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We report that a series of lanthanide-based bulk metallic glasses show a pressure-induced polyamorphic phase transition observed by in situ angle-dispersive x-ray diffraction under high pressures. The transition started from a low-density state at lower pressures, and went through continuous densification ending with a high-density state at higher pressures. We demonstrate that, under high pressure, this new type of polyamorphism in densely packed metallic glasses is inherited from its lanthanide-solvent constituent and related to the electronic structure of 4f electrons. The found electronic structure inheritance could provide the guidance for designing new metallic glasses with unique functional physical properties.
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The issue, composition dependence of glass-forming ability (GFA) in metallic glasses (MG), has been investigated by systematic experimental measurements coupled with theoretical calculations in Cu-Zr and Ni-Nb alloy systems. It is found that the atomic-level packing efficiency strongly relates to their GFA. The best GFA is located at the largest difference in the packing efficiency of the solute-centered clusters between the glassy and crystal alloys in both MG systems. This work provides an understanding of GFA from atomic level and will shed light on the development of new MGs with larger critical sizes.
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The ability to predict and understand phases in high-entropy alloys (HEAs) is still being debated, and primarily true predictive capabilities derive from the known thermodynamics of materials. The present work demonstrates that prior work using high-throughput first-principles calculations may be further utilized to provide direct insight into the temperature- and composition-dependent phase evolution in HEAs, particularly Al-containing HEAs with a strengthening multiphase microstructure. Using a simple model with parameters derived from first-principles calculations, we reproduce the major features associated with Al-containing phases, demonstrating a generalizable approach for exploring potential phase evolution where little experimental data exists. Neutron scattering, in situ microscopy, and calorimetry measurements suggest that our high-throughput Monte Carlo technique captures both qualitative and quantitative features for both intermetallic phase formation and microstructure evolution at lower temperatures. This study provides a simple approach to guide HEA development, including ordered multi-phase HEAs, which may prove valuable for structural applications.
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The mechanical behavior of a single phase (fcc) Al0.3CoCrFeNi high-entropy alloy (HEA) was studied in the low and high strain-rate regimes. The combination of multiple strengthening mechanisms such as solid solution hardening, forest dislocation hardening, as well as mechanical twinning leads to a high work hardening rate, which is significantly larger than that for Al and is retained in the dynamic regime. The resistance to shear localization was studied by dynamically-loading hat-shaped specimens to induce forced shear localization. However, no adiabatic shear band could be observed. It is therefore proposed that the excellent strain hardening ability gives rise to remarkable resistance to shear localization, which makes this material an excellent candidate for penetration protection applications such as armors.
Assuntos
Ligas/química , Fenômenos Mecânicos , Alumínio/análise , Cromo/análise , Cobalto/análise , Ferro/análise , Teste de Materiais , Níquel/análiseRESUMO
Remarkable tensile ductility was first obtained in an in-situ Ti-based bulk metallic glass (BMG) composite at cryogenic temperature (77 K). The novel cryogenic tensile plasticity is related to the effective accommodation of ductile body-centered cubic dendrites at 77 K, characteristic of the prevailing slip bands and dislocations, as well as lattice disorder, which can effectively hinder the propagation of critical shear bands. The greatly increased yield strength of dendrites contributes to the high yield strength of composite at 77 K. A trend of stronger softening is observed at low temperature, and a criterion is proposed to understand the softening behavior. The current research could also provide a guidance to the promising cryogenic application of these new advanced BMG composites.
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We report the magnetic field dependence of the critical solidification rate for the stability of liquid-solid interfaces. For a certain temperature gradient, the critical solidification rate first increases, then decreases, and subsequently increases with increasing magnetic field. The effect of the magnetic field on the critical solidification rate is more pronounced at low than at high temperature gradients. The numerical simulations show that the magnetic-field dependent changes of convection velocity and contour at the interface agree with the experimental results. The convection velocity first increases, then decreases, and finally increases again with increasing the magnetic field intensity. The variation of the convection contour at the interface first decreases, then increases slightly, and finally increases remarkably with increasing the magnetic field intensity. Thermoelectromagnetic convection (TEMC) plays the role of micro-stirring the melt and is responsible for the increase of interface stability within the initially increasing range of magnetic field intensity. The weak and significant extents of the magneto-hydrodynamic damping (MHD)-dependent solute build-up at the interface front result, respectively, in the gradual decrease and increase of interfacial stability with increasing the magnetic field intensity. The variation of the liquid-side concentration at the liquid-solid interface with the magnetic field supports the proposed mechanism.
