Atomic structure evolution related to the Invar effect in Fe-based bulk metallic glasses.

The Invar effect is universally observed in Fe-based bulk metallic glasses. However, there is limited understanding on how this effect manifests at the atomic scale. Here, we use in-situ synchrotron-based high-energy X-ray diffraction to study the structural transformations of (Fe71.2B24Y4.8)96Nb4 and (Fe73.2B22Y4.8)95Mo5 bulk metallic glasses around the Curie temperature to understand the Invar effect they exhibit. The first two diffraction peaks shift in accordance with the macroscopically measured thermal expansion, which reveals the Invar effect. Additionally, the nearest-neighbor Fe-Fe pair distance correlates well with the macroscopic thermal expansion. In-situ X-ray diffraction is thus able to elucidate the Invar effect in Fe-based metallic glasses at the atomic scale. Here, we find that the Invar effect is not just a macroscopic effect but has a clear atomistic equivalent in the average Fe-Fe pair distance and also shows itself in higher-order atomic shells composed of multiple atom species.

Oral Anticoagulant Treatment in Patients with Atrial Fibrillation and Chronic Kidney Disease.

Over the past few decades, a series of innovative medicines have been developed in order to optimize anticoagulation therapy for atrial fibrillation (AF). As a result, a number of nonvitamin K antagonist oral anticoagulants (NOAC) that directly target the enzymatic activity of factor II and factor Xa have been successfully licensed providing a more predictable effect and better safety profile compared to conventional anticoagulants (heparins and vitamin K antagonists (VKAs)). However, comparative efficacy and safety data is limited in patients with advanced chronic kidney disease (i.e., CKD stage 4/5 and end stage renal disease) because patients with estimated glomerular filtration rate (eGFR) < 30 mL/min/1.73 m2 were actively excluded from landmark trials, thus representing a major clinical limitation for the currently available agents. However, the renal function of AF patients can be altered over time. On the other hand, patients with CKD have an increased risk of developing AF. This review article will provide an overview of current concepts and recent evidence guiding the clinical use of NOACs in patients with CKD requiring chronic anticoagulation, and the associated risks and benefits of treatment in this specific patient population.

X-ray Diffraction Computed Nanotomography Applied to Solve the Structure of Hierarchically Phase-Separated Metallic Glass.

The structure of matter at the nanoscale, in particular that of amorphous metallic alloys, is of vital importance for functionalization. With the availability of synchrotron radiation, it is now possible to visualize the internal features of metallic samples without physically destroying them. Methods based on computed tomography have recently been employed to explore the local features. Tomographic reconstruction, while it is relatively uncomplicated for crystalline materials, may generate undesired artifacts when applied to featureless amorphous or nanostructured metallic alloys. In this study we show that X-ray diffraction computed nanotomography can provide accurate details of the internal structure of a metallic glass. We demonstrate the power of the method by applying it to a hierarchically phase-separated amorphous sample with a small volume fraction of crystalline inclusions, focusing the X-ray beam to 500 nm and ensuring a sub-micrometer 2D resolution via the number of scans.

Soft Ferromagnetic Bulk Metallic Glass with Potential Self-Healing Ability.

A new concept of soft ferromagnetic bulk metallic glass (BMG) with self-healing ability is proposed. The specific [Fe36Co36B19.2Si4.8Nb4]100-x(Ga)x (x = 0, 0.5, 1 and1.5) BMGs prepared by copper mold casting were investigated as a function of Ga content. The Ga-containing BMGs still hold soft magnetic properties and exhibit large plastic strain of 1.53% in compression. Local melting during shearing produces molten droplets of several µm size throughout the fracture surface. This concept of local melting during shearing can be utilized to produce BMGs with self-healing ability. The molten regions play a vital role in deflecting shear transformation zones, thereby enhancing the mechanical properties.

Routes to control diffusive pathways and thermal expansion in Ti-alloys.

ß-stabilized Ti-alloys present several unexplored and intriguing surprises in relation to orthorhombic α″ phases. Among them are (i) the diffusion-controlled formation of transitional α″iso, α″lean and α″rich phases and ii) the highly anisotropic thermal expansion of martensitic α″. Using the prototypical Ti-Nb system, we demonstrate that the thermodynamic energy landscape reveals formation pathways for the diffusional forms of α″ and may lead to a stable ß-phase miscibility gap. In this way, we derive temperature-composition criteria for the occurrence of α″iso and resolve reaction sequences during thermal cycling. Moreover, we show that the thermal expansion anisotropy of martensitic α″ gives rise to directions of zero thermal strain depending on Nb content. Utilizing this knowledge, we propose processing routes to achieve null linear expansion in α″ containing Ti-alloys. These concepts are expected to be transferable to other Ti-alloys and offer new avenues for their tailoring and technological exploitation.

