Kink bands promote exceptional fracture resistance in a NbTaTiHf refractory medium-entropy alloy.

Single-phase body-centered cubic (bcc) refractory medium- or high-entropy alloys can retain compressive strength at elevated temperatures but suffer from extremely low tensile ductility and fracture toughness. We examined the strength and fracture toughness of a bcc refractory alloy, NbTaTiHf, from 77 to 1473 kelvin. This alloy's behavior differed from that of comparable systems by having fracture toughness over 253 MPa·m1/2, which we attribute to a dynamic competition between screw and edge dislocations in controlling the plasticity at a crack tip. Whereas the glide and intersection of screw and mixed dislocations promotes strain hardening controlling uniform deformation, the coordinated slip of <111> edge dislocations with {110} and {112} glide planes prolongs nonuniform strain through formation of kink bands. These bands suppress strain hardening by reorienting microscale bands of the crystal along directions of higher resolved shear stress and continually nucleate to accommodate localized strain and distribute damage away from a crack tip.

In situ observation of melt pool evolution in ultrasonic vibration-assisted directed energy deposition.

The presence of defects, such as pores, in materials processed using additive manufacturing represents a challenge during the manufacturing of many engineering components. Recently, ultrasonic vibration-assisted (UV-A) directed energy deposition (DED) has been shown to reduce porosity, promote grain refinement, and enhance mechanical performance in metal components. Whereas it is evident that the formation of such microstructural features is affected by the melt pool behavior, the specific mechanisms by which ultrasonic vibration (UV) influences the melt pool remain elusive. In the present investigation, UV was applied in situ to DED of 316L stainless steel single tracks and bulk parts. For the first time, high-speed video imaging and thermal imaging were implemented in situ to quantitatively correlate the application of UV to melt pool evolution in DED. Extensive imaging data were coupled with in-depth microstructural characterization to develop a statistically robust dataset describing the observed phenomena. Our findings show that UV increases the melt pool peak temperature and dimensions, while improving the wettability of injected particles with the melt pool surface and reducing particle residence time. Near the substrate, we observe that UV results in a 92% decrease in porosity, and a 54% decrease in dendritic arm spacing. The effect of UV on the melt pool is caused by the combined mechanisms of acoustic cavitation, ultrasound absorption, and acoustic streaming. Through in situ imaging we demonstrate quantitatively that these phenomena, acting simultaneously, effectively diminish with increasing build height and size due to acoustic attenuation, consequently decreasing the positive effect of implementing UV-A DED. Thus, this research provides valuable insight into the value of in situ imaging, as well as the effects of UV on DED melt pool dynamics, the stochastic interactions between the melt pool and incoming powder particles, and the limitations of build geometry on the UV-A DED technique.

Visualization and validation of twin nucleation and early-stage growth in magnesium.

The abrupt occurrence of twinning when Mg is deformed leads to a highly anisotropic response, making it too unreliable for structural use and too unpredictable for observation. Here, we describe an in-situ transmission electron microscopy experiment on Mg crystals with strategically designed geometries for visualization of a long-proposed but unverified twinning mechanism. Combining with atomistic simulations and topological analysis, we conclude that twin nucleation occurs through a pure-shuffle mechanism that requires prismatic-basal transformations. Also, we verified a crystal geometry dependent twin growth mechanism, that is the early-stage growth associated with instability of plasticity flow, which can be dominated either by slower movement of prismatic-basal boundary steps, or by faster glide-shuffle along the twinning plane. The fundamental understanding of twinning provides a pathway to understand deformation from a scientific standpoint and the microstructure design principles to engineer metals with enhanced behavior from a technological standpoint.

Embracing the Chaos: Alloying Adds Stochasticity to Twin Embryo Growth.

High-throughput atomistic simulations reveal the unique effect of solute atoms on twin variant selection in Mg-Al alloys. Twin embryo growth first undergoes a stochastic incubation stage when embryos choose which twin variant to adopt, and then a deterministic growth stage when embryos expand without changing the selected twin variant. An increase in Al composition promotes the stochastic incubation behavior on the atomic level due to nucleation and pinning of interfacial disconnections. At compositions above a critical value, disconnection pinning results in multiple twin variant selection.

