Differences in structure and dynamics of ternary Pd–Ni-based bulk metallic glasses containing sulfur or phosphorous

The composition Pd$_{31}$Ni$_{42}$S$_{27}$ has been shown to be the best glass former in the family of recently discovered glass forming PdNiS alloys. In this study, this sample system was systematically investigated using fluctuation- and correlation electron microscopy of which the results are compared to a Pd$_{40}$Ni$_{40}$P$_{20}$ bulk metallic glass that serves as a model system for metallic glasses. Strong differences in the local atomic correlations beyond the short-range order were observed, which are assumed to be a reason for their discrepancy in thermal stability. The relaxation dynamics at room temperature revealed faster dynamics in the sulfur-containing Pd$_{31}$Ni$_{42}$S$_{27}$ glass

Development and optimization of novel sulfur-containing Ti-based bulk metallic glasses and the correlation between primarily crystallizing phases, thermal stability and mechanical properties

The effect of sulfur on the glass forming ability, thermal stability and mechanical properties of the eutectic alloy Ti33.4Zr33.3Cu33.3 was investigated by conventional X-ray diffraction, differential scanning calorimetry and 3-point flexural experiments. A novel region of bulk glass formation with a critical casting diameter of up to 4 mm was found in the quaternary Ti-Zr-Cu-S system, however, brittle fracture behavior was predominant. Various alloying strategies were employed to improve mechanical properties and a compositional transition from brittle to ductile fracture has been identified (e.g. for Ti36Zr33.5Cu24.5S6). A change of the primary precipitating phases from a C14 Laves to an intermetallic (Ti,Zr)2Cu phase can be observed, as well as a stabilization of the supercooled liquid. The origin of the thermally unstable behavior in Ti-based bulk metallic glasses is traced back to the easy formation of the icosahedral phase upon heating, which is structurally close to the supposedly predominant icosahedral short-range order in the amorphous state. The systematic study carried out in this work indicates a strong correlation between primary crystallizing phase and thermal stability, both pointing to the frozen short-range order in the amorphous state which is predetermining the mechanical properties. The transition from the Laves to the intermetallic (Ti,Zr)2Cu phase as well as the enlarged supercooled liquid region appear to be directly related to a destabilization of the icosahedral short-range order and ultimately to the improved mechanical properties

Effect of composition and thermal history on deformation behavior and cluster connections in model bulk metallic glasses

The compositional dependence and influence of relaxation state on the deformation behavior of a Pt-Pd-based bulk metallic glasses model system was investigated, where platinum is systematically replaced by topologically equivalent palladium atoms. The hardness and modulus increased with rising Pd content as well as by annealing below the glass transition temperature. Decreasing strain-rate sensitivity and increasing serration length are observed in nano indentation with increase in Pd content as well as thermal relaxation. Micro-pillar compression for alloys with different Pt/Pd ratios validated the greater tendency for shear localization and brittle behavior of the Pd-rich alloys. Based on total scattering experiments with synchrotron X-ray radiation, a correlation between the increase in stiffer 3-atom cluster connections and reduction in strain-rate sensitivity, as a measure of ductility, with Pd content and thermal history is suggested

Disentangling structural and kinetic components of the {\alpha}-relaxation in supercooled metallic liquids

The particle motion associated to the {\alpha}-relaxation in supercooled liquids is still challenging scientists due to its difficulty to be probed experimentally. By combining synchrotron techniques, we found the existence of microscopic structure-dynamics relationships in Pt42.5Cu27Ni9.5P21 and Pd42.5Cu27Ni9.5P21 liquids which allows us to disentangle structural and kinetic contributions to the {\alpha}-process. While the two alloys show similar kinetic fragilities, their structural fragilities differ and correlate with the temperature dependence of the stretching parameter describing the decay of the density fluctuations. This implies that the evolution of dynamical heterogeneities in supercooled alloys is determined by the rigidity of the melt structure. We find also that the atomic motion not only reflects the topological order but also the chemical short-range order, which can lead to a surprising slowdown of the {\alpha}-process at the mesoscopic length scale. These results will contribute to the comprehension of the glass transition, which is still missing

Disentangling structural and kinetic components of the α-relaxation in supercooled metallic liquids

The particle motion associated to the α-relaxation in supercooled liquids is still challenging scientists due to its difficulty to be probed experimentally. By combining synchrotron techniques, we report the existence of microscopic structure-dynamics relationships in Pt42.5Cu27Ni9.5P21 and Pd42.5Cu27Ni9.5P21 liquids which allows us to disentangle structural and kinetic contributions to the α-process. While the two alloys show similar kinetic fragilities, their structural fragilities differ and correlate with the temperature dependence of the stretching parameter describing the decay of the density fluctuations. This implies that the evolution of dynamical heterogeneities in supercooled alloys is determined by the rigidity of the melt structure. We find also that the atomic motion not only reflects the topological order but also the chemical short-range order, which can lead to a surprising slowdown of the αprocess at the mesoscopic length scale. These results will contribute to the comprehension of the glass transition, which is still missing

Laser powder bed fusion of Cu-Ti-Zr-Ni bulk metallic glasses in the Vit101 alloy system

Laser powder bed fusion (PBF-LB/M) of bulk metallic glasses (BMGs) has experienced growing scientific and industrial interest in the last years, with a special focus on application relevant systems based on zirconium. The high cooling rates and the layer-wise build-up process allow overcoming size and geometry limitations typical for conventional casting routes. Yet, the novel production approach requires different alloy characteristics than casting processes. The present work reports for the first time on the PBF-LB/M-processing of three CuTi-based bulk metallic glass formers in the Vit101 system, allowing to exceed the mechanical performance of most additively formed Zr-based BMGs. Furthermore, the influence of alloy properties like thermal stability and toughness on the PBF-LB/M applicability are systematically studied. Thermal stability plays a minor role to produce amorphous specimen, while notch toughness is found to be a more crucial aspect to achieve parts with low defect density and resulting high mechanical performance. The results suggest fundamentally different alloy development strategies adapted to the needs of the PBF-LB/M-process, leaving classical casting-based optimization of glass forming ability behind and evolving towards a rather toughness-oriented optimization

