Hierarchical Surface Pattern on Ni-Free Ti-Based Bulk Metallic Glass to Control Cell Interactions.

Ni-free Ti-based bulk metallic glasses (BMGs) are exciting materials for biomedical applications because of their outstanding biocompatibility and advantageous mechanical properties. The glassy nature of BMGs allows them to be shaped and patterned via thermoplastic forming (TPF). This work demonstrates the versatility of the TPF technique to create micro- and nano-patterns and hierarchical structures on Ti40Zr10Cu34Pd14Sn2 BMG. Particularly, a hierarchical structure fabricated by a two-step TPF process integrates 400 nm hexagonal close-packed protrusions on 2.5 µm square protuberances while preserving the advantageous mechanical properties from the as-cast material state. The correlations between thermal history, structure, and mechanical properties are explored. Regarding biocompatibility, Ti40Zr10Cu34Pd14Sn2 BMGs with four surface topographies (flat, micro-patterned, nano-patterned, and hierarchical-structured surfaces) are investigated using Saos-2 cell lines. Alamar Blue assay and live/dead analysis show that all tested surfaces have good cell proliferation and viability. Patterned surfaces are observed to promote the formation of longer filopodia on the edge of the cytoskeleton, leading to star-shaped and dendritic cell morphologies compared with the flat surface. In addition to potential implant applications, TPF-patterned Ti-BMGs enable a high level of order and design flexibility on the surface topography, expanding the available toolbox for studying cell behavior on rigid and ordered surfaces.

Beam Effects on Atomic Dynamics in Metallic Glasses Studied With Electron Correlation Microscopy.

Electron correlation microscopy (ECM) is used to investigate atomic dynamics in metallic glasses (MG) close to metastable equilibrium. It temporally correlates diffracted intensities of a time series of dark-field images to deduce a metric for structural decays. The measurement parameters, such as time and temperature, must be chosen according to the material of interest. In this work, ECM was extended to measurements at room temperature. To ensure, or select, a time window with quasi-thermodynamic equilibrium/steady-state measurement conditions, two-time correlation functions of diffracted intensities were calculated. The dynamics at room temperature are partly driven by the electron beam, thus affecting the material and the results. A systematic analysis of the influence of the electron beam is presented, revealing an inverse relation between electron dose rate and intensity correlation decay times at 300 kV acceleration voltage. However, the underlying dynamical mechanisms, described by a stretching exponent, are found to be independent of the applied electron dose rate for a Pd40Ni40P20 MG. An extrapolation of the results to infinite long measurement times and zero dose rate agrees with X-ray photon correlation spectroscopy data and justifies the application of beam-driven ECM at room temperature to study the dynamics of disordered systems.

Metastable quasicrystal-induced nucleation in a bulk glass-forming liquid.

This study presents a unique Mg-based alloy composition in the Mg-Zn-Yb system which exhibits bulk metallic glass, metastable icosahedral quasicrystals (iQCs), and crystalline approximant phases in the as-cast condition. Microscopy revealed a smooth gradual transition from glass to QC. We also report the complete melting of a metastable eutectic phase mixture (including a QC phase), generated via suppression of the metastable-to-stable phase transition at high heating rates using fast differential scanning calorimetry (FDSC). The melting temperature and enthalpy of fusion of this phase mixture could be measured directly, which unambiguously proves its metastability in any temperature range. The kinetic pathway from liquid state to stable solid state (an approximant phase) minimizes the free-energy barrier for nucleation through an intermediate state (metastable QC phase) because of its low solid-liquid interfacial energy. At high undercooling of the liquid, where diffusion is limited, another approximant phase with near-liquid composition forms just above the glass-transition temperature. These experimental results shed light on the competition between metastable and stable crystals, and on glass formation via system frustration associated with the presence of several free-energy minima.

How the toughness in metallic glasses depends on topological and chemical heterogeneity.