Alloying effects on the plasticity of magnesium: comprehensive analysis of influences of all five slip systems.

Low plasticity has been a major issue for the application of Mg alloys. Here, based on the generalized stacking fault energy curves and Arrhenius equation, we systematically study alloying effects on the stacking fault energies and the activation probability of basal and non-basal 〈a〉, and pyramidal 〈c + a〉 slip systems in twenty-one Mg alloys. Our results reveal that activation of 〈c + a〉 slip systems on pyramidal II plane can significantly improve the plasticity. For example, Ca is found to promote the activation probability of this slip system by one order of magnitude and dramatically improve the plasticity of Mg.

Aluminum with dispersed nanoparticles by laser additive manufacturing.

While laser-printed metals do not tend to match the mechanical properties and thermal stability of conventionally-processed metals, incorporating and dispersing nanoparticles in them should enhance their performance. However, this remains difficult to do during laser additive manufacturing. Here, we show that aluminum reinforced by nanoparticles can be deposited layer-by-layer via laser melting of nanocomposite powders, which enhance the laser absorption by almost one order of magnitude compared to pure aluminum powders. The laser printed nanocomposite delivers a yield strength of up to 1000 MPa, plasticity over 10%, and Young's modulus of approximately 200 GPa, offering one of the highest specific Young's modulus and specific yield strengths among structural metals, as well as an improved specific strength and thermal stability up to 400 °C compared to other aluminum-based materials. The improved performance is attributed to a high density of well-dispersed nanoparticles, strong interfacial bonding between nanoparticles and Al matrix, and ultrafine grain sizes.

Bulk ultrafine grained/nanocrystalline metals via slow cooling.

Cooling, nucleation, and phase growth are ubiquitous processes in nature. Effective control of nucleation and phase growth is of significance to yield refined microstructures with enhanced performance for materials. Recent studies reveal that ultrafine grained (UFG)/nanocrystalline metals exhibit extraordinary properties. However, conventional microstructure refinement methods, such as fast cooling and inoculation, have reached certain fundamental limits. It has been considered impossible to fabricate bulk UFG/nanocrystalline metals via slow cooling. Here, we report a new discovery that nanoparticles can refine metal grains to ultrafine/nanoscale by instilling a continuous nucleation and growth control mechanism during slow cooling. The bulk UFG/nanocrystalline metal with nanoparticles also reveals an unprecedented thermal stability. This method overcomes the grain refinement limits and may be extended to any other processes that involve cooling, nucleation, and phase growth for widespread applications.

In-Situ Imaging of Molten High-Entropy Alloys Using Cold Neutrons.

Real-time neutron imaging was utilized to produce a movie-like series of radiographs for in-situ observation of the remixing of liquid state immiscibility that occurs in equiatomic CoCrCu with the addition of Ni. A previous neutron imaging study demonstrated that liquid state immiscibility can be observed in-situ for the equiatomic CoCrCu alloy. In this follow-up study, equiatomic buttons of CoCrCu were placed alongside small Ni buttons inside an alumina crucible in a high-temperature vacuum furnace. The mass of the Ni buttons was specifically selected such that when melted in the same crucible as the CoCrCu buttons, the overall composition would become equiatomic CoCrCuNi. Neutron imaging was simultaneously carried out to capture 10 radiographs in 20 °C steps from 1000 °C to 1500 °C and back down to 1000 °C. This, in turn, produced a movie-like series of radiographs that allow for the observation of the buttons melting, the transition from immiscible to miscible as Ni is alloyed into the CoCrCu system, and solidification. This novel imaging process showed the phase-separated liquids remixing into a single-phase liquid when Ni dissolves into the melt, which makes this technique crucial for understanding the liquid state behavior of these complex alloy systems. As metals are not transparent to X-ray imaging techniques at this scale, neutron imaging of melting and solidification allows for the observation of liquid state phase changes in real time. Thermodynamic calculations of the isopleth for CoCrCuNix were carried out to compare the observed results to the predictions resulting from the current Thermo-Calc TCHEA3 thermodynamic database. The calculations show a very good agreement with the experimental results, as the calculations indicate that the CoCrCuNix alloy solidifies from a single-phase liquid when x ≥ 0.275, which is close to the nominal concentration of the CoCrCuNi alloy (x = 0.25). The neutron imaging shows that the solidification of CoCrCuNi results from a single-phase liquid. This is evident as no changes in the neutron attenuation were observed during the solidification of the CoCrCuNi alloy.

