Development of quaternary Fe-based bulk metallic glasses

Fe-based bulk metallic glasses have been designed using several modeling criteria. Quaternary alloys were successfully developed in the Fe-rich compositional region where the only solutes used were Cr, Nb, and B. Furthermore, the exceedingly high level of Fe, exceeding 75 wt.% in some alloys, makes this series of alloys, compositionally very close to conventional steel alloys. Therefore, their production using conventional facilities and materials is more easily attainable than previously developed bulk metallic glasses. The modeling criteria used, simultaneously analyzes the thermodynamics and kinetics of the vitrification behavior in a potential glass-forming alloy. A liquidus model, which determines and ranks the presence of deep eutectics, is used to determine the optimal compositional region. This criterion is cross-checked with an elastic strain model. Alloys compositionally located near a deep eutectic, while simultaneously containing a topology that induces significant elastic strain in a developing crystalline lattice exhibits experimentally good glass forming ability.     

Extrusion properties of a Zr-based bulk metallic glass

The extrusion behavior of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 metallic glasses in the supercooled liquid region was investigated. Good extrusion formability was observed under low strain rates at temperatures higher than 395 °C. The metallic glasses were fully extruded without crystallization and failure within the range of T = 395-415 °C under strain rates from 5 × 10^− 3 s^− 1 to 5 × 10^− 2 s^− 1, and the deformation behavior of the metallic glasses during the extrusion was found to be in a Newtonian viscous flow mode by a strain rate sensitivity of 1.0.     

Strengthening and toughening of Mg-Cu-(Y, Gd) bulk metallic glasses by minor addition of Be

Mg₆₅Cu₂₅Re₁₀ and Mg₆₅Cu₂₄Be₁Re₁₀ (Re = Y, Gd) bulk metallic glasses (BMGs) were successfully fabricated by conventional Cu-mold casting method. By the addition of 1 at.% Be, the compressive strengths of Mg₆₅Cu₂₄Be₁Y₁₀ and Mg₆₅Cu₂₄Be₁Gd₁₀ alloys are increased from 760 MPa and 860 MPa to 930 MPa and 1025 MPa, respectively. The fracture morphology is changed from nanometer scale corrugation to micrometer scale dimple and vein pattern, indicating that the addition of minor Be obviously improves the toughness of the alloys. The fracture morphologies with different size of plastic zone in Mg-based BMGs provide probability for understanding the fracture mechanism of BMGs.     

Dual magnetic phases in Nd-based bulk metallic glass

Numerous nanocrystals dispersed homogenously in an amorphous matrix were observed in the die-cast cylindrical Nd₅₅Fe₂₈Al₉Ni₈ bulk metallic glass. Most of the nanocrystals are less than 5 nm in size. At room temperature, only one magnetically hard phase was observed. But below room temperature, another magnetically hard phase was also detected. The appearance of the phases was associated with the different exchange coupling effect of the nanocrystalline grains and the amorphous matrix, and the coercivity of the alloy was related to the size of the nanocrystals. It was shown that nanocrytals with a size larger than 1.3 nm might contribute to a larger coercivity of the alloy.     

Micro and nano indentation studies on Zr60Cu10Al15Ni15 bulk metallic glass

Partially vitrified Zr₆₀Cu₁₀Al₁₅Ni₁₅ bulk metallic glass has been synthesized using water cooled copper mold drop casting technique. Kinetically favorable microstructures having different morphologies are observed throughout the volume of the bulk metallic glass sample. X-ray diffraction studies indicate formation of hard intermetallic compounds such as Zr₃Al₂ and Zr₂Ni in certain regions along with amorphous structures. Microindentation studies carried out in different regions of the sample reveal microstructure dependent deformation behavior. Highest hardness is observed in the fully crystallized regions compared to pure glassy regions in the same sample. Further nanoindentation in the same sample is used to understand dynamic mechanical properties of microstructures in different regions. The pile-up morphologies around the indent and differences in load–displacement curves provide vital information on deformation behavior of sample in different microstructure sensitive regions.     

