When a glassy material or its liquid state is subjected to sufficiently high pressure, significant changes can take place in the short- and medium-range structure, vibrational density of states, and physical properties. It is crucial to determine and understand the structure-property relations under high pressure from both scientific and technological perspectives, since the glass structures frozen-in under elevated pressure may give rise to properties unattainable under ambient pressure. However, the structural and topological origins of the pressure-induced changes in macroscopic properties are not yet well understood. Here, we address this problem by subjecting various isostatically compressed glasses to isothermal annealing at ambient pressure and monitor the relaxation of glass structure and properties as a function of time and temperature. For different glass systems, density is found to relax in a stretched exponential manner with an exponent close to the Phillips value of 3/5 for relaxation in three dimensions when both short- and long-range interactions are activated [1]. For a compressed soda lime borate glass, we find that upon annealing at 0.9T_g, the pressure-induced increase in boron coordination remains unchanged, while the pressurized values of macroscopic properties such as density, refractive index, and hardness are relaxing [2]. Hence, the pressure-induced changes in macroscopic properties are not necessarily attributed to changes in the short-range order in the glass, but rather to changes in overall atomic packing density and medium-range structures. Moreover, we show that the relaxation mechanism depends on the annealing temperature and different physical properties (e.g., density and hardness) are found to relax on different timescales. [1] M. M. Smedskjaer, S. J. Rzoska, M. Bockowski, J. C. Mauro, Journal of Chemical Physics140, 054511 (2014). [2] M. M. Smedskjaer, R. E. Yougnman, S. Striepe, M. Potuzak, U. Bauer, J. Deubener, H. Behrens, J. C. Mauro, Y. Z. Yue, Scientific Reports4, 3770 (2014).

This talk reports on two interesting new phenomena recently discovered in glasses.
The first part of the talk will discuss the elastic properties of vitreous silica submitted to high pressures in a diamond anvil cell. We show that the compressibility of a silica sample immersed in helium or neon fluid is much smaller than expected from its elastic properties measured by Brillouin light scattering. It results from gas atom penetration into the interstitial free volume of the glass network. This adsorption-induced expansion can be described by a generalized poromechanical model. The second part of the talk will address the long-standing question of the nature of the glassy state. It is commonly believed that far below the glass transition temperature, dynamics in glasses is frozen, i.e. relaxations occur on time scales too large to be observed. X-rays photon correlation spectroscopy is used to reveal the existence of surprisingly fast atomic rearrangements in a sodium silicate glass, even at room temperature. These results challenge our conception of the glassy state and call for a new microscopic theory.
References:
(1) C. Weigel, A. Polian, M. Kint, B. Rufflé, M. Foret, and R. Vacher, Vitreous Silica Distends in Helium Gas: Acoustic Versus Static Compressibilities, Phys. Rev. Lett. 109, 245504 (2012).
(2) B. Coasne, C. Weigel, A. Polian, M. Kint, J. Rouquette, J. Haines, M. Foret, R. Vacher, and B. Rufflé, submitted.
(3) B. Ruta, G. Baldi, Y. Chushkin, B. Rufflé, L. Cristofolini, A. Fontana, M. Zanatta, and F. Nazzani, Revealing the fast atomic motion of network glasses, Nat. Commun. 5, 3939 (2014).

The constituents of any network glass can be broadly classified as either network formers or network modifiers. Network formers, such as SiO₂, Al₂O₃, B₂O₃, P₂O₅, etc., provide the backbone of the glass network and are the primary source of its rigid constraints. Network modifiers play a supporting role, such as charge stabilization of the network formers or alteration of the network topology through rupture of bridging bonds and introduction of floppy modes. The specific role of the modifiers depends on which network formers are present in the glass and the relative free energies of modifier interactions with each type of network former site. This variation of free energy with modifier speciation is responsible for the so-called mixed network former effect, i.e., the nonlinear scaling of property values in glasses having fixed modifier concentration but a varying ratio of network formers. In this talk, a general theoretical framework is presented describing the statistical mechanics of modifier speciation in mixed network glasses. The model provides a natural explanation for the mixed network former effect and also accounts for the impact of thermal history and relaxation on glass network topology.

