Zr–(Cu,Ag)–Al bulk metallic glasses

In this paper, we report the formation of a series Zr–(Cu,Ag)–Al bulk metallic glasses (BMGs) with diameters at least 20 mm and demonstrate the formation of about 25 g amorphous metallic ingots in a wide Zr–(Cu,Ag)–Al composition range using a conventional arc-melting machine. The origin of high glass-forming ability (GFA) of the Zr–(Cu,Ag)–Al alloy system has been investigated from the structural, thermodynamic and kinetic points of view. The high GFA of the Zr–(Cu,Ag)–Al system is attributed to denser local atomic packing and the smaller difference in Gibbs free energy between amorphous and crystalline phases. The thermal, mechanical and corrosion properties, as well as elastic constants for the newly developed Zr–(Cu,Ag)–Al BMGs, are also presented. These newly developed Ni-free Zr–(Cu,Ag)–Al BMGs exhibit excellent combined properties: strong GFA, high strength, high compressive plasticity, cheap and non-toxic raw materials and biocompatible property, as compared with other BMGs, leading to their potential industrial applications.     

Structural origins for the high plasticity of a Zr–Cu–Ni–Al bulk metallic glass

The structural origins for the high plasticity of a Zr₅₃Cu_18.7Ni₁₂Al_16.3 (at.%) bulk metallic glass are explored. Under plastic flow conditions, in situ synchrotron high-energy X-ray diffraction reveals that the atomic strain saturates to the closest packing in the longitudinal direction of the applied load while atoms yield in the transverse plane. Scanning electron microscopy investigation reveals that global plasticity benefits from abundant shear band multiplication and interactions. Atomic level flows are seen to accompany profuse shear bands. The plasticity enhancement of this metallic glass benefits from such atomic level flows. Atomic level flow facilitates the activation of shear transformation zones that further self-assemble to promote shear band multiplication. On the other hand, it also mitigates the shear band propagation that prevents catastrophic shear band extension.     

Crack-resistance curve of a Zr–Ti–Cu–Al bulk metallic glass with extraordinary fracture toughness

For the emerging bulk metallic glasses (BMGs), damage tolerance is a key mechanical property needed for their practical applications. To reach a fracture toughness on a par with, or even better than, conventional engineering alloys, the only route reported so far is to compositionally base the BMG on high-cost palladium (Pd), which has a very high Poisson’s ratio (～0.42). Here we report the discovery of a Zr₆₁Ti₂Cu₂₅Al₁₂ (ZT1) BMG that has a toughness as high as the Pd-based BMG, but at the same time consists of common engineering metals and has robust glass-forming ability. The new BMG, while having an unimpressive Poisson’s ratio of 0.367, derives its high toughness from its high propensity for crack deflection and local loading-mode change at the crack tip due to extensive shear band interactions. The crack-resistance curve (R-curve) of this BMG has been obtained from fatigue pre-crack samples, employing standard “single-specimen” and “multiple-specimen” techniques.     

Machining of a Zr–Ti–Al–Cu–Ni metallic glass

Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ metallic glass machining chips were characterized using SEM, X-ray diffraction and nano-indentation. Above a threshold cutting speed, oxidation of the Zr produces high flash temperatures and causes crystallization. The chip morphology was unique and showed the presence of shear bands, void formation and viscous flow.     

Corrosion behavior of Zr–Cu–Ni–Al bulk metallic glasses in chloride medium

Polarization and passivation behavior of three Zr-based BMGs, i.e. Zr_58.3Al_14.6Ni_8.3Cu_18.8, Zr₅₈Al₁₆Ni₁₁Cu₁₅ and Zr_57.5Al_17.5Ni_13.8Cu_11.3 were investigated in 3% NaCl aqueous solution. Electrochemical investigations were carried out by potentiodynamic polarization method at room temperature. The corroded sample surfaces were examined using scanning electron microscope having energy dispersive spectroscopy (EDS) attachment. The results of the present investigation revealed that Zr₅₈Al₁₆Ni₁₁Cu₁₅ and Zr_57.5Al_17.5Ni_13.8Cu_11.3 BMGs having relatively larger supercooled liquid region (ΔT_x) and pitting overpotential (η_pit) values exhibit low corrosion current density (i_corr) and corrosion penetration rate (CPR) values.     