Structure⁻Property Relationships in Shape Memory Metallic Glass Composites.

Metallic glass composites with shape memory crystals show enhanced plasticity and work-hardening capability. We investigate the influence of various critical structural aspects such as, the density of crystalline precipitates, their distribution and size, and the structural features and intrinsic properties of the phase on the deformation behavior of metallic amorphous Cu 64 Zr 36 composites with B2 CuZr inclusions using molecular dynamics simulations. We find that a low density of small B2 inclusions with spacing smaller than the critical shear band length controls the formation and distribution of plastic zones in the composite and hinders the formation of critical shear bands. When the free path for shearing allows the formation of mature shear bands a high volume fraction of large B2 precipitates is necessary to stabilize the shear flow and avoid runaway instability. Additionally, we also investigate the deformation mechanism of composites with pure copper crystals for comparison, in order to understand the superior mechanical properties of metallic glass composites with shape memory crystals in more detail. The complex and competing mechanisms of deformation occurring in shape memory metallic glass composites allow this class of materials to sustain large tensile deformation, even though only a low-volume fraction of crystalline inclusions is present.

Fast and direct determination of fragility in metallic glasses using chip calorimetry.

We directly determine the thermodynamic fragility index of two metallic glasses (Mg65Cu25Gd10 and Au49Cu26.9Si16.3Ag5.5Pd2.3) from fictive temperature shifts induced by a variation of the quenching rate using fast differential scanning calorimetry (FDSC). Recent chip calorimeters are able to achieve the cooling rates necessary to perform such an evaluation. For the Mg65Cu25Gd10 and Au49Cu26.9Si16.3Ag5.5Pd2.3 metallic glasses studied, we find very good agreement of the kinetic fragility index with literature data obtained by conventional calorimetry and rheology. The thermodynamic fragility indices are m=25.5 ± 1.5 for Mg65Cu25Gd10 and m=50.3 ± 2.3 for Au49Cu26.9Si16.3Ag5.5Pd2.3, respectively. The FDSC method discussed here allows for fast and reliable determination of the kinetic fragility of metallic glasses, and is thus competitive with high-frequency methods.

In Situ Synchrotron X-Ray Diffraction Characterization of Corrosion Products of a Ti-Based Metallic Glass for Implant Applications.

Ti-based bulk metallic glasses are under consideration for implants due to their high yield strength and biocompatibility. In this work, in situ synchrotron X-ray diffraction (XRD) is used to investigate the corrosion products formed from corrosion of Ti40 Zr10 Cu34 Pd14 Sn2 bulk metallic glass in artificial corrosion pits in physiological saline (NaCl). It is found that Pd nanoparticles form in the interior of the pits during electrochemical dissolution. At a low pit growth potential, the change in lattice parameter of the Pd nanoparticles is consistent with the formation of palladium hydride. In addition, a salt layer very close to the dissolving interface is found to contain CuCl, PdCl2 , ZrOCl2 ∙8H2 O, Cu, Cu2 O, and several unidentified phases. The formation of Pd nanoparticles (16 ± 10 nm at 0.7 V vs Ag/AgCl) containing small amounts of the other alloying elements is confirmed by transmission electron microscopy. The addition of albumin and/or H2 O2 does not significantly influence the nature of the corrosion products. When considering the biological compatibility of the alloy, the biological reactivity of the corrosion products identified should be explored.

Author Correction: Origin of large plasticity and multiscale effects in iron-based metallic glasses.

The authors became aware of a mistake in the original version of this Article. Specifically, where discussing the Curie temperature of the amorphous phase, Tc, in the 'Thermal characterization' section of the Results and in Fig. 2, the authors should have been discussing the Curie temperature of the magnetic crystalline phases T'c. While the Curie temperature of the glass is lower than previously reported, this error does not affect the original discussion or conclusions of the Article. The authors apologize for the confusion caused by this mistake. In addition to this, there were errors in some of the equations in the main text, and the glass composition. A number of changes have been made in both the PDF and HTML versions of the Article to reflect these errors. A full list of these changes is available online.

Origin of large plasticity and multiscale effects in iron-based metallic glasses.

