Ductile Bulk Metallic Glass

We report on experimental evidence of pronounced global plasticity measured in monolithic Pt57.5Cu14.7Ni5.3P22.5 bulk metallic glass under both bending and unconfined compression loading conditions. A plastic strain of 20% is measured, never before seen in metallic glasses. Also, permanent deformation and a strain exceeding 3% before failure is observed during bending of 4 mm thick samples. To date, no monolithic metallic material has exhibited such a combination of high strength, extensive ductility, and high elastic limit. The large plasticity is reflected in a high Poisson ratio of 0.42, which causes the tip of a shear band to extend rather than initiate a crack. This results in the formation of multiple shear bands and is the origin of the observed large global ductility and very high fracture toughness, approximately 80 MPa m^-1/2

Highly processable bulk metallic glass-forming alloys in the Pt–Co–Ni–Cu–P system

Highly processable bulk metallic glass alloys in the Pt–Co–Ni–Cu–P system were discovered. The alloys show low liquidus temperature below 900 K, excellent processability with low critical cooling rate reflecting in maximum casting thicknesses in quartz tubes of up to 20 mm, and a large supercooled liquid region. The Pt57.5Cu14.7Ni5.3P22.5 composition has a liquidus temperature of 795 K, a glass transition temperature of 508 K with a supercooled liquid region of 98 K. For medical and jewelry applications a Ni-free alloy, Pt60Cu16Co2P22 was discovered with a liquidus temperature of 881 K, a glass transition temperature of 506 K, and a supercooled liquid region of 63 K. Glass formation was observed in a wider composition range. Vickers hardness of these alloys is in the 400 Hv range. The alloys can be processed in the supercooled liquid region in air without any measurable oxidation. In this region, a large processing window is available in which the material does not embrittle. Embrittlement in these alloys is correlated with crystallization. It can be avoided as long as substantial crystallization does not take place during isothermal processing in the supercooled liquid region. Also, liquid processing can be performed in air when flux with B2O3

History dependent crystallization of Zr41Ti14Cu12Ni10Be23 melts

The crystallization of Zr41Ti14Cu12Ni10Be23 (Vit 1) melts during constant heating is investigated. (Vit 1) melts are cooled with different rates into the amorphous state and the crystallization temperature upon subsequent heating is studied. In addition, Vit 1 melts are cooled using a constant rate to different temperatures and subsequently heated from this temperature with a constant rate. We investigate the influence of the temperature to which the melt was cooled on the crystallization temperature measured upon heating. In both cases the onset temperature of crystallization shows strong history dependence. This can be explained by an accumulating process during cooling and heating. An attempt is made to consider this process in a simple model by steady state nucleation and subsequent growth of the nuclei which results in different crystallization kinetics during cooling or heating. Calculations show qualitative agreement with the experimental results. However, calculated and experimental results differ quantitatively. This difference can be explained by a decomposition process leading to a nonsteady nucleation rate which continuously increases with decreasing temperature

Extremely low critical cooling rate measured on dispersed Pd43Ni10Cu27P20

Crystallization of dispersed Pd43Ni10Cu27P20 melts is studied during constant cooling and heating. Investigations are carried out on samples that are dispersed into several hundred particles which are fluxed in B2O3. The size of the particles is chosen in such a way that crystallization of individual particles can be observed. Constant cooling experiments with rates between 0.3 and 0.0016 K/s are performed. In order to determine the fraction of particles that crystallize upon cooling, the crystallization during subsequent heating at 0.3 K/s is utilized. 10%–15% of the particles do not crystallize during cooling with a rate as low as 0.005 K/s. This is the lowest rate that avoids crystallization ever measured for a metallic system. This extremely low critical cooling rate suggests that a fraction of the particles do not contain the impurities that act as nuclei in bulk samples. Therefore, in these particles, nuclei first have to form and crystallization does not take place, as it was found for bulk Pd43Ni10Cu27P20, by the growth on pre-existing nuclei formed by impurities

Strain Rate Induced Crystallization in Bulk Metallic Glass-Forming Liquid

We report on the solidification of Au49Ag5.5Pd2.3Cu26.9Si16.3 bulk metallic glass under various strain rates. Using a copper mold casting technique with a low strain rate during solidification, this alloy is capable of forming glassy rods of at least 5 mm in diameter. Surprisingly, when the liquid alloy is splat cooled at much higher cooling rates and large strain rates, the solidified alloy is no longer fully amorphous. Our finding suggests that the large strain rate during splat cooling induces crystallization. The pronounced difference in crystallization behavior cannot be explained by the previously observed strain rate effect on viscosity alone. A strain rate induced phase separation process is suggested as one of the explanations for this crystallization behavior. The strain-rate-dependent critical cooling rate must be considered in order to assess the intrinsic glass forming ability of metallic liquid

Nanoimprinting with Amorphous Metals

The random structure in amorphous metals (AM) is homogeneous down to the atomic length scale and results in highest strength and hardness, combined with other attractive properties as a structural material. Even more unique is the softening behavior of AM; they can be considered high strength metals that can be processed like plastics. Recently, we showed that some AM can massively replicate features as small as ~10 nm through direct embossing by utilizing favorable wetting conditions between the AM and the mold material. The unique softening behavior in combination with a wider range of softening temperatures, which span a range of 50 degrees C - 500 degrees C among AM provides a versatile toolbox for nanoimprinting. This includes the ability to use AM as a hard mold or, alternatively, a soft imprint material. This toolbox can be used for example in nanoimprint lithography where the robust AM would replace the fragile Si mold in the imprinting process. The low softening temperature of AM and the associate low strength permits to directly write onto the AM as in nano probe lithography. Furthermore, the ability to erase multiple times (103-104 times) features through the action of the surface tension alone before crystallization sets in, can be combined with direct writing and used for high density data storage