A high-entropy alloy with hierarchical nanoprecipitates and ultrahigh strength.

High-entropy alloys (HEAs) are a class of metallic materials that have revolutionized alloy design. They are known for their high compressive strengths, often greater than 1 GPa; however, the tensile strengths of most reported HEAs are limited. Here, we report a strategy for the design and fabrication of HEAs that can achieve ultrahigh tensile strengths. The proposed strategy involves the introduction of a high density of hierarchical intragranular nanoprecipitates. To establish the validity of this strategy, we designed and fabricated a bulk Fe25Co25Ni25Al10Ti15 HEA to consist of a principal face-centered cubic (fcc) phase containing hierarchical intragranular nanoprecipitates. Our results show that precipitation strengthening, as one of the main strengthening mechanisms, contributes to a tensile yield strength (σ0.2) of ~1.86 GPa and an ultimate tensile strength of ~2.52 GPa at room temperature, which heretofore represents the highest strength reported for an HEA with an appreciable failure strain of ~5.2%.

Precipitation phenomena in Al-Zn-Mg alloy matrix composites reinforced with B4C particles.

To provide insight into precipitation phenomena in age-hardening Al-Zn-Mg(-Cu) matrix composites, an Al 7075 alloy composite reinforced with B4C particles was selected as a model system. The bulk composites were fabricated via plasma activated sintering and followed by a peak aged (T6) heat treatment. Two types of Al matrix zones were identified in the composite: (1) the regions in the vicinity of the matrix/reinforcement interface, defined as "matrix plastic zone" (MPZ) hereafter, and (2) the regions away from the matrix/reinforcement interface, simply defined as matrix hereafter. The precipitation behavior in the MPZ was characterized and compared to that in the matrix. The MPZ contained a high density of dislocations. The number density of GP zones in the MPZ is lower than that in the matrix while the average size of the GP zones in MPZ is coarser. In addition, semi-coherent platelet η' precipitates were observed but only in the MPZ. The dislocations and the Al/B4C interfaces provide more heterogeneous nucleation sites for the η' precipitates in the MPZ. The growth and coarsening of the η' precipitates caused rapid depletion of Mg and Zn solute atoms in the MPZ.

Deformation of a ceramic/metal interface at the nanoscale.

The mechanical response of heterophase interfaces has attracted substantial attention in recent years. Here, we utilized an in situ transmission electron microscopy (TEM) technique to isolate an individual nanoscale ceramic/metal interface and characterize its nanomechanical response. The interface, at which there was a Mg-rich segregation nanolayer between the single crystal ceramic (B4C) and the polycrystalline metal (Al alloy, AA5083), was determined to have a bond strength greater than 1.5 GPa. Bimodal failure and metallic grain rotation occurred in the metallic region, allowing the interface to accommodate a deformation strain of 5.4%. The roles of elemental segregation and nanoscale dimensions on interfacial debonding mechanisms are discussed.

Microstructure and Electrical Properties of AZO/Graphene Nanosheets Fabricated by Spark Plasma Sintering.

In this study we report on the sintering behavior, microstructure and electrical properties of Al-doped ZnO ceramics containing 0-0.2 wt. % graphene sheets (AZO-GNSs) and processed using spark plasma sintering (SPS). Our results show that the addition of <0.25 wt. % GNSs enhances both the relative density and the electrical resistivity of AZO ceramics. In terms of the microstructure, the GNSs are distributed at grain boundaries. In addition, the GNSs are also present between ZnO and secondary phases (e.g., ZnAl2O4) and likely contribute to the measured enhancement of Hall mobility (up to 105.1 cm²·V-1·s-1) in these AZO ceramics. The minimum resistivity of the AZO-GNS composite ceramics is 3.1 × 10-4 Ω·cm which compares favorably to the value of AZO ceramics which typically have a resistivity of 1.7 × 10-3 Ω·cm.

