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.     

Experimental characterization of plastic flow initiation in a bulk metallic glass via intermittent compression test

Intermittently plastic compression tests of the Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glass were performed under a geometrically constrained condition at different cross-head displacement rates. A flow stress-overshoot phenomenon was observed during the macroscopically plastic deformation. It was found that there is a close correlation between the stress-overshoot intensity and the spatial density of shear bands. The stress-overshoot intensity can be used as a parameter to characterize the ability of plastic flow initiation caused by the spatial nucleation of shear bands in the bulk metallic glass. The micromechanisms of shear band multiplication were discussed.     

Structure and crystallization kinetics of a Cu50Zr45Ti5 glassy alloy

The crystallization kinetics and structure changes in a melt-spun Cu₅₀Zr₄₅Ti₅ glassy alloy on heating were investigated by X-ray diffractometry, transmission electron microscopy, differential scanning calorimetry and differential isothermal calorimetry. The glassy phase in the Cu₅₀Zr₄₅Ti₅ alloy was crystallized forming Cu₁₀Zr₇ and CuZr₂ phases upon thermal annealing. The activation energy for crystallization obtained by the Arrhenius equation was 435 kJ/mol. The crystallization process took place by nucleation and growth mechanism, and an Avrami exponent of about 3.3 may indicate a three-dimensional interface-controlled growth of nuclei with a decreasing nucleation rate.     

Crystallization kinetics of bulk Cu58.1Zr35.9Al6 alloy

The crystallization kinetics of the bulk amorphous Cu_58.1Zr_35.9Al₆ alloy was examined by differential scanning calorimetry under continuous heating and isothermal annealing. During continuous heating, the activation energy of crystallization was determined to be 383 kJ/mol by Kissinger method. However, on the isothermal annealing, the activation energy was determined to be 459.2 kJ/mol by the Arrhenius method, which was much larger than that obtained from the Kissinger method. The different temperatures at which crystallization occurs are responsible for the discrepancy in the activation energy. The average Avrami exponent of about 3.5 implies that the crystallization process of the bulk amorphous Cu_58.1Zr_35.9Al₆ alloy is diffusion-controlled with a nucleation rate decreasing with time.     

Microstructural studies of crystallization of a Zr-based bulk metallic glass

The evolution of the microstructure of a Zr_52.5Ti₅Cu_17.9Ni_14.6Al₁₀ alloy during isothermal annealing near the glass transition temperature was studied by transmission electron microscopy (TEM), small-angle neutron scattering (SANS), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). In situ SANS experiments show that an interference maximum develops with isothermal annealing, which is attributed to decomposition in the undercooled liquid state. In agreement with these results, TEM observations show the formation of structural inhomogeneities in the glassy alloy in the early stages of annealing, which are correlated with the partially crystalline microstructure in the later stages. The TEM and XRD data show that finally two nanocrystalline phases form after long-term annealing as a result of the decomposition process in the early stages. Direct evidence for decomposition was obtained using Z-contrast imaging technique that showed a systematic variation of the Zr concentration between the two nanocrystalline phases.     

Thermal stability and crystallization of Zr–Al–Cu–Ni based amorphous alloy added with boron and silicon

