Thermodynamic approach to free volume kinetics during isothermal relaxation in bulk Pd–Cu–Ni–P20 glasses

Isothermal relaxation behavior just under glass transition region was investigated for bulk Pd₄₀Ni₄₀P₂₀ and Pd_42.5Cu₃₀Ni_7.5P₂₀ metallic glasses. The densification of the bulk sample during relaxation was examined directly by density measurement using conventional Archimedean technique. The density of as-quenched Pd₄₀Ni₄₀P₂₀ increased monotonously with time. From the density data of Pd₄₀Ni₄₀P₂₀ glass, the free volume relaxation was examined and the kinetics was well described by a stretched exponential function with Kohlrausch exponent less than unity. These glasses also showed a clear two-step relaxation that may be a feature peculiar to bulk metallic glasses.     

Pd20Pt20Cu20Ni20P20 high-entropy alloy as a bulk metallic glass in the centimeter

A Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ bulk metallic glass (BMG) with a high-entropy (HE) alloy composition and a maximum diameter of 10 mm was fabricated by fluxed water quenching. The system and composition of the Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ alloy were determined from a prototype ternary Pd₄₀Ni₄₀P₂₀ BMG in accordance with two strategic alloy designs of (1) HE alloy defined by an equi-atomic alloy with five or more elements and (2) exchangeability of the constituent elements with a similar chemical nature in the periodic table. Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ HE-BMG had a supercooled liquid range of 65 K and a reduced glass transition temperature of 0.71. Successful formation of Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ HE-BMG is significant to develop new alloys for HE alloys and BMGs.     

Pd20Pt20Cu20Ni20P20 高熵金属玻璃的热稳定性和热塑成形性

采用差示扫描量热法、X射线衍射和热力学分析研究了Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀高熵金属玻璃（HEMG）的热稳定性和热力学性能。结果表明,与其他经典贵金属基金属玻璃相比,Pd₂₀Pt₂₀Cu₂₀Ni₂₀P₂₀ HEMG具有相当的性能和鲜明的特点。     

Electronic structure of Pd42.5Ni7.5Cu30P20, an excellent bulk metallic glass former: Comparison to the Pd40Ni40P20 reference glass

In-house photoemission and inverse-photoemission spectra (PES and IPES) were measured on Pd_42.5Ni_7.5Cu₃₀P₂₀ and Pd₄₀Ni₄₀P₂₀ bulk metallic glasses in order to clarify the origin of excellent glass-forming ability from the viewpoint of electronic structure. Minima are observed for both the metallic glasses at a slightly higher energy than the Fermi level. Incident photon-energy dependent PES spectra were obtained using synchrotron radiation and the Pd 4d partial density of states (DOS) was estimated from the PES data. Soft X-ray emission spectra were also measured near the Ni and Cu 2p_3/2 absorption edges to evaluate, respectively, the Ni and Cu 3d partial DOS in the valence band. The Pd 4d and the Ni and Cu 3d partials in the conduction band were obtained from X-ray absorption spectra around the Pd 3p_3/2 and Ni and Cu 2p_3/2 absorption edges, respectively. It was found that the Pd 4d partial DOS near the Fermi energy largely decreases and becomes localized by replacing the Ni atoms with the Cu atoms, which may be closely related to the excellent glass-forming ability of the Pd_42.5Ni_7.5Cu₃₀P₂₀ bulk metallic glass due to a selective formation of Pd–P covalent bonds.     

Thermal behaviour of Pd40Cu30Ni10P20 bulk metallic glass

The thermal behaviour of differently milled Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass through the glass transition has been investigated by in situ high-energy synchrotron X-ray diffraction. Repeated heating and cooling were performed between the glassy and the supercooled liquid state. The changes in positions and intensities of the first and second diffraction maxima of the as-milled powder indicate irreversible changes during first heating up to the glass transition temperature T_g due to structural relaxation. After annealing, reversible structural changes with temperature are observed upon heating and cooling in the glassy phase, and in the supercooled liquid state respectively. The shift in the position of the first maximum scales approximately with the linear thermal expansion for the glassy state; however, this relation does not hold for the supercooled liquid. The structural transition from the glass to the supercooled liquid at the glass transition temperature is reflected by the intensity of the diffraction maxima and by a reversed temperature dependence of the position of the second diffuse maximum below and above T_g. The changes of the glass structure for the decrease of free volume by annealing are found to be different from those observed for the reversible volume expansion or shrinkage by varying the temperature. Therefore, the shift of the first diffuse maximum position of bulk metallic glasses cannot be used as a measure of the change in free volume.     