The development of effective new tools for structural characterization of disordered materials and systems is becoming increasingly important as such tools provide the key to understanding, and ultimately controlling, their properties. The relatively novel technique of correlograph analysis (i.e. the approach calculating angular autocorrelations within diffraction patterns) promises unique advantages for probing the local symmetries of disordered structures. Because correlograph analysis examines a component of the high-order four-body correlation function, it is more sensitive to medium-range orders than conventional diffraction methods. Generally, electron correlograph analysis would be implemented in a transmission electron microscope (TEM) operating in the STEM mode where a nanoscale probe can be controllably created and translated to regions of interest on the specimen. It can be primarily used for characterizing local diffraction symmetry of disordered solid materials, such as amorphous semiconductors, oxides, and metallic glasses. Like fluctuation electron microscopy, electron correlograph analysis is a statistical method, replying on a sufficiently large sampling to distinguish between random and truly persistent structural correlations. The Friedel correlation in the mean electron correlograph unveils the crystallinity of samples with medium-range orders, an important structural parameter that cannot be measured by other techniques. In the presentation, I will describe the practical experimental method and common systematic errors of electron correlograph analysis. First, I will discuss the effects of beamstop, diffraction center locating, and distortions on the electron correlograph analysis. Second, by using both experimental data and numerical simulations, I will elucidate why those seemingly real correlations showing up in one or a few correlographs do not actually reflect the local symmetries of disordered structures, and emphasize that reliable structural information about the sample can only be obtained from the mean correlograph, which is averaged over results from an adequate number of individual diffraction patterns (typically > 50).

I will review our previous work in B₂O₃ glass [1,2] as well as its recent extensions in the liquid phase and in other systems. Using ab-initio simulations, we predicted new low-density crystalline polymorphs [1] which provide a framework to understand the glass properties [2]. Thanks to NMR, the new crystals are shown to be structurally much more similar to the glass than is any of the known polymorphs. Some possible routes to synthetise these crystals will be mentionned. I will also discuss the implications of these findings for the liquid behavior. In particular, the possible existence of a liquid-liquid transition, much similar to that hypothetized in water will be raised.
[1] G. Ferlat et al., Nature Materials, 11, 925 (2012)
[2] G. Ferlat et al., Phys. Rev. Lett., 101, 065504 (2008)

Amorphous transparent conducting oxides (TCO) are of considerable technological interest due to their unusually high electron mobilities, excellent optical properties, wide thermal stability and ease of processing. Significant progress has been made regarding the synthesis and optimization of these thin films (notably Zn and Sn-doped In₂O₃) for a wide range of applications. However, the structural changes upon doping as well as the exact role played by the short and intermediate-range order in defining their valuable optical and electronic properties is still lacking. This knowledge is desirable as it can be leveraged to direct research efforts towards other materials more abundant than Indium, or even point towards compounds hitherto unexplored. Short-range order (typically < 5Å) can be obtained through analysis of extended x-ray absorption fine structure (EXAFS) data which yields a partial structure function centered on the absorber atom. A complementary technique yielding structural information on longer length-scales, i.e. medium-range order, is to analyze the complete pair distribution function (PDF) obtained from total X-ray scattering data. Essentially, total scattering data is the properly corrected and normalized elastic scattering i.e. I(Q) vs. Q, where Q is the scattering vector. The PDF is a real-space distribution of atoms obtained through an appropriately weighted Fourier transform of this function. Taken together, EXAFS and PDF data contain important structural information such as bond distances, bond angles, coordination numbers and structural coherence lengths which are otherwise challenging to access in poorly ordered materials. In this study, we analyze EXAFS and grazing-incidence PDF data on amorphous In-Zn-O films with varying In:Zn ratios. Samples of a given composition but possessing significantly different electronic conductivities displayed only subtle changes in both XAS and PDF data. Further, the PDF data show clear ordering up to almost 3 nm indicating that the films are not truly amorphous. These observations have implications for both theoretical and experimental studies and will be discussed along with other structural insights on the In-Zn-O thin films with the broader aim of arriving at a better understanding of the short and medium-range order in amorphous TCO materials.