To gain insight into the large toughness variability observed between metallic glasses (MGs), we examine the origin of fracture toughness through bending experiments and molecular dynamics (MD) simulations for two binary MGs: Pd82Si18 and Cu46Zr54 The bending experiments show that Pd82Si18 is considerably tougher than Cu46Zr54, and the higher toughness of Pd82Si18 is attributed to an ability to deform plastically in the absence of crack nucleation through cavitation. The MD simulations study the initial stages of cavitation in both materials and extract the critical factors controlling cavitation. We find that for the tougher Pd82Si18, cavitation is governed by chemical inhomogeneity in addition to topological structures. In contrast, no such chemical correlations are observed in the more brittle Cu46Zr54, where topological low coordination number polyhedra are still observed around the critical cavity. As such, chemical inhomogeneity leads to more difficult cavitation initiation in Pd82Si18 than in Cu46Zr54, leading to a higher toughness. The absence of chemical separation during cavitation initiation in Cu46Zr54 decreases the energy barrier for a cavitation event, leading to lower toughness.

Biocompatibility and Osteogenic Capacity of Mg-Zn-Ca Bulk Metallic Glass for Rabbit Tendon-Bone Interference Fixation.

Mg-based alloys have great potential for development into fixation implants because of their highly biocompatible and biodegradable metallic properties. In this study, we sought to determine the biocompatibility of Mg60Zn35Ca5 bulk metallic glass composite (BMGC) with fabricated implants in a rabbit tendon-bone interference fixation model. We investigated the cellular cytotoxicity of Mg60Zn35Ca5 BMGC toward rabbit osteoblasts and compared it with conventional titanium alloy (Ti6Al4V) and polylactic acid (PLA). The results show that Mg60Zn35Ca5 BMGC may be classed as slightly toxic on the basis of the standard ISO 10993-5. We further characterized the osteogenic effect of the Mg60Zn35Ca5 BMGC extraction medium on rabbit osteoblasts by quantifying extracellular calcium and mineral deposition, as well as cellular alkaline phosphatase activity. The results of these tests were found to be promising. The chemotactic effect of the Mg60Zn35Ca5 BMGC extraction medium on rabbit osteoblasts was demonstrated through a transwell migration assay. For the in vivo section of this study, a rabbit tendon-bone interference fixation model was established to determine the biocompatibility and osteogenic potential of Mg60Zn35Ca5 BMGC in a created bony tunnel for a period of up to 24 weeks. The results show that Mg60Zn35Ca5 BMGC induced considerable new bone formation at the implant site in comparison with conventional titanium alloy after 24 weeks of implantation. In conclusion, this study revealed that Mg60Zn35Ca5 BMGC demonstrated adequate biocompatibility and exhibited significant osteogenic potential both in vitro and in vivo. These advantages may be clinically beneficial to the development of Mg60Zn35Ca5 BMGC implants for future applications.

Deformation Behavior of Bulk Metallic Glasses and High Entropy Alloys under Complex Stress Fields: A Review.

The plastic deformation of bulk metallic glasses (BMGs) depends significantly on applied stress states, and more importantly, in practical applications of BMGs as structural materials, they always deform under complex stress fields. The understanding of deformation behavior of BMGs under complex stress fields is important not only for uncovering the plastic deformation mechanisms of BMGs, but also for developing BMG components with excellent mechanical performance. In this article, we briefly summarize the recent research progress on the deformation behavior of BMGs under complex stress fields, including the formation and propagation of shear bands, tunable macroscopic plasticity, and serrated plastic flows. The effect of complex stress fields on the plastic deformation mechanisms of BMGs is discussed from simple stress gradient to tailored complex stress fields. The deformation behavior of high entropy alloys (HEAs) under complex stress states has also been discussed. Challenges, potential implications and some unresolved issues are proposed.

The microfabrication of mold for polymer microfluidic devices with Zr-based metallic glass.