New nickel-based bulk metallic glasses with extremely high nickel content

The effect of boron addition on glass formation in the Ni₇₀Pd₁₀P₂₀ alloy was investigated. The composition containing 4 at% boron showed an improved glass-forming ability. A glassy Ni₇₀Pd₁₀P₁₆B₄ alloy rod with a diameter of 2.5 mm was prepared by a copper mold casting technique. This is the first time that a Ni-based bulk metallic glass with such an extremely high Ni content of 70 at% has been produced. The obtained glassy Ni₇₀Pd₁₀P₁₆B₄ alloy exhibited rather good mechanical properties and corrosion resistance.     

Influence of minor Si addition on the glass-forming ability and mechanical properties of Pd40Ni40P20 alloy

The influence of a minor Si addition on the glass-forming ability and mechanical properties of Pd₄₀Ni₄₀P₂₀ alloy was investigated. It is suggested that the minor Si addition can adjust the composition to be closer to eutectic, which favors a large undercooling. Furthermore, Si addition led to an enhancement in the ductility of Pd–Ni–P bulk metallic glasses. Simultaneously it is of great interest that there are nanoscale and microscale wavy steps observed on the fracture surface of Pd₄₀Ni₄₀Si₄P₁₆ metallic glass. It is suggested that a quickly running crack dissipates excess energy in terms of stress wave, leaving such wavy traces on the fracture surface of the deformed Pd-based metallic glass.     

Elastic constants of amorphous and single-crystal Pd40Cu40P20

We have measured the adiabatic second-order elastic constants of amorphous Pd₄₀Cu₄₀P₂₀ (isotropic, two independent elastic constants) and single-crystal Pd₄₀Cu₄₀P₂₀ (tetragonal, six independent elastic constants) over the range 3.9 < T < 300 K. Below ∼20 K, the elastic constants of single-crystal Pd₄₀Cu₄₀P₂₀ vary as C(T) = C(0)[1 − bT² − dT⁴], which is the same temperature dependence found in metallic elements. In contrast, below ∼20 K the elastic constants of amorphous Pd₄₀Cu₄₀P₂₀ vary as C(T) = C(0¹)[1 − aT]. The bulk modulus of amorphous Pd₄₀Cu₄₀P₂₀ is approximately 2% lower than that of crystalline Pd₄₀Cu₄₀P₂₀, whereas the shear modulus of the glass is 13–36% lower than the four independent shear moduli of the tetragonal crystal. The lower moduli of the glass are best explained by additional atomic displacements, beyond those experienced by the atoms in a crystal, that occur because the atoms in glasses do not occupy centers of symmetry.     

Optimized interface and mechanical properties of W fiber/Zr-based bulk metallic glass composites by minor Nb addition

W fiber/Zr-based bulk metallic glass composites were prepared by melt infiltration casting and the interface reaction in composites was studied in detail. It was found that minor Nb addition to the matrix can suppress the interface peritectic reaction and optimize the interface structure in W fiber/Zr-based bulk metallic glass composites. Taking the interface characteristics of composites and glass forming ability of the matrix into account, an optimized alloy Zr₄₇Ti₁₃Cu₁₁Ni₁₀Be₁₆Nb₃ was selected as a new metallic glass matrix. The interface in the W fiber/Zr₄₇Ti₁₃Cu₁₁Ni₁₀Be₁₆Nb₃ bulk metallic glass composite has excellent interface bonding, and the compressive strength of 70% W fiber/Zr₄₇Ti₁₃Cu₁₁Ni₁₀Be₁₆Nb₃ metallic glass composite is 2.6 GPa, 58% higher than the unreinfored matrix. Multiple shear band formation in the matrix, which results from the interaction between W fiber and the matrix, can answer for the high ultimate fraction strength and excellent plastic deformation of the composite.     

Effect of hydrostatic pressure on the decomposition behavior of Cu54Zr22Ti18Ni6 bulk metallic glass alloy in supercooled liquid region

The effect that hydrostatic pressure has on the decomposition behavior in Cu₅₄Ni₆Zr₂₂Ti₁₈ bulk metallic glass (BMG) alloy was assessed using samples, which were isothermally annealed in the supercooled liquid region (SLR) with and without application of hydrostatic pressure. During subsequent annealing for the thermal analysis, the samples annealed under hydrostatic pressure displayed a slower crystallization process in the SLR, which is attributed to a retarded compositional decomposition of the BMG alloy under pressure.     