Drawing inspiration from nature, where some organisms can control the short-range order of amorphous minerals, we successfully manipulated the short-range order of amorphous alumina by surface and size effects. By utilizing the Atomic Layer Deposition (ALD) method to grow amorphous nanometrically thin films, combined with state-of-the-art electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS), we show experimentally that the short-range order in such films is strongly influenced by size. This phenomenon is equivalent to the well-known size effect on lattice parameters and on the relative stability of different polymorphs in crystalline materials. Additionally, direct measurements of crystallization temperature have shown a dramatic increase in amorphous to crystalline phase transition temperature for thinner amorphous Al₂O₃ films. Finally, we show that the short-range order changes while still in the amorphous phase, before the amorphous to crystalline transformation takes place.
¹ Leonid Bloch, Yaron Kauffmann, and Boaz Pokroy. Crystal Growth & Design. In press 2014.

Originally, rigidity in glasses was formulated by J.C. Phillips in order to understand the relationship between cooling speed, which measures glass formation ability, and chemical composition. Although in the last years much of this picture has been confirmed by many experiments and simulations, still it is not clear how minimal cooling speed depends on the composition. Here a simple model is provided in which two key ingredients are considered in the glass, metastable states and their multiplicity. Metastable states are considered as in two level system models. However, their multiplicity and topology allows a phase transition in the thermodynamic limit, while a transition to the glass is obtained for fast cooling. By solving the corresponding master equation, the minimal speed of cooling required to produce the glass is obtained as a function of the distribution of metastable and stable states. This allows to understand cooling trends due to rigidity considerations in chalcogenide glasses as in metallic glasses doped with group IV impurities, like the Pd-Ni-P-Si compound.

We report that the properties of metallic glasses can be dramatically tailored by slow deposition at high temperatures without altering chemical composition. The glass transition and crystallization temperatures of the metallic glass can be increased as high as 83 K and 269 K, respectively, compared to the room-temperature deposited one and melt-spun ribbons. The high-temperature deposited glass also shows ultrahigh hardness, over 60 % higher than room-temperature deposited glass. Atomic structure characterization reveals that the exceptional properties of the high-temperature glasses are associated with abundance of medium range order contains mainly distorted icosahedral order with partially cubic symmetry. The finding of the high-temperature deposited glass gives insight on atomic mechanisms of metallic glass formation and has important impact on the technological applications of metallic glasses.

That shear causes dilatation in densely packed granular systems has been known and studied since the days of Osborne Reynolds (1885). A similar effect occurs in dense packings of hard spheres, which are a useful analogues of metallic glasses. It is now possible to follow this process directly in colloidal hard-sphere glasses, by tracking the invidual particles by confocal microscopy. In dense hard-sphere systems, the moduli are strong functions of the density (they diverge at close packing). These moduli can be measured from the thermal distribution of the local strain energy densities. These measurements show a decrease in the shear modulus (and hence density) upon plastic shear deformation, and a relaxation back to the initial state after the deformation stops. Microscopic mechanisms for these density changes as well as their implications for strain softening and shear instabilities in metallic glasses will be discussed.

Owing to the high cooling rates necessary for glass formation in metallic glasses, parts with a complex geometry have been difficult to cast directly. The metallic glasses' remarkable softening behaviour above the glass transition temperature T_g has led many to suggest, then develop, thermoplastic forming as an alternative manufacturing method for complex parts. Cerium-based BMGs, exhibiting very low T_g as well as a large supercooled liquid region (SCLR), provide an excellent platform on which to study such thermoplastic forming. In order to investigate and develop new thermoplastic forming processes, the SCLR of these alloys must first be appropriately characterised. Heating rate, processing temperature, and strain rate have been examined; their effects on viscosity, flow, and devitrification explored; and the results and conclusions are hereby reported.

Many materials have a high propensity to crystallize as this is the energetically most favorable state; it is thus difficult to make these materials amorphous. However, for certain applications, it would be highly beneficial to make these materials amorphous as many of their physicochemical properties differ from those of their crystalline couterparts. For example, amorphous materials have a much higher solubility than crystalline ones. I will present a microfluidic spray drier, we call it a microfluidic nebulator, that produces very small drops through the use of supersonic air. These small drops serve as containers to form small amorphous nanoparticles; the size of these nanoparticles is determined by the number of solute molecules contained in the drop. The nanoparticle structure is determined by the probability for a crystalline nucleus to form as the drop evaporates; this probability is typically very high in supersaturated solutions as crystalline solids readily form under these conditions. However, the formation of a crystalline nucleus itself entails some time delay. We demonstrate that the nebulator can kinetically suppress the formation of crystalline nuclei; thereby, it produces amorphous nanoparticles from many different materials, even from materials that have a very high propensity to crystallize.

