic effect in dealloying and facilitates the development of advanced intermetallic catalysts for energy applications.

A Fabry-Pérot cavity coupled surface plasmon photodiode for electrical biomolecular sensing.

Surface plasmon resonance is a well-established technology for real-time highly sensitive label-free detection and measurement of binding kinetics between biological samples. A common drawback, however, of surface plasmon resonance detection is the necessity for far field angular resolved measurement of specular reflection, which increases the size as well as requiring precise calibration of the optical apparatus. Here we present an alternative optoelectronic approach in which the plasmonic sensor is integrated within a photovoltaic cell. Incident light generates an electronic signal that is sensitive to the refractive index of a solution via interaction with the plasmon. The photogenerated current is enhanced due to the coupling of the plasmon mode with Fabry-Pérot modes in the absorbing layer of the photovoltaic cell. The near field electrical detection of surface plasmon resonance we demonstrate will enable a next generation of cheap, compact and high throughput biosensors.

Decoupling between calorimetric and dynamical glass transitions in high-entropy metallic glasses.

Glass transition is one of the unresolved critical issues in solid-state physics and materials science, during which a viscous liquid is frozen into a solid or structurally arrested state. On account of the uniform arrested mechanism, the calorimetric glass transition temperature (Tg) always follows the same trend as the dynamical glass transition (or α-relaxation) temperature (Tα) determined by dynamic mechanical analysis (DMA). Here, we explored the correlations between the calorimetric and dynamical glass transitions of three prototypical high-entropy metallic glasses (HEMGs) systems. We found that the HEMGs present a depressed dynamical glass transition phenomenon, i.e., HEMGs with moderate calorimetric Tg represent the highest Tα and the maximum activation energy of α-relaxation. These decoupled glass transitions from thermal and mechanical measurements reveal the effect of high configurational entropy on the structure and dynamics of supercooled liquids and metallic glasses, which are associated with sluggish diffusion and decreased dynamic and spatial heterogeneities from high mixing entropy. The results have important implications in understanding the entropy effect on the structure and properties of metallic glasses for designing new materials with plenteous physical and mechanical performances.

Microstructure Refinement of a Transformation-Induced Plasticity High-Entropy Alloy.

High-entropy alloys (HEAs) have attracted extensive interest due to their unprecedented structure and mechanical performance. We recently proposed a series of novel corich twinning induced plasticity (TWIP) and transformation induced plasticity (TRIP) HEAs with superior tensile properties at room temperature; however, the hot deformation behavior has not been reported. Here, we investigated the dynamic recrystallization behavior and grain refinement of a representative TRIP-HEA, compressed at temperatures of 1123-1273 K with strain rates of 0.1-0.001 s-1. We characterized the impact of the temperature and strain rate on the grain structure evolution. A constitutive equation was constructed to reveal the correlations between the flow stress, strain rate, temperature, and strain. The apparent activation energy was estimated to be ~385.7 kJ/mol. The discontinuous dynamic recrystallization played an important role in the grain refinement, particularly at a relatively higher temperature and a lower strain rate, and the volume fraction and morphology of the recrystallized grains exhibited a strong dependency on the Zener-Hollomon parameter. The study provides guidelines for the grain refinement of HEAs through thermomechanical processing.

Surface Functionalization of Biomedical Ti-6Al-7Nb Alloy by Liquid Metal Dealloying.

Surface functionalization is an effective approach to change the surface properties of a material to achieve a specific goal such as improving the biocompatibility of the material. Here, the surface of the commercial biomedical Ti-6Al-7Nb alloy was functionalized through synthesizing of a porous surface layer by liquid metal dealloying (LMD). During LMD, the Ti-6Al-7Nb alloy is immersed in liquid magnesium (Mg) and both materials react with each other. Particularly, aluminum (Al) is selectively dissolved from the Ti-6Al-7Nb alloy into liquid Mg while titanium (Ti) and niobium (Nb) diffuse along the metal/liquid interface to form a porous structure. We demonstrate that the porous surface layer in the Ti-6Al-7Nb alloy can be successfully tailored by LMD. Furthermore, the concentration of harmful Al in this porous layer is reduced by about 48% (from 5.62 ± 0.11 wt.% to 2.95 ± 0.05 wt.%) after 30 min of dealloying at 1150 K. The properties of the porous layer (e.g., layer thickness) can be tuned by varying the dealloying conditions. In-vitro tests suggest improved bone formation on the functionalized porous surface of the Ti-6Al-7Nb alloy.

Beating Thermal Coarsening in Nanoporous Materials via High-Entropy Design.