Polymer microfluidic devices are used for many purposes such as microarrays and biochips. The key tool for manufacturing these chips in bulk is an appropriate mold. However, the popular material for making molds is nickel or nickel alloys, which have low stiffness and wear out easily. Zr-based metallic glass is a promising material for micro- or nanomolds because it has good mechanical properties and can be easily formed with high precision. In this paper, Zr-based metallic glass is proposed for use as micromold insert to make poly-(methyl methacrylate) (PMMA) microfluidic devices. Our experiments show that they have good feature integrity and replication quality. Microchannels we fabricated using these replicas did not leak and had good flow performance. Zr-based metallic glass can greatly ease the manufacture of plastic microfluidic devices for research and commercial applications.

Electron Correlation Microscopy: A New Technique for Studying Local Atom Dynamics Applied to a Supercooled Liquid.

Electron correlation microscopy (ECM) is a new technique that utilizes time-resolved coherent electron nanodiffraction to study dynamic atomic rearrangements in materials. It is the electron scattering equivalent of photon correlation spectroscopy with the added advantage of nanometer-scale spatial resolution. We have applied ECM to a Pd40Ni40P20 metallic glass, heated inside a scanning transmission electron microscope into a supercooled liquid to measure the structural relaxation time τ between the glass transition temperature T g and the crystallization temperature, T x . τ determined from the mean diffraction intensity autocorrelation function g 2(t) decreases with temperature following an Arrhenius relationship between T g and T g +25 K, and then increases as temperature approaches T x . The distribution of τ determined from the g 2(t) of single speckles is broad and changes significantly with temperature.

Deformation behavior of thermally rejuvenated Zr-Cu-Al-(Ti) bulk metallic glass.

The deformation behavior of metallic glasses has been shown in prior studies to be often dependent on its structural state, namely higher energy "rejuvenated" state versus lower energy "relaxed" state. Here, the deformation behavior of thermally rejuvenated Zr-Cu-Al-(Ti) bulk metallic glasses (BMGs) was evaluated. Rejuvenation was achieved by cryogenic thermal cycling with increase of free volume measured in terms of enthalpy of relaxation. Hardness, stiffness, and yield strength of the BMGs were all found to decrease while plasticity increased after rejuvenation. More free volume in the rejuvenated BMG resulted in homogeneous plastic deformation as was evident from the high strain rate sensitivity and more pronounced shear band multiplication during uniaxial compression. Shear transformation zone (STZ) volume was calculated by cooperative shear model and correlated well with the change in structural state after rejuvenation. The enhanced plasticity with the addition of 1 at. % Ti as well as after cryogenic thermal cycling was explained by lower activation energy for shear flow initiation due to increased heterogeneity induced in the system. Molecular dynamics simulation demonstrated that the variation in plastic deformation behavior is correlated with local atomic structure changes.

Effect of Chemical Composition on the Thermoplastic Formability and Nanoindentation of Ti-Based Bulk Metallic Glasses.

A series of Ti41Zr25Be34-xNix (x = 4, 6, 8, 10 at.%) and Ti41Zr25Be34-xCux (x = 4, 6, 8 at.%) bulk metallic glasses were investigated to examine the influence of Ni and Cu content on the viscosity, thermoplastic formability, and nanoindentation of Ti-based bulk metallic glasses. The results demonstrate that Ti41Zr25Be30Ni4 and Ti41Zr25Be26Cu8 amorphous alloys have superior thermoplastic formability among the Ti41Zr25Be34-xNix and Ti41Zr25Be34-xCux amorphous alloys due to their low viscosity in the supercooled liquid region and wider supercooled liquid region. The hardness and modulus exhibit obvious variations with increasing Ni and Cu content in Ti-based bulk metallic glasses, which can be attributed to alterations in atomic density. Optimal amounts of Ni and Cu in Ti-based bulk metallic glasses enhance thermoplastic formability and mechanical properties. The influence of Ni and Cu content on the hardness of Ti-based bulk metallic glasses is discussed from the perspective of the mean atomic distance.

Tensile Deformation Mechanism of an In Situ Formed Ti-Based Bulk Metallic Glass Composites.