One of the most intriguing issues in supercooled liquids and glassy materials is their dynamic relaxation behaviors, which underlies their physical and mechanical properties. Recently, Yu et al. found that the b-relaxations in metallic glass-forming liquids is sensitive to the chemical interactions among all the constituent atoms. In other words, b-relaxations in metallic glasses are linked to a large mixing enthalpy for the atoms.
We use mechanical spectroscopy to investigate the mechanical relaxation (a and b relaxations) in several typical bulk metallic glasses in isochronal route as well as isothermal mode: Pd-Ni-Cu-P, La-Ni-Cu-Al and Cu-Zr-Al-Dy systems. We investigated the dependence of the mechanical relaxation on the physical aging to study the evolution of the localized atomic mobility with the physical aging. The pronounced JG b relaxations in metallic glasses are associated to large negative values of the enthalpy of mixing among the constituting atoms, these results are in good agreement with the recent report by Yu et al.

Resistive switches offer the prospect of improved performance, efficiency and scalability over current data storage methods. Many device architectures have been proposed, reliant upon a wide variety of materials whose conductance switches in a non-volatile manner with the application of an applied field. Silicon-based switching materials are of particular interest in these devices as they offer the added potential for integration into existing CMOS infrastructures. It is of great importance that the underlying physics of switching is well-understood, such that device optimisation and integration into commercial hardware may be realised. Our device layers are sputter-deposited to create a 37nm thick, amorphous, non-stoichiometric silicon-rich layer of silica sandwiched between conductive electrodes. We report on the material changes leading to reversible resistive switching in silicon suboxide using secondary ion mass spectroscopy (SIMS), x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and conductive atomic force microscopy (cAFM). Analysis with a range of techniques serves to highlight the broad dynamics of device behaviour, and supports the model of an ionic and defect-dependent switching mechanism which relies upon the presence of nanoscale grain boundaries within the amorphous silica switching layer.

Our recent research accomplishments led us believe that Ga substitution on Al sites need not permit it to remain in trivalent state only. The monovalent Ga atom, has atomic radius is greater than that of trivalent one. In contrast, pentavalent state of Ga has atomic radius smaller than that of trivalent one. The change of valency of Ga in metallic glass composition will lead to change in geometry of main cluster that promotes glass forming ability of the melt. Further, the mixed states of Ga may facilitate formation of clusters of different types leading to phase separation in the melt and thereby in metallic glasses. Keeping these in mind we have recently investigated two such compositions. They refer to Zr_69.5Al_7.5minus;xGa_xCu₁₂Ni₁₁ and Ce₇₅Al_25-xGa_x metallic glass compositions. The purpose of this presentation will be to bring out aforesaid features after Ga substitution on the nature of glass forming ability based on our studies on these alloy systems.
The first part of the presentation deals with the behavior of Zr_69.5Al_7.5minus;xGa_xCu₁₂Ni₁₁ (x = 0, 1.5, 7.5 at.%) alloys. A comparison between their nanohardness and reduced elastic modulus values of the as-synthesized glassy phase with their nanocomposites has been made. The indentation characteristics of a novel Ga substituted glass composition corresponding to x = 7.5 have shown significant improvement in regard to hardness and elastic modulus. The evidence of pile up has been observed in case of as-synthesized glassy ribbons. The load (P) versus depth (h) curves for as-synthesized melt-spun ribbons displayed the presence of displacement burst, which are known as pop-ins. The amount of energy per unit volume required for the shear band formation in glassy state has been estimated based on the pop-ins observed in P-h curve. This seems to decrease with Ga addition. Based on transmission electron microscopic observations of indented glassy specimen, the possibility of nanocrystallization has been ruled out.
The glass forming ability and indentation characteristics of melt-spun Ce₇₅Al_25-xGa_x (x = 0, 2, 4 and 6 at.%) metallic glasses will also be presented. The substitution of Ga decreases the glass transition temperature, while increases the supercooled liquid region. The small amount of Ga substitution has led to appearance of second diffuse halos in the X-ray diffraction (XRD) pattern. The observation of phase separation is thus asserted. The transmission electron microscopic images led us to conclude the formation of nano-amorphous domains after Ga substitution in a glassy matrix. The load dependent hardness behaviour of metallic glasses with and without Ga substitution has been studied. The substitution of Ga improves the microhardness property of Ce-Al alloy. The formation of shear bands around the indentation periphery has been observed. The value of yield strength and Meyer exponent of these alloys has been compared.