Controlling the feature sizes of 3D bicontinuous nanoporous (3DNP) materials is essential for their advanced applications in catalysis, sensing, energy systems, etc., requiring high specific surface area. However, the intrinsic coarsening of nanoporous materials naturally reduces their surface energy leading to the deterioration of physical properties over time, even at ambient temperatures. A novel 3DNP material beating the universal relationship of thermal coarsening is reported via high-entropy alloy (HEA) design. In newly developed TiVNbMoTa 3DNP HEAs, the nanoporous structure is constructed by very fine nanoscale ligaments of a solid-solution phase due to enhanced phase stability by maximizing the configuration entropy and suppressed surface diffusion. The smallest size of 3DNP HEA synthesized at 873 K is about 10 nm, which is one order of magnitude smaller than that of conventional porous materials. More importantly, the yield strength of ligament in 3DNP HEA approaches its theoretical strength of G/2π of the corresponding HEA alloy even after thermal exposure. This finding signifies the key benefit of high-entropy design in nanoporous materials-exceptional stability of size-related physical properties. This high-entropy strategy should thus open new opportunities for developing ultrastable nanomaterials against its environment.

Interaction of a Ti⁻Cu Alloy with Carbon: Synthesis of Composites and Model Experiments.

Titanium carbide (TiC), is the most thermodynamically stable compound in the Ti-C-Cu system, which makes it a suitable reinforcement phase for copper matrix composites. In this work, the interaction of a Ti-Cu alloy with different forms of carbon was investigated to trace the structural evolution leading to the formation of in-situ TiC-Cu composite structures. The reaction mixtures were prepared from Ti25Cu75 alloy ribbons and carbon black or nanodiamonds to test the possibilities of obtaining fine particles of TiC using ball milling and Spark Plasma Sintering (SPS). It was found that the behavior of the reaction mixtures during ball milling depends on the nature of the carbon source. Model experiments were conducted to observe the outcomes of the diffusion processes at the alloy/carbon interface. It was found that titanium atoms diffuse to the alloy/graphite interface and react with carbon forming a titanium carbide layer, but carbon does not diffuse into the alloy. The diffusion experiments as well as the synthesis by ball milling and SPS indicated that the distribution of TiC particles in the composite structures obtained via reactive solid-state processing of Ti25Cu75+C follows the distribution of carbon particles in the reaction mixtures. This justifies the use of carbon sources that have fine particles to prepare the reaction mixtures as well as efficient dispersion of the carbon component in the alloy-carbon mixture when the goal is to synthesize fine particles of TiC in the copper matrix.

Nano-imprinting potential of magnetic FeCo-based metallic glass.

Fabrication of magnetic nanostructures at low cost is strongly desired for applications such as sensors, actuators, magnetic memory, etc. In conventional nano-patterning techniques, the magnetic field of a magnetic material interferes with the patterning process, making nano-patterning challenging. Here, we report on the low cost patterning potential of FeCo-based magnetic metallic glass using a nano-imprinting technique. We show that out of a large number of magnetic metallic glasses, Fe40Co35P10C10B5 glassy alloy exhibits high saturation magnetic flux density (B s  âˆ¼ 1.24 T), a large super-cooled liquid temperature range (ΔT x  âˆ¼ 49 °C), and a relatively low glass transition temperature (T g  âˆ¼ 430 °C) with good thermal stability. The quasi-static viscosity (∼108 Pa.s at a heating rate of ∼40 °C min-1) in ΔT x , which is one of the most important parameters for nano-imprinting, is lowest among the reported magnetic metallic glasses. The deformability of this magnetic alloy is similar to the well-known non-magnetic metallic glasses, which can be patterned to a few tens of nanometers. Crystallization of Fe40Co35P10C10B5 glassy alloy leads to the precipitation of a high B s FeCo phase that may exhibit high magnetocrystalline anisotropy. Based on detailed investigations of structural, thermal, and magnetic behavior, along with imprinting experiments, we show that the Fe40Co35P10C10B5 glassy alloy is the most desirable material for making various nano-patterns with tailorable magnetic properties.

Porous NiTi Particle Dispersed Mg-Zn-Ca Bulk Metallic Glass Matrix Composites.

Even though the Mg-based bulk metallic glasses (BMGs) have shown superior anti-corrosion properties compared with their crystalline counterparts, the brittleness of them limits the widespread application of these materials. In the present study, we have firstly introduced porous NiTi shape memory alloy particles into an Mg-Zn-Ca BMG by the direct adding method. This composite showed both improved compressive strength and corrosion resistance in Hank's solutions than its monolithic glassy counterpart. The NiTi dispersoids among the matrix were likely to hinder the main shear band propagation, and also acted as the corrosion barriers. Furthermore, the porous nature of present added particle could further increase the interface areas, which should enhance the reinforcing effects compared with solid ones. This low-cost, high-anticorrosive composite was a good candidate as an engineering material.