Crystallization kinetics of the bulk-glass-forming Pd43Ni10Cu27P20 melt

The crystallization of undercooled Pd43Ni10Cu27P20 melts is studied under isothermal conditions and at constant heating and cooling rates. Investigations are carried out by fluxing the melt with B2O3 and without any fluxing material. The isothermal experiments allow us to determine the complete time–temperature-transformation diagram with a minimum crystallization time of about 200 s for the fluxed melt and about 130 s for the unfluxed Pd43Ni10Cu27P20 melt. The results of the experiments at constant cooling and heating rates are summarized in a continuous heating and cooling diagram. The critical cooling rate for the fluxed alloy is determined to be 0.09 K/s, whereas the critical heating rate is 6 K/s. For the unfluxed Pd43Ni10 Cu27P20, 0.4 and 9 K/s are found, respectively. This alloy exhibits the most sluggish crystallization kinetics of all metallic systems known so far

Timescales of crystallization and viscous flow of the bulk glass-forming Zr-Ti-Ni-Cu-Be alloys

Crystallization behavior and equilibrium viscosity of a series of alloys in the Zr-Ti-Cu-Ni-Be system are studied using multiple techniques to determine the various contributions to glass-forming ability. Low-temperature time-temperature-transformation diagrams of alloys whose compositions lie at equally spaced points along the tie line from Zr38.5Ti16.5Cu15.25Ni9.75Be20 to Zr46.25Ti8.25Cu7.5Ni10Be27.5 are measured during isothermal annealing of initially amorphous specimens. Surprisingly, for all investigated alloys, a primary quasicrystalline phase forms at a rate which varies substantially with alloy composition. Subsequent constant heating measurements, x-ray-diffraction patterns obtained after various states of annealing, beam bending viscosity results, and previous thermal analysis are all used to describe the influences on crystallization in this series. The description of both the kinetic and thermodynamic aspects of crystallization allows for an explanation of the crystallization mechanism. In addition, it explains why, in this series, thermal stability is greatest in those alloys with the poorest glass-forming ability. Overall, the investigations reveal that simple criteria like thermal stability or high viscosity fail to predict the glass-forming ability in complex bulk glass-forming systems

Repeated crystallization in undercooled Zr41Ti14Cu12Ni10Be23 liquids

Isothermal crystallization studies are performed on Zr41Ti14Cu12Ni10Be23 melts. Undercooling experiments are carried out repeatedly at 907, 860, and 750 K. The scattering of the time to reach the onset of crystallization is investigated. Results from experiments performed at 907 K show a large scatter of the onset time of crystallization. For the experiments carried out at 860 and 750 K, scattering of the onset time is two orders of magnitude smaller. These results indicate that, at high temperatures, the crystallization is governed by the time scale of the statistical nucleation events. At low temperatures, the crystallization is controlled by diffusion, resulting in a well-defined onset time for crystallization

GIS-based modeling of land use systems - Common Agricultural Policy reform and its impact on agricultural land use and plant species richness

An assessment of agricultural policy measures and their sustainability needs to consider economic, social, and ecological aspects. The current paradigm shift of the European Union’s Common Agricultural Policy (CAP) from coupled to decoupled transfer payments calls for such an evaluation. Land users have to reevaluate their production program and its spatial allocation. Consequently, agricultural policy influences regional land use patterns and shares of land use systems, which in turn influence regional plant species richness. Connecting land use and ecological models allows to assess socioeconomic and ecologic effects of policy measures by identifying interactions and estimating potential trade-offs. The paper presents the land use model ProLand and the fuzzy expert system UPAL. ProLand models the regional distribution of land use systems while UPAL predicts plant species richness. The models are connected through a GIS and applied to a study area in Hesse, Germany, in order to simulate the effects of changing conditions on land use, economic and social key indicators, and plant species richness. ProLand is a spatially explicit comparative static model that simulates a region’s land use pattern based on natural, socioeconomic, political, and technological parameters. The model assumes land rent maximizing behavior of land users. It calculates and assigns the land rent maximizing land use system for every investigated decision unit, generally a field. A land use system is characterized through crop rotation, corresponding outdoor operations, animal husbandry if applicable, and the relevant political and socioeconomic attributes. The fuzzy expert system derives the values of ecologically relevant parameters from several site specific attributes and land use operations. Land use dependent site characteristics that influence plant species richness are derived from predictions generated by ProLand. Detailed information on crop rotation, fertilization and pesticide strategy, and outdoor operations are considered. The expert system then classifies natural and land use dependent site characteristics into aggregate factors. Based on a set of rules it assigns the number of species to the classes and thus to the decision units. Simulation results for the study area show that the CAP reform causes a rise in grassland area. These land use changes mainly occur in areas currently used for arable farming but with natural conditions favoring grassland. Plant species richness is positively influenced by the increase in extensive grassland area.