Ti-based bulk metallic glass composites (BMGMCs) containing an in situ formed metastable ß phase normally exhibit enhanced plasticity attributed to induced phase transformation or twinning. However, the underlying deformation micromechanism remains controversial. This study investigates a novel deformation mechanism of Ti-based BMGMCs with a composition of Ti42.3Zr28Cu8.3Nb4.7Ni1.7Be15 (at%). The microstructures after tension were analyzed using advanced electron microscopy. The dendrites were homogeneously distributed in the glassy matrix with a volume fraction of 55 ± 2% and a size of 1~5 µm. The BMGMCs deformed in a serrated manner with a fracture strength (σf) of ~1710 MPa and a fracture strain of ~7.1%, accompanying strain hardening. The plastic deformation beyond yielding was achieved by a synergistic action, which includes shear banding, localized amorphization and a localized BCC (ß-Ti) to HCP (α-Ti) structural transition. The localized amorphization was caused by high local strain rates during shear band extension from the amorphous matrix to the crystalline reinforcements. The localized structural transition from BCC to HCP resulted from accumulating concentrated stress during deformation. The synergistic action enriches our understanding of the deformation mechanism of Ti-based BMGMCs and also sheds light on material design and performance improvement.

Composition Design Strategy for High Entropy Amorphous Alloys.

High entropy amorphous alloys (HEAAs) are materials that have received much attention in recent years. They exhibit many unique properties; however, research on their composition design method has not been deep enough. In this paper, we summarized some effective composition design strategies for HEAAs. By adjusting the atomic ratio from quinary bulk metallic glasses, Ti20Zr20Cu20Ni20Be20 HEAA with a high fracture strength of 2315 MPa was designed. By similar element addition/substitution, a series of Ti-(Zr, Hf, Nb)-Cu-Ni-Be HEAAs was developed. They possess good glass-forming ability with a maximum critical diameter of 30 mm. Combining elements from those ternary/quaternary bulk metallic glasses has also proved to be an effective method for designing new HEAAs. The effect of high entropy on the property of the alloy, possible composition design methods, and potential applications were also discussed. This paper may provide helpful inspiration for future development of HEAAs.

Comparative Study of Microstructure and Phase Composition of Amorphous-Nanocrystalline Fe-Based Composite Material Produced by Laser Powder Bed Fusion in Argon and Helium Atmosphere.

Laser powder bed fusion (LPBF) is a prospective and promising technique of additive manufacturing of which there is a growing interest for the development and production of Fe-based bulk metallic glasses and amorphous-nanocrystalline composites. Many factors affect the quality and properties of the resulting material, and these factors are being actively investigated by many researchers, however, the factor of the inert gas atmosphere used in the process remains virtually unexplored for Fe-based metallic glasses and composites at this time. Here, we present the results of producing amorphous-nanocrystalline composites from amorphous Fe-based powder via LPBF using argon and helium atmospheres. The analysis of the microstructures and phase compositions demonstrated that using helium as an inert gas in the LPBF resulted in a nearly three-fold increase in the amorphization degree of the material. Additionally, it had a beneficial impact on phase composition and structure in a heat-affected zone. The received results may help to develop approaches to control and improve the structural-phase state of amorphous-nanocrystalline compositional materials obtained via LPBF.

Multi-Scale Traditional and Non-Traditional Machining of Bulk Metallic Glasses (BMGs)-Review of Challenges, Recent Advances, and Future Directions.

Bulk metallic glasses (BMGs) are growing in popularity prominently due to their potential in micro-electromechanical systems (MEMSs) and aerospace applications. BMGs have unique mechanical properties, i.e., high strength, hardness, modulus of elasticity, and wear resistance, due to their disordered atomic structure. Due to their unique mechanical properties and amorphous structures, machining of BMGs remains a challenge. This paper aims to carry out a detailed literature review on various aspects of the machining of bulk metallic glasses using both conventional and non-conventional processes, including experimental approaches, modeling, statistical findings, challenges, and guidelines for machining this difficult-to-machine material. Conventional machining processes were found to be challenging for machining bulk metallic glasses due to their high hardness, brittleness, and tendency to convert their amorphous structure into a crystalline structure, especially at the machined surface and sub-surface. Although their high electrical conductivity makes them suitable for machining by non-conventional processes, they impose new challenges such as heat-affected zones and crystallization. Therefore, the successful machining of BMGs requires more in-depth analysis of cutting forces, tool wear, burr formation, surface finish, recast layers or heat-affected zones, crystallization, and mechanical property changes among different varieties of BMGs. This review paper provides guidelines emerging from in-depth analysis of previous studies, as well as offering directions for future research in the machining of BMGs.