On the Potential of Bulk Metallic Glasses for Dental Implantology: Case Study on Ti40Zr10Cu36Pd14.

Ti40Zr10Cu36Pd14 Bulk Metallic Glass (BMG) appears very attractive for future biomedical applications thanks to its high glass forming ability, the absence of toxic elements such as Ni, Al or Be and its good mechanical properties. For the first time, a complete and exhaustive characterization of a unique batch of this glassy alloy was performed, together with ISO standard mechanical tests on machined implant-abutment assemblies. The results were compared to the benchmark Ti-6Al-4V ELI (Extra-Low-Interstitial) to assess its potential in dental implantology. The thermal stability, corrosion and sterilization resistance, cytocompatibility and mechanical properties were measured on samples with a simple geometry, but also on implant-abutment assemblies' prototypes. Results show that the glassy alloy exhibits a quite high thermal stability, with a temperature range of 38 °C between the glass transition and crystallization, a compressive strength of 2 GPa, a certain plastic deformation (0.7%), a hardness of 5.5 GPa and a toughness of 56 MPa.√m. Moreover, the alloy shows a relatively lower Young's modulus (96 GPa) than the Ti-6Al-4V alloy (110-115 GPa), which is beneficial to limit bone stress shielding. The BMG shows a satisfactory cytocompatibility, a high resistance to sterilization and a good corrosion resistance (corrosion potential of -0.07 V/SCE and corrosion current density of 6.0 nA/cm²), which may ensure its use as a biomaterial. Tests on dental implants reveal a load to failure 1.5-times higher than that of Ti-6Al-4V and a comparable fatigue limit. Moreover, implants could be machined and sandblasted by methods usually conducted for titanium implants, without significant degradation of their amorphous nature. All these properties place this metallic glass among a promising class of materials for mechanically-challenging applications such as dental implants.

Three-Dimensional Morphological and Chemical Evolution of Nanoporous Stainless Steel by Liquid Metal Dealloying.

Nanoporous materials, especially those fabricated by liquid metal dealloying processes, possess great potential in a wide range of applications due to their high surface area, bicontinuous structure with both open pores for transport and solid phase for conductivity or support, and low material cost. Here, we used X-ray nanotomography and X-ray fluorescence microscopy to reveal the three-dimensional (3D) morphology and elemental distribution within materials. Focusing on nanoporous stainless steel, we evaluated the 3D morphology of the dealloying front and established a quantitative processing-structure-property relationship at a later stage of dealloying. The morphological differences of samples created by liquid metal dealloying and aqueous dealloying methods were also discussed. We concluded that it is particularly important to consider the dealloying, coarsening, and densification mechanisms in influencing the performance-determining, critical 3D parameters, such as tortuosity, pore size, porosity, curvature, and interfacial shape.

Edge-illumination x-ray phase contrast imaging with Pt-based metallic glass masks.

Edge-illumination x-ray phase contrast imaging (EI XPCI) is a non-interferometric phase-sensitive method where two absorption masks are employed. These masks are fabricated through a photolithography process followed by electroplating which is challenging in terms of yield as well as time- and cost-effectiveness. We report on the first implementation of EI XPCI with Pt-based metallic glass masks fabricated by an imprinting method. The new tested alloy exhibits good characteristics including high workability beside high x-ray attenuation. The fabrication process is easy and cheap, and can produce large-size masks for high x-ray energies within minutes. Imaging experiments show a good quality phase image, which confirms the potential of these masks to make the EI XPCI technique widely available and affordable.

A novel method of surface modification by electrochemical deoxidation: Effect on surface characteristics and initial bioactivity of zirconia.

The aim of this study was to investigate and compare the surface characteristics and initial bioactivity of ceria-stabilized zirconia/alumina nanocomposite (NANOZR) with those of yttria-stabilized zirconia (3Y-TZP) and pure titanium (CpTi) following the use of three surface modification methods; polishing, sandblasting/acid-etching (SB-E) and electrochemical deoxidation (ECD). Physical properties including surface morphology, chemical composition, X-ray diffraction, surface wettability, surface roughness, and hardness were measured. Osteoblast-like MC3T3-E1 cells were used to examine cell morphology and attachment to the surfaces of the materials. ECD treated NANOZR (NANOZR-E) showed a well-arranged, self-organized microporous surface structure with significantly low contact angles when compared with the other specimens (p < 0.05). NANOZR-E also demonstrated a slight decrease in monoclinic phase content (-4.4 wt %). The morphology and attachment of MC3T3-E1 cells on NANOZR-E were similar to those on polished and SBE-treated CpTi surfaces. Higher cell affinity was observed on NANOZR-E when compared with ECD treated 3Y-TZP. The findings of this study indicate the effectiveness of the novel technique, ECD, in the formation of a microporous surface on NANOZR when compared with both CpTi and 3Y-TZP. Moreover, this method also appears to improve the biological activity of NANOZR during the initial stage. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2641-2652, 2017.