The amorphous Zr_65−x−yAl_7.5 Cu_17.5Ni₁₀Si_xB_y alloy ribbons, x=1–4 and y=1–2, with 0.1 mm thickness were prepared by melt spinning. The thermal properties and microstructure development during the annealing of amorphous alloys were investigated by the combination of differential thermal analysis, differential scanning calorimetry, X-ray diffractometry, and TEM. Both of the glass transition temperature and the crystallization temperature for Zr_65−x−yAl_7.5 Cu_17.5Ni₁₀Si_xB_y alloys increases with the silicon and boron additions and reaches 674 and 754 K, respectively for Zr₆₀Al_7.5 Cu_17.5Ni₁₀Si₄B₁ alloy. The highest T_rg (0.62) and γ value (0.43) occurred at the Zr₆₀Al_7.5Cu_17.5Ni₁₀Si₄B₁ alloy. In addition, the Zr₆₀Al_7.5Cu_17.5Ni₁₀Si₄B₁ alloy was revealed to have the highest activation energy of crystallization (about 370 kJ/mol as determined by the Kissinger plot). This value is about 20% higher than the activation energy of crystallization for the Zr₆₅Al_7.5Cu_17.5Ni₁₀ based alloy (314 kJ/mol). In parallel, the alloy 4Si1B also performs a longer incubation time at higher isothermally annealing temperature. All of the evidence implies that Zr₆₀Al_7.5 Cu_17.5Ni₁₀Si₄B₁ alloy exhibits the highest thermal stability among those alloys in this study. The crystallization behavior for the alloy 4Si1B isothermally annealed at the supercooled temperature region for different time has also been examined by TEM and discussed.     

Effects of ion irradiation on Zr52.5Cu17.9Ni14.6Al10Ti5 (BAM-11) bulk metallic glass

Bulk metallic glasses are intriguing candidates for nuclear applications due to their inherent amorphous structure, but their radiation response is largely unknown due to the relatively recent nature of innovations in bulk metallic glass fabrication. Here, microstructural and mechanical property evaluations have been performed on a Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ bulk metallic glass (BAM-11) irradiated with 3 MeV Ni⁺ ions to 0.1 and 1.0 dpa at room temperature and 200 °C. Nanoindentation hardness and Young's modulus both decreased by 6–20% in samples irradiated at room temperature, with the sample irradiated to 1.0 dpa experiencing the greatest change in mechanical properties. However, no significant changes in properties were observed in the samples irradiated at 200 °C, and transmission electron microscopy showed no visible evidence of radiation damage or crystallization following ion irradiation at any of the tested conditions. These results suggest that BAM-11 bulk metallic glass may be useful for certain applications in nuclear environments.     

Microwave-induced heating and sintering of metallic glasses

Metallic glasses exhibit low viscosity in a temperature range between the glass-transition and crystallization temperature which allows successful sintering of glassy powders. Microwave heating being a volumetric heating has significant advantages over conventional heating in materials processing, such as substantial energy savings, rapid heating rates and process cleanness. In the present study, we investigate the stability of the Fe₇₃Si₇B₁₇Nb₃, Fe₆₅Co₁₀Ga₅P₁₂C₄B₄, Ni_52.5Zr₁₅Nb₁₀Ti₁₅Pt_7.5, Ni₆₀Nb₂₀Ti₁₅Zr₅, Zr₅₅Cu₃₀Al₁₀Ni₅ and Ti_47.5Zr₁₀Cu₃₀Pd_7.5Sn₅ glassy powders and formation of the porous bulk metallic glassy samples by microwave heating in a single-mode cavity with separated electric (E) and magnetic (H) field maxima in an inert atmosphere. The Fe₇₃Si₇B₁₇Nb₃ and Fe₆₅Co₁₀Ga₅P₁₂C₄B₄ alloys crystallized upon MW heating in both E- and H-field maxima forming a nanostructure. The Ni_52.5Zr₁₅Nb₁₀Ti₁₅Pt_7.5 and Zr₅₅Cu₃₀Al₁₀Ni₅ alloys were heated well in H-field and were not heated well enough in E-field. In case of Ni_52.5Zr₁₅Nb₁₀Ti₁₅Pt_7.5 and Ni₆₀Nb₂₀Ti₁₅Zr₅ alloys sintered samples were obtained.     

Tribological studies of a Zr-based bulk metallic glass

In the present study, the tribological behavior of a Zr_52.5Cu_17.9Ni_14.6Ti₅Al₁₀ bulk metallic glass (BMG) was investigated using pin-on-disk sliding measurements under an argon atmosphere, rubbing against a type 303 stainless steel counterface. The tested pins and disk were examined using X-ray diffractometry, optical microscopy, profilometry, scanning electron microscopy and transmission electron microscopy. The results showed that the wear of the BMG pins was substantially larger compared with previous tests performed against a zirconia counterface. Strain softening was found in the near-surface region of the glassy pin due to the highly localized shearing. Frictional heating contributed to the occurrence of viscous flow and material transfer on the worn surface of the wear pin and the disk, respectively. Thus, the pin exhibited a severe adhesive-dominated sliding wear.     