We investigate the crystallization of an amorphous eutectic Ni-P alloy, fabricated by electroless deposition as a 10 um thick continuous layer. The purpose of this work is to obtain a detailed understanding of the microscopic mechanisms of crystallization and phase formation upon heating. To this end, we combine a variety of complimentary characterization techniques. DSC (differential scanning calorimetry) during isothermal and isochronal heating reveals the crystallization kinetics. XRD (X-ray diffractometry) provides quantitative information on phase composition as a function of tempering time. Conventional-, high-resolution-, and analytical TEM (transmission electron microscopy) and TEM-based electron diffraction provide high-spatial-resolution information on phase nucleation and spatial distribution of atom species, particularly the crystallography of the nucleating crystalline phases (Ni3P and Ni) and the spatial distribution of phosphorus in the partially and completely crystallized alloy. Our results confirm earlier observations, according to which crystallization proceeds by formation of barrel-shaped grains. Internally, these exhibit a radial microstructure of of slightly misoriented subgrains of Ni3P containing Ni needles with unique ORs (orientation relationships) to Ni3P. However, the preferred Ni-Ni3P ORs we observe differ from those reported in the literature. Combining our observations on the structure and microstructure of partially and completely crystallized Ni-P with the observed crystallization kinetics leads to a new model for the microscopic mechanism of crystallization. This may be useful for understanding the effect of ternary alloying elements on the crystallization behavior and temperature.

V-Zr amorphous thin films potentially have a number of applications as coatings for components subject to aggressive chemical and physical conditions. In this work V-Zr thin films were produced by magnetron sputtering at room temperature and were subsequently characterized and modelled; using atomic scale techniques, to understand the alloys&’ stability and the relationship the amorphous material has to the crystalline Zr, V and V₂Zr phases.
Atomic scale modelling using density functional theory was used to investigate three compositions in the V-Zr system: equimolar VZr, the V rich V₂Zr and Zr rich VZr₂ compositions. Amorphous supercells were created and minimised under constant pressure with a variety of starting densities and supercell sizes. We find that the simulation conditions are pivotal in reproducing the experimentally observed structure. Bulk X-ray diffraction techniques were used as a first check to compare experiment and theory with encouraging results.
Ensembles of electron nanodifraction patterns were collected from the three formulations of amorphous V-Zr films. The electron beam was tuned to the diameter of the nearest-neighbour clusters. In this geometry, and collecting diffraction patterns from sub-4 nm thick regions, angular correlations in the diffraction patterns reflect the symmetries of nearest-neighbour polyhedra. [1] An angular autocorrelation technique was used to quantify the statistical incidence of symmetries in the diffraction patterns of each specimen as a function of the scattering angle. It was found that the symmetries in the diffracted intensities from all the films could not be explained by BCC local ordering alone, but required the presence of more complex intermetallic local ordering, such as the C15 Laves phase (V₂Zr). The experimental data matched simulations from the amorphous supercells.
[1] A. C. Y. Liu, M. J. Neish, G. Stokol, G. A. Buckley, L. A. Smillie, M. D. de Jonge, R. T. Ott, M. J. Kramer, and L. Bourgeois, Phys. Rev. Lett., 110, 205505 (2013)