Finite element simulation and experimental investigation of forming micro-gear with Zr–Cu–Ni–Al bulk metallic glass

Bulk metallic glasses exhibit some unique physical properties as compared to their corresponding crystalline alloys. Due to the superplasticity by behaving like a Newtonian fluid in their supercooled liquid region, the bulk metallic glasses can be used to make high strength microparts by net-shape forming. In this paper, the compressive tests of Zr–Cu–Ni–Al metallic glass are performed with different strain rates at a temperature of 683 K. According to the experimental results, the forming evolution of a metallic glass micro-gear is simulated using a finite element simulation software DEFORM 3D, and the forming load is predicted at different processing parameters. Meanwhile, the filling stages of bulk metallic glass in the micro-gear mold cavity are investigated by finite element simulation and experiment. The predicted workpiece geometry shows good agreement with experimental result. The forming experiments for micro-gear of Zr–Cu–Ni–Al metallic glass are carried out by hot embossing process, and the amorphous micro-gears are obtained successfully. It is found that the finite element simulation results are in reasonable agreement with the experimental observation.     

Composition dependence of the microstructure and mechanical behavior of Ti–Zr–Cu–Pd–Sn–Nb bulk metallic glass composites

Ti-based bulk metallic glass composite alloys Ti₅₆Zr₆Cu_19.8Pd_8.4Sn_1.8Nb₈, Ti₆₄Zr₄Cu_13.2Pd_5.6Sn_1.2Nb₁₂ and Ti₆₈Cu_13.2Pd_5.6Sn_1.2Nb₁₂ were designed to obtain the microstructure composing of β-Ti dendrites and glassy matrix. The compressive and three-point bending properties were investigated. It was found that the actual microstructure of the Nb-added alloys consisted of primarily precipitated β-Ti dendrites, network-like glassy matrix, and extra island-like Ti₂Cu intermetallic phase with different volume fractions. Under compressive loading, all the Nb-added alloys presented higher yield strength combined with remarkably increased plasticity. Under bending condition, however, the alloys Ti₅₆Zr₆Cu_19.8Pd_8.4Sn_1.8Nb₈ and Ti₆₄Zr₄Cu_13.2Pd_5.6Sn_1.2Nb₁₂ with higher Ti₂Cu volume fractions became completely brittle. The alloy Ti₆₈Cu_13.2Pd_5.6Sn_1.2Nb₁₂ could keep its plastic deformability due to the decreased Ti₂Cu volume fraction. Compressive deforming behavior of the Nb-added alloys was determined by the ductile β-Ti phase and glassy matrix, nevertheless, bending deforming behavior of the alloys was determined by the volume fraction and distribution of the brittle intermetallics.     

Correlation between mechanical behavior and glass forming ability of Zr–Cu metallic glasses

A series of Zr–Cu glassy ribbons were fabricated, and the compositional dependence of microhardness in the as-quenched and annealed state was systematically investigated. The as-quenched microhardness exhibits a positive deviation from linearity at the compositions which correspond to local maximum in glass forming ability (GFA). Upon annealing, the microhardness change is relatively smaller for the high GFA compositions. High atomic packing density at the special compositions should be responsible for the microhardness behavior.     

Criteria for tensile plasticity in Cu–Zr–Al bulk metallic glasses

(Cu_0.5Zr_0.5)_100?xAl_x (x = 5, 6, 8) bulk metallic glasses (BMGs) were deformed in tension. Besides ductility up to 0.5%, the material shows work-hardening behaviour. Both effects are attributed to the deformation-induced precipitation of B2 CuZr nanocrystals and the formation of twins in the nanocrystals larger than 20 nm. The precipitation of the nanocrystals alters the stress field in the matrix and is expected to retard shear band propagation, which in turn allows stresses in the nanocrystals to rise. This stress build-up is more severe in the larger grains and might be responsible for the subsequent twinning. Both deformation-induced nanocrystallization and twinning consume energy and avoid crack formation and with it premature failure.     

Fe–C micro-alloying effect on properties of Zr53Al11.6Ni11.7Cu23.7 bulk metallic glass

(Zr₅₃Al_11.6Ni_11.7Cu_23.7)_1–x(Fe_77.1C_22.9)_x (x=0−2.2, at.%) bulk metallic glasses (BMGs) were prepared by copper mold suction casting method. Their glass forming ability and physical and chemical properties were systematically investigated. The glass forming ability is firstly improved with increasing x, and then decreased when x exceeds 0.44 at.%. Both glass transition temperature and crystallization temperature are increased, while the supercooled liquid region is narrowed, with Fe–C micro-alloying. The hardness, yielding and fracture strength, and plasticity firstly increase and then decrease when x reaches up to 1.32 at.%. The plasticity of the BMG (x=1.32 at.%) is six times that of the Fe-free and C-free BMG. In addition, by the Fe–C micro-alloying, the corrosion potential is slightly decreased, while the corrosion current density increases. The pitting corrosion becomes increasingly serious with the increase of Fe and C content.     