Effect of Er on properties of Zr-based bulk metallic glasses

(Zr_0.6336Cu_0.1452Ni_0.1012Al_0.12)_100-xEr_x(x?=?0～6) bulk metallic glasses were fabricated by copper mould suction casting method, and the effect of Er on properties was studied. The compressive plastic strain (ε_p) and compressive strength (σ_max) at room temperature increases first and then decreases with the increase of Er content. The compressive plastic strain (ε_p) of the specimen is 35.1% when x?=?2.6, which is about eight times than that of the specimen with x?=?0. The compressive strength (σ_max) is 2513?MPa, which is much higher than that of the specimen with x?=?0. It indicates that Zr-based bulk metallic glasses could be strengthened and toughened by adding Er. The thermal stability decreases gradually and the glass-forming ability increases first and then decreases with the increase of Er content.     

Study of mechanical deformation of Zr55Cu30Al10Ni5 bulk metallic glass through instrumented indentation

Instrumented sharp indentation experiments using both conical and Vickers diamond pyramidal indenters were carried out to study deformation characteristics of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk metallic glass. Finite element simulations of instrumented indentation were also performed to formulate an overall constitutive response. Comparing the experimentally obtained results with the finite element predictions, it can be stated that mechanical deformation of the bulk metallic glass can be described well by both Mohr-Coulomb and Drucker-Prager constitutive criteria. Using these criteria, the extent of material pile-up observed around the indenter was also estimated very well.     

Internal friction and elastic modulus of bulk metallic glasses

The mechanical relaxation in binary, ternary, quaternary, and quitary bulk metallic glasses with widely different glass-forming ability, or the critical cooling rate, has been studied. A single-roller melt-spinning apparatus was used for preparing thin specimens. The internal friction Q⁻¹ and the oscillation frequency f of the specimens were measured using an inverted torsion pendulum with the free decay method. The measurements were performed from room temperature, through the glass transition temperature T_g, up to the crystallization temperature T_x. As the temperature is increased, the background Q⁻¹ increases, and peaks can usually be seen near T_g and T_x. The shear modulus, which is proportional to f², is changed near the Q⁻¹ peak. The experimental data are presented and overall features of the results are discussed.     

An experimental study on grinding of Zr-based bulk metallic glass

There are limited studies in the literature about machinability of bulk metallic glass(BMG).As a novel and promising structural material,BMG material machining characteristics need to be verified before its utilization.In this paper,the effects of cutting speed,feed rate,depth of cut,abrasive particle size/type on the BMG grinding in dry conditions were experimentally investigated.The experimental evaluations were carried out using cubic boron nitride(CBN) and Al_2O_3 cup wheel grinding tools.The parameters were evaluated along with the results of cutting force,temperature and surface roughness measurements,X-ray,scanning electron microscope(SEM)and surface roughness analyse.The results demonstrated that the grinding forces reduced with the increasing cutting speed as specific grinding energy increased.The effect of feed rate was opposite to the cutting speed effect,and increasing feed rate caused higher grinding forces and substantially lower specific energy.Some voids like cracks parallel to the grinding direction were observed at the edge of the grinding tracks.The present investigations on ground surface and grinding chips morphologies showed that material removal and surface formation of the BMG were mainly due to the ductile chip formation and ploughing as well as brittle fracture of some particles from the edge of the tracks.The roughness values obtained with the CBN wheels were found to be acceptable for the grinding operation of the structural materials and were in the range of 0.34-0.58 μm.This study also demonstrates that conventional Al_2O_3 wheel is not suitable for grinding of the BMG in dry conditions.     

CuZr-based bulk metallic glass and glass matrix composites fabricated by selective laser melting

Monolithic bulk metallic glass and glass matrix composites with a relative density above 98 ％ were produced by processing Cu46Zr46Al8 (at.％) via selective laser melting (SLM).Their microstructures and mechanical properties were systematically examined.B2 CuZr nanocrystals (30-100 nm in diameter) are uniformly dispersed in the glassy matrix when SLM is conducted at an intermediate energy input.These B2 CuZr nanocrystals nucleate the oxygen-stabilized big cube phase during a remelting step.The presence of these nanocrystals increases the structural heterogeneity as indirectly revealed by mircrohardness and nanoindentation measurements.The corresponding maps in combination with calorimetric data indicate that the glassy phase is altered by the processing conditions.Despite the formation of crystals and a high overall free volume content,all additively manufactured samples fail at lower stress than the as-cast glass and without any plastic strain.The inherent brittleness is attributed to the presence of relatively large pores and the increased oxygen content after selective laser melting.     