An Efficient and Cost-Effective Method for Preparing Transmission Electron Microscopy Samples from Powders.

The preparation of transmission electron microcopy (TEM) samples from powders with particle sizes larger than ~100 nm poses a challenge. The existing methods are complicated and expensive, or have a low probability of success. Herein, we report a modified methodology for preparation of TEM samples from powders, which is efficient, cost-effective, and easy to perform. This method involves mixing powders with an epoxy on a piece of weighing paper, curing the powder-epoxy mixture to form a bulk material, grinding the bulk to obtain a thin foil, punching TEM discs from the foil, dimpling the discs, and ion milling the dimpled discs to electron transparency. Compared with the well established and robust grinding-dimpling-ion-milling method for TEM sample preparation for bulk materials, our modified approach for preparing TEM samples from powders only requires two additional simple steps. In this article, step-by-step procedures for our methodology are described in detail, and important strategies to ensure success are elucidated. Our methodology has been applied successfully for preparing TEM samples with large thin areas and high quality for many different mechanically milled metallic powders.

Nanocrystalline ß-Ti alloy with high hardness, low Young's modulus and excellent in vitro biocompatibility for biomedical applications.

High strength, low Young's modulus and good biocompatibility are desirable but difficult to simultaneously achieve in metallic implant materials for load bearing applications, and these impose significant challenges in material design. Here we report that a nano-grained ß-Ti alloy prepared by high-pressure torsion exhibits remarkable mechanical and biological properties. The hardness and modulus of the nano-grained Ti alloy were respectively 23% higher and 34% lower than those of its coarse-grained counterpart. Fibroblast cell attachment and proliferation were enhanced, demonstrating good in vitro biocompatibility of the nano-grained Ti alloy, consistent with demonstrated increased nano-roughness on the nano-grained Ti alloy. Results suggest that the nano-grained ß-Ti alloy may have significant application as an implant material in dental and orthopedic applications.

Structure modulation driven by cyclic deformation in nanocrystalline NiFe.

Theoretical modeling suggests that the grain size remains unchanged during fatigue crack growth in nanocrystalline metals. Here we demonstrate that a modulated structure is generated in a nanocrystalline Ni-Fe alloy under cyclic deformation. Substantial grain coarsening and loss of growth twins are observed in the path of fatigue cracks, while the grains away from the cracks remain largely unaffected. Statistical analyses suggest that the grain coarsening is realized through the grain lattice rotation and coalescence and the loss of growth twins may be related to the detwinning process near crack tip.

Nanostructural hierarchy increases the strength of aluminium alloys.

Increasing the strength of metallic alloys while maintaining formability is an interesting challenge for enabling new generations of lightweight structures and technologies. In this paper, we engineer aluminium alloys to contain a hierarchy of nanostructures and possess mechanical properties that expand known performance boundaries-an aerospace-grade 7075 alloy exhibits a yield strength and uniform elongation approaching 1 GPa and 5%, respectively. The nanostructural architecture was observed using novel high-resolution microscopy techniques and comprises a solid solution, free of precipitation, featuring (i) a high density of dislocations, (ii) subnanometre intragranular solute clusters, (iii) two geometries of nanometre-scale intergranular solute structures and (iv) grain sizes tens of nanometres in diameter. Our results demonstrate that this novel architecture offers a design pathway towards a new generation of super-strong materials with new regimes of property-performance space.

Oxidation of CO catalyzed by a Cu cluster: influence of an electric field.

Adsorption ability and reaction rate are two essential parameters that define the efficiency of a catalyst. Herein, we implement density functional theory (DFT) and report that CO can be oxidized by a pyramidal Cu cluster with an associated reaction barrier E(b)=1.317 eV. In this case, our transition state calculations reveal that the barrier can be significantly lowered after superimposing a negative electric field. Moreover, when the field intensity corresponds to F=-0.010 au, the magnitude of E(b)=0.698 eV is equivalent to-or lower than-those of typical catalysts such as Pt, Rh, and Pd. The superimposition of a positive field is found to enhance the release of the nascent CO(2) molecule. Our study demonstrates that small Cu clusters have better adsorption ability than the corresponding flat surface while the field can be used to enhance the purification of the exhaust gas.