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The plastic flow of bulk metallic glasses (BMGs) is characterized by intermittent bursts of avalanches, and this trend results in disastrous failures of BMGs. In the present work, a double-side-notched BMG specimen is designed, which exhibits chaotic plastic flows consisting of several catastrophic avalanches under the applied loading. The disastrous shear avalanches have, then, been delayed by forming a stable plastic-flow stage in the specimens with tailored distances between the bottoms of the notches, where the distribution of a complex stress field is acquired. Differing from the conventional compressive testing results, such a delaying process is independent of loading rate. The statistical analysis shows that in the specimens with delayed catastrophic failures, the plastic flow can evolve to a critical dynamics, making the catastrophic failure more predictable than the ones with chaotic plastic flows. The findings are of significance in understanding the plastic-flow mechanisms in BMGs and controlling the avalanches in relating solids.
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Bulk metallic glasses (BMGs) represent an emerging class of materials with an amorphous structure and a unique combination of properties. The objectives of this investigation were to define the electrochemical behavior of a specific Zr-based BMG alloy in a physiologically relevant environment and to compare these properties to standard, crystalline biomaterials as well as other Zr-based BMG compositions. Cyclic-anodic-polarization studies were conducted with a Zr52.5Cu17.9Ni14.6Al10.0Ti5.0 (at %) BMG in a phosphate-buffered saline electrolyte with a physiologically relevant oxygen content at 37 degrees C. The results were compared to three common, crystalline biomaterials: CoCrMo, 316L stainless steel, and Ti-6Al-4V. The BMG alloy was found to have a lower corrosion penetration rate (CPR), as compared to the 316L stainless steel, and an equivalent CPR, as compared to the CoCrMo and Ti-6Al-4V alloys. Furthermore, the BMG alloy demonstrated better localized corrosion resistance than the 316L stainless steel. However, the localized corrosion resistance of the BMG alloy was not as high as those of the CoCrMo and Ti-6Al-4V alloys in the tested environment. The excellent electrochemical properties demonstrated by the BMG alloy are combined with a low modulus and unparalleled strength. This unique combination of properties dramatically demonstrates the potential for amorphous alloys as a new generation of biomaterials.
Assuntos
Eletroquímica , Vidro/química , Zircônio/química , Soluções Tampão , Eletrodos , Compostos de Mercúrio , Fosfatos , Cloreto de Sódio , Difração de Raios XRESUMO
Slowly-compressed single crystals, bulk metallic glasses (BMGs), rocks, granular materials, and the earth all deform via intermittent slips or "quakes". We find that although these systems span 12 decades in length scale, they all show the same scaling behavior for their slip size distributions and other statistical properties. Remarkably, the size distributions follow the same power law multiplied with the same exponential cutoff. The cutoff grows with applied force for materials spanning length scales from nanometers to kilometers. The tuneability of the cutoff with stress reflects "tuned critical" behavior, rather than self-organized criticality (SOC), which would imply stress-independence. A simple mean field model for avalanches of slipping weak spots explains the agreement across scales. It predicts the observed slip-size distributions and the observed stress-dependent cutoff function. The results enable extrapolations from one scale to another, and from one force to another, across different materials and structures, from nanocrystals to earthquakes.
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A closed-loop electrohydraulic fatigue apparatus was constructed for testing from above room temperature to 77 K. Several important improvements in the electronics of the reference function generator and the servo controller over previous apparatus are described. The electronics allows cool-down of the specimen to 77 K at zero stress, correction for thermal contraction, and then cyclic fatigue testing under strain control, all without interruption of hydraulic power.
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The glass-coated melt spinning method offers a route for the manufacture of metal filaments with a few micrometers in diameter in a single operation directly from the melt. Cobalt-based amorphous wires, Cu-15.0 atomic percent (at. %) Sn shape-memory wires, and Ni2MnGa (atomic percent) ferromagnetic wires were successfully produced by this method. The cobalt-based amorphous wire is flexible, and Cu-15.0 at. % Sn shape-memory wires have the tensile elongation of 14%. However, because of chemical reaction with glass and oxidation, it is hard to make Cu-Al-Ni shape-memory wires and Ni-Nb-Sn amorphous wires. Conditions for preparing these materials were summarized, and the differences of the solidification processes among glass-coated amorphous cobalt-based wires, Cu-15.0 at. % Sn shape-memory wires, and Ni2MnGa wires were analyzed and discussed.