Zr–Cu–Ni–Al bulk metallic glasses with superhigh glass-forming ability

Zr–Cu–Ni–Al quaternary amorphous alloy compositions with varying glass-forming ability are developed by an efficient method of proportional mixing of binary eutectics. The critical diameter of the glassy sample is improved from 6 mm for Zr₅₃Cu_18.7Ni₁₂Al_16.3 to 14 mm for Zr_50.7Cu₂₈Ni₉Al_12.3 by straightforwardly adjusting the eutectic unit’s coefficients. The drastic improvement in GFA is attributed to balancing the chemical affinities of the Zr, Cu, Ni and Al components in the melt prior to solidification which makes the precipitation of competing crystalline phases more difficult. As the glass-forming ability increases, the concentration of Cu in the alloys exhibits a same trend. Based on synchrotron radiation high-energy X-ray diffraction analysis and Miracle’s structural model, it is envisioned that the substitution of additional Cu atoms for Zr atoms in the investigated alloys stabilizes the efficient cluster packing structure of the amorphous alloys, leading to the pronounced increase in their glass-forming ability.     

Effects of Cu on the corrosion behavior and microstructure of Mg–Zn–Ca bulk metallic glass

For the purpose of developing biodegradable magnesium alloys with suitable properties for biomedical applications, Mg–Zn–Ca–Cu metallic glasses were prepared by copper mold injection methods. In the present work, the effect of Cu doping on mechanical properties, corrosion behavior, and glass-forming ability of Mg₆₆Zn₃₀Ca₄ alloy was studied. The experimental findings demonstrated that the incorporation of Cu decreases the corrosion resistance of alloys, but increases the microhardness and degradation rate slightly. However, the addition of a trace amount of Cu can make the samples have antibacterial properties. Therefore, Mg–Zn–Ca–Cu has great advantages in clinical implantation and is the potential implant material.     

Composition optimization of the Al–Co–Zr bulk metallic glasses

Composition optimization for locating the composition with the largest glass forming ability in the Al–Co–Zr system is attempted in this investigation. The criteria that we have developed are respectively related to a specific conduction electron concentration, termed the e/a-constant criterion, and to a specific cluster structure, termed the e/a-variant criterion. For this system, the two criteria are incarnated into the composition line with constant e/a=1.5 and the Co₄Zr₉–Al composition line. Bulk metallic glasses are obtained by suction casting for compositions with e/a=1.3–1.5, with their thermal stabilities and glass forming abilities being increased with increasing e/a ratios. The crossing point of the e/a=1.5 line and the Co₄Zr₉–Al line gives the composition Al_23.5Co_23.5Zr₅₃ with the largest GFA (e.g. T_g/T_m=0.637), superior to the reported Al₂₀Co₂₅Zr₅₅ alloy with T_g/T_m=0.621.     

Improved mechanical behavior of Cu–Ti-based bulk metallic glass by in situ formation of nanoscale precipitates

The mechanical properties of Cu₄₇Ti₃₄Zr₁₁Ni₈, Cu₄₇Ti₃₃Zr₁₁Ni₈Fe₁, and Cu₄₇Ti₃₃Zr₁₁Ni₈Si₁ bulk metallic glasses prepared by copper mold casting are investigated. Room temperature compression tests reveal fracture strengths above 2000 MPa, Young’s moduli around 100 GPa and elastic strains slightly exceeding 2.0%. Only Cu₄₇Ti₃₃Zr₁₁Ni₈Si₁ exhibits distinct plastic strain due to a unique composite microstructure with in situ formed nanoscale precipitates in the glassy matrix.     

Superplastic and diffusion bonding behavior on Zr–Al–Ni–Cu metallic glass in supercooled liquid region

The superplasticity and diffusion bonding behavior were examined on the Zr–10Al–10Ni–15Cu metallic glass indicating amorphous structure. The material behaved in a superplastic manner in supercooled liquid region, and successfully diffusion bonded at these conditions.