Atom probe tomography study of the decomposition of a bulk metallic glass

The microstructural evolution of a Pd₄₀Ni₄₀P₂₀ bulk metallic glass that was isothermally annealed at 260 °C for 14 h, and then aged at 340 °C for times up to 1280 min has been studied. Differential scanning calorimetry (DSC) curves of the aged samples show an endothermic peak at approximately 370 °C in addition to the ubiquitous glass transition. The endothermic peak appears after 20 min aging and disappears after 320 min aging. The corresponding X-ray diffraction (XRD) data show no Bragg peaks that could indicate the formation of a crystalline phase. Near-atomic-resolution atom probe tomography (APT) was used to study changes in the atomic spatial distributions as a function of aging time. The chemical environment around each of the atomic species, and the tendencies for solute clustering and chemical short range ordering, were determined from statistical analysis of the APT data. Clustering and possible phase separation are identified by APT after only 20 min aging at 340 °C, which correlates with the appearance of the peak in the DSC signal. Crystallization is apparent in the APT and XRD data after aging for 320 min. The study suggests that the amorphous Pd₄₀Ni₄₀P₂₀ annealed at a temperature 40 °C above T_g phase separates into two or more amorphous phases. The endothermic peak in the DSC trace is produced by the dissolution of the phase separation.     

Dynamic response of a Pd40Ni40P20 bulk metallic glass in tension

Tensile behavior of a bulk metallic glass Pd₄₀Ni₄₀P₂₀ was characterized under both quasi-static and dynamic strain rate conditions. No major difference was observed. Multiple shear bands formed in samples tested at the dynamic strain rate. However, shear band interaction appears to have an insignificant effect on the plasticity of the alloy.     

Stability and nucleation behavior of glass-forming Pd–Cu–Ni–P alloy with a critical cooling rate of 0.067 K/s

An undercooled Pd_42.5Cu₃₀Ni_7.5P₂₀ melt having a eutectic composition exhibits the lowest critical cooling rate for glass formation of 0.067 K/s. Nucleation and crystal growth behaviors of the undercooled melt were investigated. For example, nucleation frequency and crystal growth rate at 683 K where the temperature is close to nose temperature were evaluated as 4.76×10⁹ nuclei/m³ s and 3.24×10⁻⁷ m/s, respectively. These values are almost the same as those for the undercooled Pd₄₀Cu₃₀Ni₁₀P₂₀ melt which has a slightly off-eutectic composition. However, the difference in incubation time for crystallization and nucleation mode was observed in both melts. The nucleation mechanism of undercooled Pd_42.5Cu₃₀Ni_7.5P₂₀ and Pd₄₀Cu₃₀Ni₁₀P₂₀ melt is compared. Based on these results, the prolongation in incubation time for crystallization is discussed in the present study.     

Assessment of rheological and thermodynamic properties of the Pd40Ni40P20 bulk metallic glass around glass transition using an indentation creep technique

The thermodynamic and rheological properties of the Pd₄₀Ni₄₀P₂₀ bulk metallic glass are explored by means of an indentation creep technique around the glass transition. We have developed a dedicated instrumented indentation apparatus allowing to assess the mechanical properties at elevated temperatures. The analysis of results is made possible by using the viscoelastic solutions of contact mechanics. We also analyse the thermodynamics of creep around glass transition to estimate the activation free energy changes from the activation free enthalpy changes via the shear modulus – temperature data. The shear viscosity values extracted using this technique allow for the derivation of activation energies (free enthalpy 210 kJ/mol, enthalpy 456 kJ/mol, entropy 410 J/mol/K) for the flow process. All these properties were found to closely match with those obtained using conventional techniques for viscosity measurements. Compared to the latter, the indentation creep technique requires small volumes and samples are easy to prepare. It is therefore expected that such a technique might be employed for the study of glass transition in metallic glasses.     

Pd40Ni40Si5P15 bulk metallic glass properties variation as a function of sample thickness

This work presents a comparative study of different properties variation of Pd₄₀Ni₄₀Si₅P₁₅ bulk metallic glass (BMG), namely: density, hardness, relaxation enthalpy and mechanical properties as a function of the sample thickness. The samples were produced in the form of a long pyramid by conventional Cu-mold casting in an Ar atmosphere. The results illustrate significantly different sensitivity of these properties of the glassy phase to the cooling rate. The difference in crystallization behavior is also discussed.     