Electron irradiation induced nano-crystallization in Zr66.7Ni33.3 amorphous alloy and Zr60Al15Ni25 metallic glass

Electron irradiation induced phase transformation behavior of an amorphous phase in Zr_66.7Ni_33.3 alloy, and an amorphous phase or supercooled liquid in Zr₆₀Al₁₅Ni₂₅ alloy was investigated. The amorphous phase could not maintain the original glassy structure under electron irradiation at 298 K, and f.c.c.-solid solution precipitated under electron irradiation in both alloys. The precipitation of C16-Zr₂Ni, big-cube (metastable f.c.c.-based Zr₂Ni intermetallic compound), Zr₆Al₂Ni and Zr₅AlNi₄ crystalline phases from an amorphous phase was not observed during electron irradiation induced crystallization. The amorphous phase in Zr₆₀Al₁₅Ni₂₅ metallic glass shows the highest phase stability against electron irradiation induced crystallization among Zr_66.7Cu_33.3, Zr_66.7Ni_33.3, Zr₆₅Al_7.5Ni_27.5, Zr₆₀Al₁₅Ni₂₅ and Zr₆₅Al_7.5Ni₁₀Cu_17.5 alloys. In Zr₆₀Al₁₅Ni₂₅ metallic glass, electron irradiation promoted the precipitation of f.c.c.-solid solution and Zr₆Al₂Ni crystalline phases from the supercooled liquid.     

Kinetic study of non-isothermal crystallization in Al80Fe10Ti5Ni5 metallic glass

This study investigated the crystallization behavior of a kinetically metastable Al₈₀Fe₁₀Ti₅Ni₅ amorphous phase. The Al₈₀Fe₁₀Ti₅Ni₅ amorphous phase was synthesized via the mechanical alloying of elemental powders of Al, Fe, Ti, and Ni. The microstructures and crystallization kinetics of the as-milled and annealed powders were characterized using X-ray diffraction, transition electron microscopy, and non-isothermal differential thermal analysis techniques. The results demonstrated that an Al₈₀Fe₁₀Ti₅Ni₅ amorphous phase was obtained after 40 h of ball milling. The produced amorphous phase exhibited one-stage crystallization on heating, i.e., the amorphous phase transforms into nanocrystalline Al₁₃(Fe,Ni)₄ (40 nm) and Al₃Ti (10 nm) intermetallic phases. The activation energy for the crystallization of the alloy evaluated from the Kissinger equation was approximately 538±5 kJ/mol using the peak temperature of the exothermic reaction. The Avrami exponent or reaction order n indicates that the nucleation rate decreases with time and the crystallization is governed by a three-dimensional diffusion-controlled growth. These results provide new opportunities for structure control through innovative alloy design and processing techniques.     

Characterization of interface between the particles in NiNbZrTiPt metallic glassy matrix composite containing SiC fabricated by spark plasma sintering

We investigated the microstructure, in particular, the interface structure between powder particles in the Ni_52.5Nb₁₀Zr₁₅Ti₁₅Pt_7.5 bulk glassy alloy composites containing 10 vol.%SiC particulates prepared by a spark plasma sintering (SPS) process by means of scanning and transmission electron microscopies. The SiC particulates were dispersed homogeneously in the Ni_52.5Nb₁₀Zr₁₅Ti₁₅Pt_7.5 glassy matrix. No crystallization of the Ni_52.5Nb₁₀Zr₁₅Ti₁₅Pt_7.5 glassy alloy took place during the SPS process. The good bonding states between SiC particulates and glassy matrix, as well as between glassy particles were recognized. No intermediate layer in the bonded interfaces was observed.     