Mechanical properties and thermal stability of a Cu-based bulk metallic glass microalloyed with silicon

(Cu₄₂Zr₄₂Al₈Ag₈)_{100? x} Si _x (x?=?0?～?1) amorphous alloy rods of 2–6?mm diameter were prepared by Cu-mold drop casting. The thermal properties, microstructure evolution, and mechanical properties were studied by differential scanning calorimetry (DSC), X-ray diffractometry (XRD), transmission electron microscopy (TEM), hardness test, and compression test. The XRD result revealed that all as-quenched (Cu₄₂Zr₄₂Al₈Ag₈)_100?x Si _x alloy rods exhibited a broad diffraction pattern in the amorphous phase. The (Cu₄₂Zr₄₂Al₈Ag₈)_99.5Si_0.5 alloy was found to possess the highest glass forming ability (GFA) as well as the best thermal stability among all tested samples. In addition, both its hardness and yield strength were increased by the microalloyed Si content. The fracture strength and the plastic strain of (Cu₄₂Zr₄₂Al₈Ag₈)_99.5Si_0.5 amorphous alloy can reach 2000?MPa and 3.5 %.     

High specific strength Mg-based bulk metallic glass matrix composite highly ductilized by Ti dispersoid

Mg-based bulk metallic glass matrix composite with hcp-Ti powders was fabricated by casting the mixtures of Mg₆₅Cu₂₅Gd₁₀ molten alloy and pure Ti powders into a copper mold. Ti powder was spherical and less than 150 μm in diameter, and its volume fraction was controlled from 5 to 40%. Thermal stability of the glassy matrix was maintanied even in the coexistence with the Ti powders. However, Ti dispersoid caused a significant improvement on compressive ductility from 0% plastic deformation for the monolithic glass to 41% plastic deformation for the composite with 40 vol.% Ti powders. This is the first success of synthesizing Mg-based alloys with high ultimate strength of 900 MPa level as well as the large plastic deformation of 40%, and suggests a novel guideline to develop Mg-based alloys having high specific strength with high ductility.     

Synthesis of Zr-based bulk metallic glass-crystalline aluminum alloy composite by co-extrusion

The effects of co-extrusion conditions like extrusion temperature and deformation rate on the fabrication of a Zr-based bulk metallic glass-Al clad material were investigated under the extrusion ratio of 5.06. The ranges of extrusion temperature and deformation rate were varied from 658 to 703 K and from 10^− 3 to 10^− 1 mm/s, respectively. Both macroscopic and microstructural characterizations reveal that sound materials compatibility could be obtained under the low deformation rate-low temperature within supercooled liquid region combination, showing homogeneous distribution of the rate of cross-sectional area between core and sleeve without crack or intermetallic compound in the vicinity of the interface.     

Numerical study of shear banding evolution in bulk metallic glass composites

In this article, a systematic simulation was performed to demonstrate the detailed shear banding evolution in bulk metallic glass (BMG) composites subjected to the tension, and the relation between microstructures and tensile ductility was therefore elucidated. Free volume was adopted as an internal state variable to characterize the shear banding nucleation, growth and coalescence in BMG matrix with the help of free volume theory, which was incorporated into ABAQUS finite element method (FEM) code as a user material subroutine. The present numerical method was firstly verified by comparing with the corresponding experimental results, and then parameter analyses were conducted to discuss the impacts of particle volume fraction, particle shape, particle orientation and particle yielding strength on the enhancement efficiency of the tensile ductility of BMG composites.     

Evolutionary intelligence in design and synthesis of bulk metallic glasses by mechanical alloying

The present work demonstrates a new approach of a combinatorial design of Bulk Metallic Glasses using evolutionary intelligence of genetic programming (GP) and genetic algorithm (GA). A glass-forming potential expression, carrying similar sense as the glass-forming ability (GFA) indicator expression, has been identified by principal component analysis and GP, enabling one to map the fitness of the composition from the multidimensional attribute space of the alloy in the course of GA search. The genetically inspired alloy compositions are evolved by GA search and subsequently validated through existing empirical knowledge. Two randomly chosen compositions are subjected to experimental trial where the glass-forming potential has been evaluated by amorphization potential through mechanical alloying. A literature-reported good glass -forming composition has been studied as a reference alloy and comparison was made for the proposed designed alloys.     