An in vivo preclinical study assessing biocompatibility of Pd-based bulk metallic glass.

BACKGROUND: The bulk metallic glass (BMG), Pd79Ag3.5P6Si9.5Ge2, has a high fracture toughness and has been found to accommodate post-yield stress, unlike most other BMG. Moreover, due to its greater noble gas composition it has a intrinsic corrosion resistance, ideal for dental and orthopedic implants. OBJECTIVE: This present study aimed to evaluate the in vivo application of Pd79Ag3.5P6Si9.5Ge2 in a large translational sheep model to assess its efficacy to be utilized as an endosteal device. METHODS: Twelve implants in the form of cylindrical rods (3 mm in diameter) were produced through rapid quenching. Each sheep (n = 12) received one osteotomy in the mandibular region using rotary instrumentation, which was filled with Pd79Ag3.5P6Si9.5Ge2. After 6- and 24-weeks the animals were euthanized, and samples collected en bloc to conduct histomorphometric analysis. The degree of osseointegration were assessed through bone-to-implant contact (BIC). RESULTS: All samples revealed favorable BIC along with with fibrous connective tissue layers at both 6- and 24-weeks. Bone along with interfacial remodeling was observed in proximity with the metallic glass surface at 6 weeks with higher degrees of bone organization being observed at the later healing time, 24 weeks. CONCLUSIONS: The synthesized BMG, given its unique combination of toughness and strength, revealed potential to serve as an alternative to commonly used Ti alloys.

Interface Characteristics of Tungsten-Particle-Reinforced Zr-Based Bulk-Metallic-Glass Composites with Different Tungsten Particle Sizes.

This study investigated the interfacial characteristics of tungsten-particle-reinforced Zr-based bulk-metallic-glass composites (Wp/Zr-BMGs) with varying tungsten-particle sizes. To this end, Wp/Zr-BMGs with three different Wp sizes were fabricated using spark plasma sintering. Subsequently, the microstructures and interfacial structures of the Wp/Zr-BMGs were extensively examined, and the mechanical properties of the microzone at the Wp/Zr-BMG interface were evaluated using a nanoindentation method. The results revealed that the interfaces of Wp/Zr-BMGs, irrespective of the Wp size, exhibited dissolution-diffusion characteristics. Moreover, the thickness of the interface diffusion layer was positively correlated to the size of Wp. The addition of Wp enhanced the elastic modulus and hardness of Zr-BMGs at the interface, as these effects are inversely related to the Wp size. Furthermore, this study established a relationship between the interfacial mechanical properties and the interfacial characteristics of particle-reinforced bulk-metallic-glass composites. Thus, this study can serve as a guide for future research in the field of Wp/Zr-BMGs and similar particle-reinforced composites.

Convective Flow Redistribution of Oxygen by Laser Melting of a Zr-Based Amorphous Alloy.

Oxygen impurities play a crucial role in the glass-forming ability and crystallisation behaviour of metallic glasses. In the present work, single laser tracks were produced on Zr59.3-xCu28.8 Al10.4Nb1.5Ox substrates (x = 0.3, 1.3) to study the redistribution of oxygen in the melt pool under laser melting, which provides the basis for laser powder bed fusion additive manufacturing. Since such substrates are commercially not available, they were fabricated by arc melting and splat quenching. X-ray diffraction revealed that the substrate with 0.3 at.% oxygen was X-ray amorphous, while the substrate with 1.3 at.% oxygen was partially crystalline. Hence, it is evident that the oxygen content affects the crystallisation kinetics. Subsequently, single laser tracks were produced on the surface of these substrates, and the melt pools attained from the laser processing were characterised by atom probe tomography and transmission electron microscopy. Surface oxidation and subsequent convective flow redistribution of oxygen by laser melting were identified as causes of the presence of CuOx and crystalline ZrO nanoparticles in the melt pool. Bands of ZrO likely originate from surface oxides that were moved deeper into the melt pool by convective flow. The findings presented here highlight the influence of oxygen redistribution from the surface into the melt pool during laser processing.