Heating rate dependence of Tg and Tx in Zr-based BMGs with characteristic structures

Heating rate dependence of glass transition and crystallization temperatures is applicable for evaluation of glass structural stability and also for discussion on the apparent activation energies for glass transition and crystallization. The glass-structure stabilities of the Zr-based BMGs (Zr₅₀Cu₄₀Al₁₀, Zr₇₀Cu₂₀Al₁₀ and Zr₇₀Ni₂₀Al₁₀) and the conventional amorphous alloys (Zr₇₀Cu₃₀ and Zr₇₀Ni₃₀) are assessed by the densely packed glass structure as well as the complicated crystallization process. By the reverse Monte Carlo (RMC) simulation with X-ray and neutron diffraction data, it is shown that the densely packed structure is built by icosahedron-like clusters. In Zr₆₅Al_7.5Ni₁₀Pd_17.5 and Zr₆₅Al_7.5Ni₁₀Cu_17.5, the effect of Pd atoms on the glass structure is also described.     

Effect of Ta on glass formation,thermal stability and mechanical properties of a Zr52.25Cu28.5Ni4.75Al9.5Ta5 bulk metallic glass

The effect of Ta on glass-forming ability, crystallization behavior and mechanical properties of Zr_52.25Cu_28.5Ni_4.75Al_9.5Ta₅ bulk metallic glass (BMG) is investigated. The solubility of Ta in the Zr-base BMG alloy depends on the arc melting conditions. 3.2 at.% Ta dissolve in the alloy inducing an increase of about 20 K in both glass transition temperature and crystallization temperature of the BMG. However, Ta does not significantly change the extension of the supercooled liquid region. The remaining Ta particles in the master alloy may induce a composition-segregation layer around the particles upon subsequent casting. This further induces the crystallization of Zr₂Cu that deteriorates the ductility of the samples. The compressive strength and ductility of the as-cast 3 mm diameter Zr_52.25Cu_28.5Ni_4.75Al_9.5Ta₅ samples are improved in comparison with the Zr₅₅Cu₃₀Ni₅Al₁₀ BMG alloy. The fracture plane of the present alloy has an angle of 31–33° with respect to the stress axis, which remarkably deviates from the maximum shear stress plane. The improvement of the mechanical properties and the peculiar fracture feature for the Zr_52.25Cu_28.5Ni_4.75Al_9.5Ta₅ BMG alloy can be attributed to the effect of dispersed Ta particles.     

Cast structure and mechanical properties of Zr–Cu–Ni–Al bulk glassy alloys

Homogeneous melting without any nuclei was performed using the cold copper nozzle arc casting furnace and ladle arc-melt type furnace. Casting of a bulk glassy alloy can be achieved by using a copper nozzle arc casting furnace, which eliminates nucleation site (cold spot) for crystallization. Besides, the pouring molten alloy was melted homogeneously by arc heating before casting into the mold, similar to a pseudo float melting state. To produce a bulk glassy alloy sheet, a combination of the ladle arc-melt type furnace and squeeze cast method was used. Using this method, we succeeded in producing Zr₅₀Cu₃₀Ni₁₀Al₁₀ bulk glassy alloys in a rod shape by the former method and in a sheet form by the later method. Tensile strength of the Zr₅₀Cu₃₀Ni₁₀Al₁₀ bulk glassy alloy sheet is about 1900 MPa and the plasticity of the alloy at room temperature is significantly improved by cold rolling.     