The stability of undercooled liquids against crystallization is affected by initial viscosity of the stable liquids, viscosity change of the melt due to temperature drop, free energy difference between undercooled liquids and crystalline phases, liquid/solid interface energy, bulk density, non-uniform nucleation, cooling rate of particle and so many other factors. If the cooling rate is fast enough that diffusion among the atoms is limited, the amorphous phase is uniformly solidified. This behavior is called glass transition behavior, and several metallic alloys with such behavior have been discovered, which can be vitrified with only radiative cooling. For example, containerless high-temperature/high-vacuum electrostatic levitation (ESL) technique, which could minimize heterogeneous sites, is useful for investigation of the undercooled liquid behavior. In particular, several high glass-forming alloys, whose cooling rate is fast enough that diffusion among the atoms is limited, can be vitrified with only radiative cooling in these ESL. In this study, we measured the thermo-physical properties and Time-Temperature-Transformation (TTT) diagram for the crystallization of various amorphous metal system from liquid temperature to glass transition temperature, using ESL technique. After that, we analyzed atomic scale structural change of the samples with high energy X-ray scattering experiments to understand the influence of compositional change on glass-forming ability. Indeed, these results could provide a clear understanding of the exceptional stability against crystallization in amorphous metal based on kinetic, thermodynamic and structural principles. Undercooled liquids&’ thermophysical properties and their own structure variation have a pronounced influence on the glass forming ability and knowledge on it is essential in understanding more precisely the crystallization mechanism of amorphous metal.

Recently, by using the techniques of HREM, HAADF and EDX line mapping, it [1] was found that Pd-Ni-P bulk metallic glasses (BMGs) undergo amorphous phase separation (APS). Later, by using small angle X-ray scattering method, it [2] was confirmed that the observed APS is consistent with a spinodal mechanism. It is not clear, however, why Pd-Ni-P BMGs, an alloy system of negative heat of mixing, undergo amorphous spinodal decomposition (ASD). In this work, we attempt to measure the metastable liquid miscibility gap by employing the same technique as described in [1].
[1] S. Lan, Y.L. Yip, M.T. Lau, H.W. Kui, J. Non-Crystalline Solids 358 (2012) 1298-1302.
[2] Z.D. Wu, X.H. Lu, Z.H. Wu, H.W. Kui, J. Non-Crystalline Solids 385 (2014) 40-46.

A key challenge for understanding plasticity in amorphous materials is the link between microscopic (i.e., atomistic) and macroscale behaviour (i.e., the scale of the sample). To establish this link, it is useful to coarse-grain the microscopic details and construct a mesoscopic model which tries to capture important aspects from the atomistic scale without fully resolving the atomic motions, being thus computationally efficient. The common approach taken in mesoscale descriptions of amorphous plasticity is to consider plastic activity as a sequence of spatially and temporally localized events, known as shear transformations, which correspond to local rearrangements of atoms within the bulk material in response to the locally acting shear stress. This rearrangement in turn induces an internal (eigen-) stress field which - together with external stresses - determines the spatial and temporal pattern of shear transformation events which characterizes the plastic deformation dynamics of the amorphous structure. We present a mesoscale approach to amorphous plasticity based on a finite element framework with quasistatic, athermal dynamics analogous to lattice based models proposed in the literature, which use the (periodically continued) elastic Green's function of an infinite body to calculate internal stresses in systems with periodic boundary conditions.
The tensorial finite element formulation allows us to analyze a rich variety of collective phenomena such as strain localization and strain avalanches, comparing and benchmarking our results against the established lattice models. The main advantage of the finite element method over these models is that the FEM approach provides natural access to analysing the effects of surfaces and boundary constraints, and hence to physical mechanisms leading to finite size effects which cannot be captured by models which employ periodic boundary conditions. We analyse the results for the deformation behavior of 2D amorphous specimens under non-trivial loadings, such as shear or bending, and analyse the influence of strain gradients, surfaces, and finite size effects. We find that we can conceptually envisage systems with free surfaces as consisting of two distinct regions: an interior “bulk-like” domain where plastic activity evolves essentially as observed in a periodic system, and another “surface-dominated” domain where the interactions between shear transformations are suppressed and deformation behaviour is controlled by surface constraints and external tractions. We quantitatively analyse the deformation behaviour arising from the interplay of surface and bulk (statistical) size effects in 2D and present some preliminary results for 3D specimens.