High Plasticity and Substantial Deformation in Nanocrystalline NiFe Alloys Under Dynamic Loading.

A nanocrystalline (NC) NiFe alloy is presented, in which both highly improved plasticity and strength are achieved by the dynamic-loading-induced deformation mechanisms of de-twinning (that is, reduction of twin density) and significant grain coarsening. This work highlights potential ingenious avenues to exploit the superior behavior of NC materials under extreme conditions.

Identification of material parameters based on Mohr-Coulomb failure criterion for bisphosphonate treated canine vertebral cancellous bone.

Nanoindentation has been widely used to study bone tissue mechanical properties. The common method and equations for analyzing nanoindentation, developed by Oliver and Pharr, are based on the assumption that the material is linearly elastic. In the present study, we adjusted the constraint of linearly elastic behavior and use nonlinear finite element analysis to determine the change in cancellous bone material properties caused by bisphosphonate treatment, based on an isotropic form of the Mohr-Coulomb failure model. Thirty-three canine lumbar vertebrae were used in this study. The dogs were treated daily for 1 year with oral doses of alendronate, risedronate, or saline vehicle at doses consistent, on a mg/kg basis, to those used clinically for the treatment of post-menopausal osteoporosis. Two sets of elastic modulus and hardness values were calculated for each specimen using the Continuous Stiffness Measurement (CSM) method (E(CSM) and H(CSM)) from the loading segment and the Oliver-Pharr method (E(O-P) and H(O-P)) from the unloading segment, respectively. Young's modulus (E(FE)), cohesion (c), and friction angle (phi) were identified using a finite element model for each nanoindentation. The bone material properties were compared among groups and between methods for property identification. Bisphosphonate treatment had a significant effect on several of the material parameters. In particular, Oliver-Pharr hardness was larger for both the risedronate- and alendronate-treated groups compared to vehicle and the Mohr-Coulomb cohesion was larger for the risedronate-treated compared to vehicle. This result suggests that bisphosphonate treatment increases the hardness and shear strength of bone tissue. Shear strength was linearly predicted by modulus and hardness measured by the Oliver-Pharr method (r(2)=0.99). These results show that bisphosphonate-induced changes in Mohr-Coulomb material properties, including tissue shear cohesive strength, can be accurately calculated from Oliver-Pharr measurements of Young's modulus and hardness.

Human iliac crest cancellous bone elastic modulus and hardness differ with bone formation rate per bone surface but not by existence of prevalent vertebral fracture.

The goals of this study were to measure tissue-level elastic moduli and hardness of human cancellous bone using nanoindentation, and determine the relationship between nanoindentation results and previously measured bone histomorphometric variables and bone mineralization. Forty iliac crest biopsies were used in this study, which were collected from Caucasian females with vertebral fracture or from a normal healthy female Caucasian population. They were also categorized into two groups according to high or low bone formation rate per bone surface (BFR/BS). Thirty-two sites were randomly selected on each specimen for nanoindentation with a Berkovich diamond indenter. Two sets of elastic moduli and hardness were calculated using the continuous stiffness measurement method and the Oliver-Pharr method, respectively. Relationships between nanoindentation results and donor age, bone mineralization, and histomorphometric variables were examined. No difference in elastic moduli or hardness was observed between the normal and fracture groups. Significantly lower elastic moduli were observed in the high BFR/BS group. The elastic moduli and hardness measurements were not significantly correlated with the bone mineralization measured independently in a previous study. Linear correlation between elastic modulus and hardness calculated using the Oliver-Pharr method was not different between the normal and fracture groups or between the high and low BFR/BS groups. Nanoindentation hardness was a very good predictor of bone tissue elastic modulus for both normal and osteoporotic bone tissues. Osteoporosis may not change the relationship between bone tissue elastic modulus, bone hardness, and bone mineralization.