The effect of cooling rate on the wear performance of a ZrCuAlAg bulk metallic glass

In the present work, the local atomic ordering and the wear performance of ZrCuAlAg bulk metallic glass (BMG) samples with different diameters have been studied using transmission electron microscopy (TEM) plus autocorrelation function analysis, and pin-on-disc dry sliding wear experiments. Differential scanning calorimetry and TEM studies show that smaller diameter BMG sample has higher free volume and less local atomic ordering. The wear experiments demonstrate that with the same chemical composition, the smaller BMG sample exhibits higher coefficient of friction, higher wear rate, and rougher worn surface than those of the larger ones. Compared with larger BMG sample, the faster cooling rate of the smaller sample results in looser atomic configuration with more free volume, which facilitates the formation of the shear bands, and thus leads to larger plasticity and lower wear resistance. The results provide more quantitative understanding on the relationship among the cooling rate, the local atomic ordering, and the wear performance of BMGs.     

The potential of Zr-based bulk metallic glasses as biomaterials

Zr-based bulk metallic glasses (BMGs) are a new type of metallic materials with disordered atomic structure that exhibit high strength and high elastic strain, relatively low Young’s modulus, and excellent corrosion resistance and biocompatibility. The combination of these unique properties makes the Zr-based BMGs very promising for biomaterials applications. In this review article, the authors give an overview of the recent progress in the study of biocompatibility of Zr-based BMGs, especially the relevant work that has been done in the metallic glasses group in Huazhong University of Science and Technology (HUST), including the development of Ni-free Zr-based BMGs, the mechanical and wear properties, the bio-corrosion resistance, the in vitro and in vivo biocompatibility and the bioactive surface modification of these newly developed BMGs.     

Dynamic fracture of berylium-bearing bulk metallic glass systems: A cross-technique comparison

We report on a detailed comparison between two different experimental techniques used to measure the dynamic initiation fracture toughness of a bulk metallic glass system (Vitreloy-1) and its β-phase composite. Both the coherent gradient sensing interferometry (CGS) and one-point impact techniques reveal very similar trends in the relationship for Vitreloy-1. A drastic increase in initiation toughness with the stress intensity rate is observed. By contrast, the one-point impact method shows a relative rate-insensitivity for the of the β-phase composite. The results are rationalized through a detailed characterization of the failure mechanisms.     

Plastic deformation of a Zr-based bulk metallic glass fabricated by selective laser melting

Fully amorphous Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glass(BMG) samples with a relative density exceeding 98% were fabricated via selective laser melting(SLM).High fracture stresses of around1700 MPa and a reproducible plastic strain of about 0.5% were obtained for cylindrical SLM samples.The analysis of the observed serrations during compressive loading implies that the shear-band dynamics in the additively manufactured samples distinctly differ from those of the as-cast glass.This phenomenon appears to originate from the presence of uniformly dispersed spherical pores as well as from the more pronounced heterogeneity of the glass itself as revealed by instrumented indentation.Despite these heterogeneities,the shear bands are straight and form in the plane of maximum shear stress.Additive manufacturing,hence,might not only allow for producing large BMG samples with complex geometries but also for manipulating their deformation behaviour through tailoring porosity and structural heterogeneity.     

Mechanical property degradation of a CuZr-based bulk metallic glass composite induced by sub-Tg annealing

The annealing effect at temperatures below glass transition temperature (T_g) on the mechanical behavior of a ductile Cu₄₈Zr₄₈Al₄ bulk metallic glass composite (BMGC) containing a B2-CuZr phase was investigated. It was found that remarkable plasticity and fracture strength degradations of the CuZr-based BMGC occurred with increasing the annealing temperature in the condition without significantly changing the crystalline volume fraction in the BMGC, which were correlated with the annealing-induced microstructure variations. It is expected that the free volume in the glassy matrix of the BMGC still played an important role for its deformation behavior, in despite of the existence of the B2-CuZr phase. The sub-T_g annealing-induced free volume annihilation depressed the shear band generation in the glassy matrix, reduced the synchronous contribution of the “blocking effect” and “deformation-induced martensitic transformation effect” of the B2-CuZr phase to the multiplication of shear bands, resultantly caused the plasticity degradation. The annealing-induced martensitic transformation of the B2-CuZr phase at the temperature close to T_g would further expand the plasticity degradation due to the absence of the “deformation-induced martensitic transformation effect”. Furthermore, the plasticity degradation simultaneously resulted in the fracture strength reduction of the BMGC because its work-hardening-like behavior was conditioned by the plastic deformation ability. The present results indicate that the ductile CuZr-based BMGC reinforced by the B2-CuZr phase similarly suffers from sub-T_g annealing-induced embrittlement, as is the case for most monolithic BMGs.