Deformation of ductile crystalline-amorphous nanolaminates is not well understood due to the complex interplay of interface mechanics, shear banding and deformation-driven chemical mixing. Here we present indentation experiments on 10 nm nanocrystalline Cu / 100 nm amorphous CuZr model multilayers to study these mechanisms down to the atomic scale. By using correlative atom probe tomography and transmission electron microscopy we find that crystallographic slip bands in the Cu layers coincide with non-crystallographic shear bands in the amorphous CuZr layers. Dislocations from the crystalline layers drag Cu atoms across the interface into the CuZr layers. Also, crystalline Cu blocks are sheared into the CuZr layers. In these sheared and thus Cu enriched zones the initially amorphous CuZr layer is rendered into an amorphous plus crystalline nanocomposite.

The alloy system, Pd-Ni-P, has a negative heat of mixing. It is therefore somewhat surprising that Pd-Ni-P bulk metallic glasses (BMGs) undergo amorphous phase separation (ASD) [1, 2]. An attempt has been made to measure the metastable liquid miscibility (MLMG) of undercooled molten Pd-Ni-P. In this work, X-ray diffraction method is employed to characterize undercooled specimens that have entered into the MLMG.
[1] S. Lan, Y.L. Yip, M.T. Lau, H.W. Kui, J. Non-Crystlline Solids 358 (2012) 1298-1302.
[2] Z.D. Wu, X.H. Lu, Z.H. Wu, H.W. Kui, J. Non-Crystalline Solids 385 (2014) 40-46.

A novel method is introduced to determine notch toughness of bulk metallic glasses (BMGs). Through thermoplastic forming of BMGs combined with Si photolithography, unprecedented control in fabricating BMG notch toughness samples can be achieved and many extrinsic influences (e.g., cooling rate, casting defects) can be drastically reduced. Our approach allows us to precisely vary the notch root radius with a high precision of ~ 1 mu;m. In order to systematically study the effect of notch root radius on the notch toughness of BMGs, notches with a broad range of radii from 3 mu;m to 380 mu;m are introduced into the test specimens. Through this method, we have fabricated ~ 100 samples with different notch radii (ρ = 3, 10, 25, 50, 100, 150, 230, 380 mu;m) in two different BMG systems, i.e., Zr₄₄Ti₁₁Cu₁₀Ni₁₀Be₂₅ and Pd₄₃Cu₂₇Ni₁₀P₂₀ BMGs. We found that there exists a critical notch radius, ρ_c, above which the apparent notch toughness scales linearly with ρ^1/2. With decreasing notch radius below ρ_c, the notch toughness retains almost constant rather than degrading. However, this critical notch radius varies in the two different investigated BMGs that exhibit distinct toughness behavior. Such observed phenomenon can be well explained within the framework of characteristic critical distance theory and is similar to previously reported for crystalline metals, ceramics, and polymers, although the mechanistic origins are different. Our finding also suggests that BMGs can be highly tolerant to sharp flaws.

The presence of minute crystalline phases in metallic glasses is unfavorable for the reliable understanding of the intrinsic properties of the bulk metallic glasses(BMG) [1]. However, the detail of the sample characterization has often been omitted in the literature. In this study, the amorphous state of the Zr-Al-Cu-(Ni,Fe) BMG are thoroughly investigated using high intensity 50mu;m X-ray beam with a 2-dimensional detector in order to probe possible existence of minute crystalline phases that are not detectable by conventional X-ray equipments. So far, the results have shown that a small amount of crystalline phases exists in the cross section of most of the Zr-based BMG that were prepared in a conventional method. Experiments are currently being undertaken to fabricate Zr-based BMG without minute crystalline phases to perform further measurements such as mechanical properties. The detail of the results will be presented at the poster.
[1]Q.S Zhang et al. Acta Materialia 58 (2010)904-909

It is generally assumed that the glass transition temperature, T_g, of a bulk metallic glass, BMG, is only a shallow function of the composition. We give evidence for several metallic glasses derived from quarternary (Pt+TM)₆₆B₂₄(Si+Ge)₁₀ systems exhibiting strong changes of T_g (from 570 K to 650K) with varying the type of TM(=transition metal) used, resulting in virtually unchanged reduced glass transition temperature over a wide range of compositions.
The access to a wide range of T_g with minor levels of substitution opens the door to investigate whether the T_g can be shifted with regard to the critical fictive temperature, T_fc, or whether the latter stays put relative to the T_g. As proposed by Kumar et al.¹, the relative position of these two temperatures essentially defines whether a BMG will be ductile, brittle or cooling-rate sensitive in its mechanical behavior.
We further present mechanical properties derived from 3-point bending test, microhardness and elastic constants from elastic wave measurements.
1. Kumar, G., Neibecker, P., Liu, Y. H. & Schroers, J. Critical fictive temperature for plasticity in metallic glasses. Nat. Commun.4, 1536 (2013).