Ni-Nb-P-based bulk glass-forming alloys: Superior material properties combined in one alloy family

Ni-Nb-based bulk glass-forming alloys are among the most promising amorphous metals for industrial applications due to their incomparable combination of strength, hardness, elasticity and plasticity. However, the main drawback is the limited glass-forming ability, narrowing the field of application to solely small components. In this study, we show that minor additions of P to the binary Ni-Nb system increase the glass-forming ability by 150 % to a record value of 5 mm. P can be easily added by using an industrial Ni-P pre-alloy which is readily available. The partial substitution of Nb by Ta further boosts the glass-forming ability to values 200 % higher than that of the binary base alloy. Besides conventional X-ray diffraction measurements, the amorphous nature of the samples is verified by high-energy synchrotron X-ray diffraction experiments. Moreover, the mechanical properties of the new alloy compositions are characterized in uniaxial compression tests and Vickers hardness measurements, showing a high engineering yield strength of 3 GPa, an extended plastic regime up to 10 % strain to failure and an increase of the hardness to a maximum value of 1000 HV5. Additionally, calorimetric measurements reveal that the modified alloys feature an extended supercooled liquid region up to 69 K upon heating, permitting thermoplastic micro molding of amorphous feedstock material

Ultrafast scanning calorimetry of newly developed Au-Ga bulk metallic glasses

The isothermal crystallization times and critical cooling rates of the liquid phase are determined for the two bulk metallic glass forming alloys Au49Ag5.5Pd2.3Cu26.9Si16.3 and Au51.6Ag5.8Pd2.4Cu20.2Ga6.7Si13.3 by using fast differential scanning calorimetry, covering the whole timescale of the crystallization event of the metallic melt. In the case of Au49Ag5.5Pd2.3Cu26.9Si16.3, a typical crystallization nose was observed, whereas for the Au51.6Ag5.8Pd2.4Cu20.2Ga6.7Si13.3, a more complex crystallization behavior with two distinct crystallization noses was found. Even for the complex crystallization behavior of the Au51.6Ag5.8Pd2.4Cu20.2Ga6.7Si13.3 alloy it is shown that the minimal isothermal nose time does allow for a quantification of the macroscopic critical thickness. It is discussed in contrast to the critical cooling rate, which is found to allow less exact calculations of the critical thickness and thus does not correlate well with the critical cooling rate from macroscopic experiments. Additionally the crystallization data of Au49Ag5.5Pd2.3Cu26.9Si16.3 was modeled using classical nucleation theory with the Johnson–Mehl–Avrami–Kolmogorov (JMAK) equation, enabling a determination of the interfacial energy

Signatures of structural differences in Pt–P- and Pd–P-based bulk glass-forming liquids

The structural differences between the compositionally related Pt–P- and Pd–P-based bulk glass-forming liquids are investigated in synchrotron X-ray scattering experiments. Although Pt and Pd are considered to be topologically equivalent in structural models, we show that drastic changes in the total structure factor and in the reduced pair distribution function are observed upon gradual substitution. These variations indicate the existence of significant structural differences on the short- (SRO) and medium-range order (MRO) length scale. The structural data suggest that the distribution of the dominant polyhedra and the distribution of their connection schemes gradually change from Pt–P- to Pd–P-based alloys, which is likely connected to the different sensitivities to annealing or cooling rate induced embrittlement. The evolution of the total structure factor and the reduced pair distribution function with increasing temperature indicate the (partial) dissolution of both, the MRO and the SRO, which reflects the thermodynamic properties of the liquids

On the thermodynamics and its connection to structure in the Pt-Pd-Cu-Ni-P bulk metallic glass forming system

Contrary to basic hard sphere structure models, recent studies revealed, significant structural differences between Pt-Cu-Ni-P and Pd-Cu-Ni-P metallic glass-forming liquids with the same stoichiometry. To cover the compositional space between both systems, Platinum is subsequently replaced by Palladium in the composition (Pt/Pd)$_{42.5}$Cu$_{27}$Ni$_{9.5}$P$_{21}$. For this systematic set of alloys, the thermodynamic properties, such as isobaric heat capacity, enthalpy and Gibbs free energy are assessed. A systematic drop of the Gibbs free energy difference between crystal and liquid, providing a lower estimate of the driving force for crystallization was observed, underlining the high glass-forming ability of the Pd-rich systems. Contrary to kinetic fragility data, a change of the thermodynamic fragility can be observed, drawing the picture of an increasing thermodynamically strong behavior with rising Pd-content. Further the temperature induced changes of the total structure factors S(Q) were monitored using high-energy synchrotron X-ray diffraction. Focus was laid on the changes on the medium-range length scale, by analyzing changes of the first sharp diffraction peak. Here a good correlation of the changes in peak-width and the thermodynamic fragility was found. From the determination of the excess enthalpy, large amounts of residual enthalpy in the glassy state were observed for the Pt-rich alloys, supporting the increased ductility of these alloys. The current findings further carve out the different roles of the topologically similar Pt and Pd in the Pt/Pd-Cu-Ni-P alloy system and how the change of the structural motifs on the medium range order is structurally influencing thermal properties such as enthalpy and heat capacity