The large plasticity observed in newly developed monolithic bulk metallic glasses under quasi-static compression raises a question about the contribution of atomic scale effects. Here, nanocrystals on the order of 1-1.5 nm in size are observed within an Fe-based bulk metallic glass using aberration-corrected high-resolution transmission electron microscopy (HRTEM). The accumulation of nanocrystals is linked to the presence of hard and soft zones, which is connected to the micro-scale hardness and elastic modulus confirmed by nanoindentation. Furthermore, we performed systematic simulations of HRTEM images at varying sample thicknesses, and established a theoretical model for the estimation of the shear transformation zone size. The findings suggest that the main mechanism behind the formation of softer regions are the homogenously dispersed nanocrystals, which are responsible for the start and stop mechanism of shear transformation zones and hence, play a key role in the enhancement of mechanical properties.

Giant thermal expansion and α-precipitation pathways in Ti-alloys.

Ti-alloys represent the principal structural materials in both aerospace development and metallic biomaterials. Key to optimizing their mechanical and functional behaviour is in-depth know-how of their phases and the complex interplay of diffusive vs. displacive phase transformations to permit the tailoring of intricate microstructures across a wide spectrum of configurations. Here, we report on structural changes and phase transformations of Ti-Nb alloys during heating by in situ synchrotron diffraction. These materials exhibit anisotropic thermal expansion yielding some of the largest linear expansion coefficients (+ 163.9×10-6 to -95.1×10-6 °C-1) ever reported. Moreover, we describe two pathways leading to the precipitation of the α-phase mediated by diffusion-based orthorhombic structures, α″lean and α″iso. Via coupling the lattice parameters to composition both phases evolve into α through rejection of Nb. These findings have the potential to promote new microstructural design approaches for Ti-Nb alloys and ß-stabilized Ti-alloys in general.

Hierarchical surface patterning of Ni- and Be-free Ti- and Zr-based bulk metallic glasses by thermoplastic net-shaping.

In order to establish a strong cell-material interaction, the surface topography of the implant material plays an important role. This contribution aims to analyze the formation kinetics of nickel and beryllium-free Ti- and Zr-based Bulk Metallic Glasses (BMGs) with potential biomedical applications. The surface patterning of the BMGs is achieved by thermoplastic net-shaping (TPN) into anisotropically etched cavities of silicon chips. The forming kinetics of the BMG alloys is assessed by thermal and mechanical measurements to determine the most suitable processing temperature and time, and load applied. Array of pyramidal micropatterns with a tip resolution down to 50nm is achievable for the Zr-BMG, where the generated hierarchical features are crucial for surface functionalization, acting as topographic cues for cell attachment. The unique processability and intrinsic properties of this new class of amorphous alloys make them competitive with the conventional biomaterials.

High pressure die casting of Fe-based metallic glass.

Soft ferromagnetic Fe-based bulk metallic glass key-shaped specimens with a maximum and minimum width of 25.4 and 5 mm, respectively, were successfully produced using a high pressure die casting (HPDC) method, The influence of die material, alloy temperature and flow rate on the microstructure, thermal stability and soft ferromagnetic properties has been studied. The results suggest that a steel die in which the molten metal flows at low rate and high temperature can be used to produce completely glassy samples. This can be attributed to the laminar filling of the mold and to a lower heat transfer coefficient, which avoids the skin effect in the steel mold. In addition, magnetic measurements reveal that the amorphous structure of the material is maintained throughout the key-shaped samples. Although it is difficult to control the flow and cooling rate of the molten metal in the corners of the key due to different cross sections, this can be overcome by proper tool geometry. The present results confirm that HPDC is a suitable method for the casting of Fe-based bulk glassy alloys even with complex geometries for a broad range of applications.

Towards the Better: Intrinsic Property Amelioration in Bulk Metallic Glasses.

Tailoring the intrinsic length-scale effects in bulk metallic glasses (BMGs) via post-heat treatment necessitates a systematic analyzing strategy. Although various achievements were made in the past years to structurally enhance the properties of different BMG alloys, the influence of short-term sub-glass transition annealing on the relaxation kinetics is still not fully covered. Here, we aim for unraveling the connection between the physical, (thermo)mechanical and structural changes as a function of selected pre-annealing temperatures and time scales with an in-house developed Cu46Zr44Al8Hf2 based BMG alloy. The controlled formation of nanocrystals below 50 nm with homogenous distribution inside the matrix phase via thermal treatment increase the material's resistance to strain softening by almost an order of magnitude. The present work determines the design aspects of metallic glasses with enhanced mechanical properties via nanostructural modifications, while postulating a counter-argument to the intrinsic property degradation accounted for long-term annealing.