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In-situ dendrite/metallic glass matrix composites (MGMCs) with a composition of Ti46Zr20V12Cu5Be17 exhibit ultimate tensile strength of 1510 MPa and fracture strain of about 7.6%. A tensile deformation model is established, based on the five-stage classification: (1) elastic-elastic, (2) elastic-plastic, (3) plastic-plastic (yield platform), (4) plastic-plastic (work hardening), and (5) plastic-plastic (softening) stages, analogous to the tensile behavior of common carbon steels. The constitutive relations strongly elucidate the tensile deformation mechanism. In parallel, the simulation results by a finite-element method (FEM) are in good agreement with the experimental findings and theoretical calculations. The present study gives a mathematical model to clarify the work-hardening behavior of dendrites and softening of the amorphous matrix. Furthermore, the model can be employed to simulate the tensile behavior of in-situ dendrite/MGMCs.
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Bulk metallic glasses (BMGs) demonstrate attractive properties for potential biomedical applications, owing to their amorphous structure. The present work has investigated the biocompatibility of Zr-based BMGs by studying the cellular behavior of bone-forming mouse MC3T3-E1 pre-osteoblast cells. A Ti-6Al-4V alloy was used as a reference material. Pre-immersion treatment was performed on BMG samples in phosphate-buffered saline prior to cell experiments. The effects of 1at.% yttrium alloying and surface roughness on cellular behavior were examined. The general biosafety of Zr-based BMGs for MC3T3-E1 cells was revealed as normal cell responses. Pre-immersion treatment was found to effectively reduce the surface concentrations of alloying elements. Micro-alloying with 1 at.% yttrium did not significantly affect cell adhesion and proliferation, but slightly decreased alkaline phosphatase (ALP) activity on rough surfaces. Lower cell adhesion and proliferation were found on smooth surfaces of Zr-based BMGs compared to their rougher counterparts. Higher ALP activity was detected on rougher surfaces. To obtain a mechanistic understanding surface free energy was correlated with cell adhesion.
Assuntos
Vidro/química , Osteoblastos/citologia , Osteoblastos/efeitos dos fármacos , Osteogênese/efeitos dos fármacos , Zircônio/farmacologia , Actinas/metabolismo , Fosfatase Alcalina/metabolismo , Animais , Adesão Celular/efeitos dos fármacos , Contagem de Células , Morte Celular/efeitos dos fármacos , Diferenciação Celular/efeitos dos fármacos , Proliferação de Células/efeitos dos fármacos , Forma Celular/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Citoesqueleto/efeitos dos fármacos , Citoesqueleto/metabolismo , Adesões Focais/efeitos dos fármacos , Adesões Focais/metabolismo , Camundongos , Minerais/metabolismo , Osteoblastos/enzimologia , Osteoblastos/ultraestrutura , Espectroscopia Fotoeletrônica , Termodinâmica , Molhabilidade/efeitos dos fármacosRESUMO
In situ synchrotron and neutron diffraction were used to study deformation mechanisms in Ni over a broad range of grain sizes. The experimental data show that unlike in coarse-grained metals, where the deformation is dominated by dislocation slip, plastic deformation in nanocrystalline Ni is mediated by grain-boundary activities, as evidenced by the lack of intergranular strain and texture development. For ultrafine-grained Ni, although dislocation slip is an active deformation mechanism, deformation twinning also plays an important role, whose propensity increases with the grain size.
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Metallic W whiskers with tip diameters of 50-250 nm and lengths of 2-4 µm have been successfully synthesized in large quantities using Co-Ni alloyed catalysts. The relatively low growth temperature of 850 °C and the large catalyst size (over 100 nm) suggest that the growth of the W whiskers must be governed by the vapor-solid-solid mechanism. Our results show that the vapor-solid-solid model is suitable not only for the growth of nano-scaled whiskers with diameters below 100 nm, but also for submicro-scaled whiskers with diameters well above 100 nm. This technique has great potential to synthesize well controlled metallic whiskers.
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The mechanical behavior of Zr-based bulk amorphous alloy composites (BAACs) was investigated at 77 K. The 5 vol. % Ta-BAAC maintained large plastic strains of approximately 13% with a 16% strength increase, when compared with that at 298 K. The interaction between shear bands and particles shows that shear extension in particles has limited penetration, and shear bands build up around particles. In addition to on the failure surface of the amorphous matrix, molten characteristics were also found on the surface of sheared particles. Pair distribution function studies were performed to understand the mechanical behavior.