Peculiarities of ball-milling induced crystalline–amorphous transformation in Cu–Zr–Al–Ni–Ti alloys

An amorphization process in (Cu₄₉Zr_45−xAl_6+x)_100−y−zNi_yTi_z (x = 1, y, z = 0; 5; 10) induced by ball-milling is reported in the present work. The aim was investigation of the effect of Ni and Ti addition to Cu₄₉Zr₄₅Al₆ and Cu₄₉Zr₄₄Al₇ based alloys as well as type of initial phases on the amorphization processes. Also the milling time sufficient for obtaining fully amorphous state was determined. The entire milling process lasted 25 h. Drastic structural changes were observed in each alloy after first 5 h of milling. In most cases, after 15 h of milling the powders had fully amorphous structure according to XRD except for those ones, where TEM revealed a few nanosized crystalline particles in the amorphous matrix. In (Cu₄₉Zr₄₅Al₆)₈₀Ni₁₀Ti₁₀ alloy the amorphization process took place after 12 h of milling and the amorphous state was stable up to 25 h of milling. In the case of (Cu₄₉Zr₄₄Al₇)₈₀Ni₁₀Ti₁₀ alloy the powders have fully amorphous structure between 12 h and 15 h of milling.     

Enhancement of plasticity in Zr-based bulk metallic glasses electroplated with copper coatings

Electrodeposition was used to coat copper films on the surface of the BMG pillars (bulk metallic glasses) of Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ (Vit. 105) with the film thicknesses of 71.5 and 161.1 μm. The experimental results of the compression tests of the bare Vit. 105 pillars and the coated Vit. 105 pillars revealed that the copper costing increased the density of shear bands in the Vit. 105 pillars formed during the tests, resulting in the improvement of plasticity. The plastic strain was 6.1% for the coated pillars with a coating thickness of 161.1 μm, which is 3.59 times of 1.7% of the bare Vit. 105 pillars. The deformation of the copper films dissipated the strain energy and limited the propagation of shear bands, which led to the initiation and formation of multiple shear bands. The technique developed in this work provides an effective way to enhance the plasticity of BMGs at room temperature.     

Tribological properties of graphite- and ZrC-reinforced bulk metallic glass composites

The influence of second-phase reinforcement on the micro-tribological properties of Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ (Vit 105) was investigated by ball-on-disc tests. It was found that monolithic amorphous Vit 105 displays a coefficient of friction (COF) similar to that of 100Cr6 bearing steel. Further, it was seen that adding a low volume content of graphite and especially of ZrC generates a significant decrease in the COF, of up to 50%. Amorphous Vit 105 and its graphite-/ZrC-reinforced composites typically display two regimes of COF. After 100–500 revolutions it drops to about 2/3 of the starting value, and jumps back up to the initial COF are also observed. These transitions take place within the space of about 10 revolutions and are accompanied by a significant change in wear track depth. Investigation of the wear rate indicates that the graphite-/ZrC-reinforced bulk metallic glass composites display an even lower wear rate than 100Cr6 bearing steel.     

Microstructural analysis of Zr55Cu30Al10Ni5 bulk metallic glasses by laser surface remelting and laser solid forming

The crystallization behavior of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk amorphous alloy during laser solid forming (LSF) was analyzed. Since laser surface remelting (LSM) is a key process for the LSF, the crystallization behavior of as-cast Zr₅₅Cu₃₀Al₁₀Ni₅ bulk metallic glasses (BMGs) during LSM was also investigated. It was found that the amorphous state of the as-cast BMGs was maintained when they were repeatedly remelted four times in a single-trace LSM, and as for the LSF of Zr₅₅Cu₃₀Al₁₀Ni₅ bulk amorphous alloy, the crystallization primarily occurred in the HAZ between the adjacent traces and layers after the two layers were deposited. The as-deposited microstructure exhibited a series of phase evolutions from the molten pool to the HAZ as follows: the amorphous → NiZr₂–type nanocrystal + amorphous → NiZr₂–type equiaxed dendrite + amorphous → Cu₁₀Zr₇–type dendrite + NiZr₂–type nanocrystal. Among these microstructural patterns, the NiZr₂–type nanocrystals and equiaxed dendrites primarily formed from the rapid solidification of the remelted liquid in the laser processing process, and the Cu₁₀Zr₇–type dendrites in the HAZ primarily formed by the crystallization of pre-existed nuclei in the already-deposited amorphous substrate.     

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.