New Cu-Free Ti-Based Composites with Residual Amorphous Matrix.

Titanium-based bulk metallic glasses (BMGs) are considered to have potential for biomedical applications because they combine favorable mechanical properties and good biocompatibility. Copper represents the most common alloying element, which provides high amorphization capacity, but reports emphasizing cytotoxic effects of this element have risen concerns about possible effects on human health. A new copper-free alloy with atomic composition Ti42Zr10Pd14Ag26Sn8, in which Cu is completely replaced by Ag, was formulated based on Morinaga's d-electron alloy design theory. Following this theory, the actual amount of alloying elements, which defines the values of covalent bond strength Bo and d-orbital energy Md, situates the newly designed alloy inside the BMG domain. By mean of centrifugal casting, cylindrical rods with diameters between 2 and 5 mm were fabricated from this new alloy. Differential scanning calorimetry (DSC) and X-rays diffraction (XRD), as well as microstructural analyses using optical and scanning electron microscopy (OM/SEM) revealed an interesting structure characterized by liquid phase-separated formation of crystalline Ag, as well as metastable intermetallic phases embedded in residual amorphous phases.

Crystallization during bending of a Pd-based metallic glass detected by x-ray microscopy.

Without the availability of slip systems and dislocation glide as in crystalline materials, metallic glasses resist irreversible deformation to elastic strains of 2% or more before undergoing heterogeneous plastic flow via the formation of shear bands. Observation of crystallite formation under compressive load was previously obtained by transmission electron microscopy. In this Letter, we present results of nondestructive x-ray diffraction microprofiling of the section of a bent glassy Pd40Cu30Ni10P20 ribbon in transmission using a synchrotron microbeam. Crystallization was clearly detected but only on the compression side of the neutral fiber. The experimental results and crystal nucleation frequency analysis are consistent with massive nucleation in shear bands forming under compressive stress but mainly for metallic glasses that show a large supercooled liquid temperature range ΔT=T(x)-T(g) between glass transition at T(g) and crystallization at T(x). The phenomenon is sensitively dependent on the volume change that accompanies crystallization in the supercooled liquid temperature range where the much larger liquid-state thermal expansion coefficient significantly increases the specific volume difference between the liquid and crystalline states. The results are also consistent with the many reports of extensive strain to fracture of metallic glasses under compressive load but not under tension.

Structural and Mechanical Characterization of Zr58.5Ti8.2Cu14.2Ni11.4Al7.7 Bulk Metallic Glass.

Thermal stability, structure and mechanical properties of the multi-component Zr58.5Ti8.2Cu14.2Ni11.4Al7.7 bulk metallic glass have been studied in detail. The glassy material displays good thermal stability against crystallization and a fairly large supercooled liquid region of 52 K. During heating, the alloy transforms into a metastable icosahedral quasicrystalline phase in the first stage of crystallization. At high temperatures, the quasicrystalline phase undergoes a transformation to form tetragonal and cubic NiZr2-type phases. Room-temperature compression tests of the as-cast sample show good mechanical properties, namely, high compressive strength of about 1,630 MPa and fracture strain of 3.3%. This is combined with a density of 6.32 g/cm³ and values of Poisson's ratio and Young's modulus of 0.377 and 77 GPa, respectively. The mechanical properties of the glass can be further improved by cold rolling. The compressive strength rises to 1,780 MPa and the fracture strain increases to 8.3% for the material cold-rolled to a diameter reduction of 10%.

Non-Isothermal Kinetic Analysis of the Crystallization of Metallic Glasses Using the Master Curve Method.

The non-isothermal transformation rate curves of metallic glasses are analyzed with the Master Curve method grounded in the Kolmogorov-Johnson-Mehl-Avrami theory. The method is applied to the study of two different metallic glasses determining the activation energy of the transformation and the experimental kinetic function that is analyzed using Avrami kinetics. The analysis of the crystallization of Cu47Ti33Zr11Ni8Si1 metallic glassy powders gives Ea = 3.8 eV, in good agreement with the calculation by other methods, and a transformation initiated by an accelerating nucleation and diffusion-controlled growth. The other studied alloy is a Nanoperm-type Fe77Nb7B15Cu1 metallic glass with a primary crystallization of bcc-Fe. An activation energy of Ea = 5.7 eV is obtained from the Master Curve analysis. It is shown that the use of Avrami kinetics is not able to explain the crystallization mechanisms in this alloy giving an Avrami exponent of n = 1.