Kinetics of crystallization process for Pd-based bulk metallic glasses

The crystallization behavior of Pd₇₉Cu₆Si₁₀P₅ and Pd₇₉Cu₄Au₂Si₁₀P₅ bulk metallic alloys was studied using differential scanning calorimeter (DSC) under different heating conditions. Under isochronal heating, the onset temperatures of the glass transition and crystallization for these glasses exhibited strong heating-rate dependence. The activation energies for the glass transition and crystallization were determined, based on the Kissinger plots, to be 540 and 452 kJ/mol, respectively, for Pd₇₉Cu₆Si₁₀P₅ glassy alloy, and 640 and 318 kJ/mol, respectively, for Pd₇₉Cu₄Au₂Si₁₀P₅ glassy alloy. The isothermal kinetics was modeled by the Johnson–Mehl–Avrami equation. For the Pd₇₉Cu₆Si₁₀P₅ glassy alloy the Avrami exponent was mostly in the range from 2.23 to 2.52, which indicated a decreasing nucleation rate and a diffusion-controlled three-dimensional growth. For the Pd₇₉Cu₄Au₂Si₁₀P₅ glassy alloy the Avrami exponent was in the range between 2.42 and 2.76, which indicated an increasing nucleation rate and a diffusion-controlled three-dimensional growth.     

Superplasticity in a bulk amorphous Pd-40Ni-20P alloy:a compression study

Compressive deformation behavior of a cast Pd₄₀Ni₄₀P₂₀ bulk metallic glass in the supercooled liquid region (589–670 K) was investigated at strain rates ranging from 10⁻⁴ to 10⁻² s⁻¹. The material exhibited excellent mechanical formability in the supercooled liquid region. However, in contrast to a Newtonian behavior generally observed in oxide glasses, the present alloy also showed a non-Newtonian behavior, depending upon the temperature and applied strain rate. Specifically, the alloy is like a Newtonian fluid at high temperatures, but becomes non-Newtonian at low temperatures and high strain rates. Structures of the amorphous material, both before and after deformation, were examined using X-ray diffraction and high-resolution transmission electron microscopy. The non-Newtonian behavior is proposed to be associated with the glass instability during deformation.     

La-based bulk metallic glasses with critical diameter up to 30 mm

We report composition optimization, thermal and physical properties of new La-based bulk metallic glasses with high glass forming ability (GFA) based on a ternary La₆₂Al₁₄Cu₂₄ alloy. By refining the (Cu, Ag)/(Ni, Co) and La/(Cu, Ag) ratios in the La–Al–(Cu,Ag)–(Ni, Co) pseudo-quaternary alloy, the formation of 30 mm diameter of La₆₅Al₁₄(Cu_5/6Ag_1/6)₁₁(Ni_1/2Co_1/2)₁₀ bulk metallic glass (BMG) alloy is achieved using water quenching. The origin of the high GFA was investigated from the kinetic, structural and thermodynamic points of view, and was found to be due to the smaller difference in Gibbs free-energy between the amorphous and crystalline phases in the pseudo-quaternary alloy. These alloys exhibit low glass transition temperatures, below 430 K, and relatively wide supercooled liquid regions of 40–60 K. Mechanical tests on these alloys show a fracture strength of 650 GPa, Vicker’s hardness 200 kg mm⁻², Young’s modulus 35 GPa, shear modulus 13 GPa and Poisson ratio 0.356. The La-based BMGs are useful for both scientific and engineering applications.     

Local atomic structure of Pd–Ni–P bulk metallic glass examined by high-resolution electron microscopy and electron diffraction

Structural fluctuation in a Pd₄₀Ni₄₀P₂₀ bulk metallic glass is investigated by transmission electron microscopy and electron diffraction. Local atomic ordered regions with a fcc-(Pd,Ni) type structure was sharply imaged by a high-resolution electron microscopy (HREM) attached with a Cs-corrector. Interference function for the glassy state was obtained from electron-diffraction intensity profiles using energy-filter and imaging-plate techniques. We used a reverse Monte Carlo (RMC) simulation method to develop a realistic structure model. The model consists of a dense-random-packing structure, in which an fcc ordered region with Pd, Ni, and P atoms was embedded. The structure model is consistent with the diffraction and HREM results. In Voronoi polyhedral analysis of the RMC simulated structure, P-centered (Pd,Ni)-P trigonal prisms are found primarily in the matrix structure embedding the fcc-cluster. Around Pd and Ni atoms deformed-fcc type polyhedra were frequently observed. From these local structural features, nanoscale phase separation was revealed to occur during the glass formation.     

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.