Work-hardening induced tensile ductility of bulk metallic glasses via high-pressure torsion.

The mechanical properties of engineering materials are key for ensuring safety and reliability. However, the plastic deformation of BMGs is confined to narrow regions in shear bands, which usually result in limited ductilities and catastrophic failures at low homologous temperatures. The quasi-brittle failure and lack of tensile ductility undercut the potential applications of BMGs. In this report, we present clear tensile ductility in a Zr-based BMG via a high-pressure torsion (HPT) process. Enhanced tensile ductility and work-hardening behavior after the HPT process were investigated, focusing on the microstructure, particularly the changed free volume, which affects deformation mechanisms (i.e., initiation, propagation, and obstruction of shear bands). Our results provide insights into the basic functions of hydrostatic pressure and shear strain in the microstructure and mechanical properties of HPT-processed BMGs.

Bulk-nanoporous-silicon negative electrode with extremely high cyclability for lithium-ion batteries prepared using a top-down process.

We synthesized freestanding bulk three-dimensional nanoporous Si using dealloying in a metallic melt, a top-down process. Using this nanoporous Si, we fabricated negative electrodes with high lithium capacity, nearing their theoretical limits, and greatly extended cycle lifetimes, considerably improving the battery performance compared with those using electrodes made from silicon nanoparticles. By operating the electrodes below the accommodation volume limit of their pores, we prolonged their cycle lifetime.

Characteristics of the structural and Johari-Goldstein relaxations in Pd-based metallic glass-forming liquids.

The dynamics of Pd-based metallic glass-forming liquids (Pd(40)Ni(10)Cu(30)P(20), Pd(42.5)Ni(7.5)Cu(30)P(20), Pd(40)Ni(40)P(20), and Pd(30)Ni(50)P(20)) was studied by mechanical spectroscopy and modulated differential scanning calorimetry (MDSC). We found that the change in composition has a significant effect on the α relaxation dynamics; the largest difference corresponds to an increase of the glass transition temperature Tg of ∼ 15 K, for materials in which 30% Ni was substituted by 30% Cu (i.e., from Pd(40)Ni(40)P(20) to Pd(40)Ni(10)Cu(30)P(20)). We also found that all Pd-based metallic glasses have very similar fragilities, 59 < m < 67, and Kohlrausch stretched exponents, 0.59 < ßKWW < 0.60. It is interesting that the values of m and ßKWW correlate well with the general relation proposed by Böhmer et al. for nonmetallic glass formers (Böhmer, R.; et al. J. Chem. Phys. 1993, 99, 4201-4209), which for the observed ßKWW values predicts 58 < m < 61. From a linear deconvolution of the α and ß relaxations, we find that the substitution of the Ni with Cu induced a large change in the time constant of the Johari-Goldstein relaxation, τß. The activation energy, Uß, of the ß relaxation was largely independent of chemical composition. In all cases, 25 < Uß/RT < 28, a range in agreement with results for other glass formers (Kudlik, A.; et al. Europhys. Lett. 1997, 40, 649-654 and Ngai, K. L.; et al. Phys. Rev. E 2004, 69, 031501). From the heat capacity and mechanical loss, estimates were obtained for the number of dynamically correlated units, Nc; we find significantly larger values for these metallic glass-forming liquids than Nc for other glass-forming materials.

Cobalt-based bulk glassy alloy with ultrahigh strength and soft magnetic properties.

Bulk metallic glasses--formed by supercooling the liquid state of certain metallic alloys--have potentially superior mechanical properties to crystalline materials. Here, we report a Co(43)Fe(20)Ta(5.5)B(31.5) glassy alloy exhibiting ultrahigh fracture strength of 5,185 MPa, high Young's modulus of 268 GPa, high specific strength of 6.0 x 10(5) Nm kg(-1) and high specific Young's modulus of 31 x 10(6) Nm kg(-1). The strength, specific strength and specific Young's modulus are higher than previous values reported for any bulk crystalline or glassy alloys. Excellent formability is manifested by large tensile elongation of 1,400% and large reduction ratio in thickness above 90% in the supercooled liquid region. The ultrahigh-strength alloy also exhibited soft magnetic properties with extremely high permeability of 550,000. This alloy is promising as a new ultrahigh-strength material with good deformability and soft magnetic properties.