Mechanical properties in nano-sized metallic glasses have been widely investigated to clearly understand the fundamental deformation mechanism of metallic glasses. In particular, the change of yield strength and the occurrence of deformation mode transition (heterogeneous to homogeneous) with sample size reduction have been reported in previous experimental studies through the nano-pillar test results. Research on nano-mechanical responses of metallic glasses could lead to an in-depth understanding of the deformation mechanism related to the nucleation and propagation of shear bands. However, during the pillar fabrication using focused ion beam for nano-pillar test, Ga+ ion beam damage on pillar surface is difficult to avoid and the fabrication takes relatively long for multiple pillar preparations. To avoid these drawbacks of nano-pillar tests, in the present study we performed nano-compression tests of metallic glass nanoparticles prepared by FIB-less method. In our experiments, metallic glass nanoparticles have been fabricated by the selective dissolution technique from phase separated metallic glasses. From the two-amorphous alloys with droplet structure, the reactive matrix phase has been selectively dissolved by chemical process. The shape of the remaining particle phases was clearly spherical, and the sizes of fabricated particles have distribution in 40~500 nm diameter range. The effect of particle size and strain rate on mechanical properties of fabricated amorphous particles has been investigated from the compression test using in-situ compression tester with electron microscope imaging. Due to the distinct morphology of particles compared to that of nano-pillars, the stress-strain relations from particle compression test results are derived based on contact mechanics theory and contact area calculation. From the stress-strain curves and in-situ electron microscope video, we confirmed the metallic glass nanoparticles are not fractured at high strain over 50% and have favorable condition for homogenous-like deformation at strain rate near ~10^-3 s^-1 based on modified Griffith criterion. These results provide us with insights on evaluation of nano-mechanical properties and understanding of fundamental deformation mechanism of metallic glasses.

It is well known that applications of bulk metallic glasses (BMGs) for structural materials are limited by their brittleness in spite of desirable mechanical properties such as high yield strength, high elastic limit, and relatively low elastic modulus. To overcome this drawback, various composite microstructures with structural heterogeneity of micrometer to nanometer scale in the amorphous matrix have been developed. The heterogeneity can result in nucleation of multiple shear bands and interruption of their propagation, which can lead to enhanced plasticity. In the present study, in order to precisely control the amorphous heterogeneities or amorphous 2nd phases in the amorphous matrix, thermally activated growth behaviors of secondary amorphous phases in Cu-(Zr,Hf)-Al-(Y,Gd) phase separating metallic glasses have been investigated using in-situ heating SAXS experiment and additional intensive structural analysis. From the combination of two ternary systems, Cu-(Zr,Hf)-Al and Cu-(Y,Gd)-Al, phase separating metallic glasses with two distinct amorphous phases were fabricated in Cu-(Zr,Hf)-Al-(Y,Gd) quaternary system. Experimentally, the growth behavior of secondary amorphous phase was investigated by SAXS analysis at elevated temperature near first T_g and T_x. Also, the chemical composition of 2nd phase was evaluated using alloy contrast variation (ACV) method from comparison of SAXS/SANS patterns of various alloy compositions. From the results, the relationship between the composition/size of 2nd phases and the mechanical properties in the phase separating metallic glasses was analyzed. This provides us with a fruitful idea on how to control the properties of metallic glass composites from manipulating the 2nd phases in nanometer scale.

A structural amorphous metal (SAM) containing 0 to 30 vol% of W nanoparticles was tested by several techniques, including micro-bending tests. The density values reached up to 10.98 g/cc with the addition of W nano particles. Nanoindentation tests were performed in order to study the compositional effects on the hardness and modulus. Indentation mapping results show a significant increase in hardness values in the areas surrounding the W particles. Extensive analysis was performed around the nanoparticles in order to study if and how the nanoparticles could aid in crack deflection and improve the fracture toughness.

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