ZrO2 Superhydrophobic Coating with an Excellent Corrosion Resistance and Stable Degradation Performance on Zr-Based Bulk Metallic Glass.

Photocatalysis is an energy-saving and high-efficiency green environmental technology. Because of its wide band gap and low light utilization, few studies have been conducted on ZrO2 used as a photocatalytic material. In this paper, a corrosion-resistant superhydrophobic ZrO2 coating was prepared on the surface of Zr-based bulk metallic glass by electrochemical etching. This coating not only showed a better corrosion resistance and easier collection, but also presented a stable degradation performance when combined with H2O2; these characteristics are necessary for photocatalysts to survive under harsh environments. This study provides a new direction for designing superhydrophobic surfaces on bulk metallic glass that possess a functional performance.

Antibacterial activity, cytocompatibility, and thermomechanical stability of Ti40Zr10Cu36Pd14 bulk metallic glass.

This paper envisions Ti40Zr10Cu36Pd14 bulk metallic glass as an oral implant material and evaluates its antibacterial performance in the inhabitation of oral biofilm formation in comparison with the gold standard Ti-6Al-4V implant material. Metallic glasses are superior in terms of biocorrosion and have a reduced stress shielding effect compared with their crystalline counterparts. Dynamic mechanical and thermal expansion analyses on Ti40Zr10Cu36Pd14 show that these materials can be thermomechanically shaped into implants. Static water contact angle measurement on samples' surface shows an increased surface wettability on the Ti-6Al-4V surface after 48 â€‹h incubation in the water while the contact angle remains constant for Ti40Zr10Cu36Pd14. Further, high-resolution transmission and scanning transmission electron microscopy analysis have revealed that Ti40Zr10Cu36Pd14 interior is fully amorphous, while a 15 â€‹nm surface oxide is formed on its surface and assigned as copper oxide. Unlike titanium oxide formed on Ti-6Al-4V, copper oxide is hydrophobic, and its formation reduces surface wettability. Further surface analysis by X-ray photoelectron spectroscopy confirmed the presence of copper oxide on the surface. Metallic glasses cytocompatibility was first demonstrated towards human gingival fibroblasts, and then the antibacterial properties were verified towards the oral pathogen Aggregatibacter actinomycetemcomitans responsible for oral biofilm formation. After 24 â€‹h of direct infection, metallic glasses reported a >70% reduction of bacteria viability and the number of viable colonies was reduced by ∼8 times, as shown by the colony-forming unit count. Field emission scanning electron microscopy and fluorescent images confirmed the lower surface colonization of metallic glasses in comparison with controls. Finally, oral biofilm obtained from healthy volunteers was cultivated onto specimens' surface, and proteomics was applied to study the surface property impact on species composition within the oral plaque.

Versatile Medium Entropy Ti-Based Bulk Metallic Glass Composites.

An ultra-strong Ti-based bulk metallic glass composite was developed via the transformation-induced plasticity (TRIP) effect to enhance both the ductility and work-hardening capability of the amorphous matrix. The functionally graded composites with a continuous gradient microstructure were obtained. It was found that the austenitic center possesses good plasticity and toughness. Furthermore, the amorphous surface exhibited high strength and hardness, as well as excellent wear corrosion resistance. Compared with the Ti-6Al-4V alloy, bulk metallic glass composites (BMGCs) exhibit better spontaneous passivation behavior during the potential dynamic polarization. No crystallization was observed on the friction surface, indicating their good friction-reduction and anti-wear properties.