Our earlier Monte Carlo simulations of metastable supercooled-liquid and glass phases of Lennard-Jones atoms found several distinct signatures for identifying the glass transition boundary; i.e., the density, enthalpy, and pair distribution function dependences on temperature and pressure are different for the two phases (F. F. Abraham, J. Chem. Phys., 72, 359 (1980)). In this extension of that study, we base our analysis on the Ackland-Jones (A-J) method for determining the local crystal packing about each atom (G. Ackland & A. Jones, PRB 73, 054104 (2006)). It focuses on the angular distribution of the local atoms surrounding each individual atom and compares it with the known FCC, HCP, BCC, icosahedron packings within a specified uncertainly from perfect packing. Remarkably, the A-J method to our simulated glass states indicates that the local atomic packings of the individual atoms are predominantly crystalline; i.e., quasi FCC, HCP or BCC.
Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear…
Glass transition and random packing in the hard sphere system have attracted great attention due to the important role of the system in the investigation of diverse real systems including liquids, colloidal dispersions, supercooled liquids, glasses and granular materials (1-12) Despite the importance and simplicity of the system, some fundamental questions, such as the existence of an ideal glass transition (5-16), the nature of the glass transition and random packing (or jamming), and the entropy crisis or Kauzmann paradox (17,18), remain open. Based on a very accurate equation of state over …
Computer simulations suggest that ultrathin metal wires should develop exotic, non-crystalline stable atomic structures, once their diameter decreases below a critical size of the order of a few atomic spacings. The new structures, whose details depend upon the material and the wire thickness, may be dominated by icosahedral packings. Helical, spiral-structured wires with multi-atom pitches are also predicted. The phenomenon, analogous to the appearance of icosahedral and other non-crystalline shapes in small clusters, can be rationalized in terms of surface energy anisotropy and optimal packi…
The crystalline garnet Mn3Fe2Si3O12 and an amorphous phase of the same nominal composition are synthesized at high pressure. The magnetic properties of the two forms are reported. Both phases order antiferromagnetically. The crystalline phase exhibits a Curie-Weiss theta of -47.2 K, with a sharp ordering transition at 12 K. The glassy phase exhibits a larger antiferromagnetic Curie-Weiss theta, of -83.0 K, with a broad ordering transition observed at 2.5 K. Both phases can be classified as magnetically frustrated, although the amorphous phase shows a much higher degree of frustration. The amor…
Although the concept of random close packing with an almost universal packing fraction of ~ 0.64 for hard spheres was introduced more than half a century ago, there are still ongoing debates. The main difficulty in searching the densest packing is that states with packing fractions beyond the glass transition at ~ 0.58 are inherently non-equilibrium systems, where the dynamics slows down with a structural relaxation time diverging with density; hence, the random close packing is inaccessible. Here we perform simulations of self-propelled hard spheres, and we find that with increasing activity …
We perform molecular dynamics simulations to compress binary hard spheres into jammed packings as a function of the compression rate $R$, size ratio $α$, and number fraction $x_S$ of small particles to determine the connection between the glass-forming ability (GFA) and packing efficiency in bulk metallic glasses (BMGs). We define the GFA by measuring the critical compression rate $R_c$, below which jammed hard-sphere packings begin to form "random crystal" structures with defects. We find that for systems with $α\gtrsim 0.8$ that do not de-mix, $R_c$ decreases strongly with $Δϕ_J$, as $R_c \s…
Transparent SrO-0.5Li2O-4.5B2O3 (SLBO) and BaO-0.5Na2O-4.5B2O3 (BNBO) glasses were fabricated via the conventional melt-quenching technique. The amorphous and glassy characteristics of the as-quenched samples were respectively confirmed by X-ray powder diffraction (XRD) and Differential Thermal Analysis (DTA) studies. Optically clear SLBO and BNBO glass nano/microcrystal composites were obtained by heat-treating the as-quenched glasses slightly above their respective glass transition temperatures. These glass nano/microcrystal composites exhibited second harmonic signals in transmission mode w…
Despite two decades of studies, the formation of metallic glasses, very promising systems for industrial applications, still remains mostly unexplained. This lack of knowledge hinders the search for new systems, still performed with combinatorial trial and error. In the past, it was speculated that some sort of "confusion" during crystallization could play a key role during their formation. In this article, we propose a heuristic descriptor quantifying such confusion. It is based on the "thermodynamic density of competing crystalline states", parameterized from high-throughput ab-initio calcul…
We develop the theory of the coupling between in-plane order and out-of-plane geometry in twisted, two-dimensionally ordered filament bundles based on the non-linear continuum elasticity theory of columnar materials. We show that twisted textures of filament backbones necessarily introduce stresses into the cross-sectional packing of bundles and that these stresses are formally equivalent to the geometrically-induced stresses generated in thin elastic sheets that are forced to adopt spherical curvature. As in the case of crystalline order on curved membranes, geometrically-induced stresses cou…
Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a "hidden" polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Ad…
The lifetime of most metals is limited by cyclic loads, ending in fatigue failure. The progressive growth of cracks ends up in catastrophic failure. An advanced method is presented for the determination of cyclic crack growth on the microscale using a nanoindenter, which allows the characterization of > 10,000 loading cycles. It uses focused ion beam fabricated notched microcantilevers. The method has been validated by cyclic bending metallic glass and tungsten microcantilevers. The experiments reveal a stable crack growth during the lifetime of both samples. The metallic glass shows less plas…
Solid-state amorphization of crystalline copper nanolayers embedded in a Cu64Zr36 metallic glass is studied by molecular dynamics simulations for different orientations of the crystalline layer. We show that solid-state amorphization is driven by a reduction of interface energy, which compensates the bulk excess energy of the amorphous nanolayer with respect to the crystalline phase up to a critical layer thickness. A simple thermodynamic model is derived, which describes the simulation results in terms of orientation-dependent interface energies. Detailed analysis reveals the structure of the…
Twisted and rope-like assemblies of filamentous molecules are common and vital structural elements in cells and tissue of living organisms. We study the intrinsic frustration occurring in these materials between the two-dimensional organization of filaments in cross section and out-of-plane interfilament twist in bundles. Using non-linear continuum elasticity theory of columnar materials, we study the favorable coupling of twist-induced stresses to the presence of edge dislocations in the lattice packing of bundles, which leads to a restructuring of the ground-state order of these materials at…
Spin glasses are a highly complex magnetic state of matter, intricately linked to spin frustration and structural disorder. They exhibit no long-range order and exude aging phenomena, distinguishing them from quantum spin liquids. We report a new type of spin glass state, the spin-Q glass, observable in bulk-like crystalline metallic neodymium thick films. Using spin-polarized scanning tunneling microscopy combined with ab initio calculations and atomistic spin-dynamics simulations, we visualize the variations in atomic-scale non-collinear order and its response to magnetic field and temperatu…
Magnetic and electric properties of a single crystal of La0.7Ca0.3CoO3 have been experimentally studied. The system attains a ferromagnetic spontaneous moment below 170 K and exhibits a re-entrant spin-glass phase below 100 K. In the ordered and the re-entrant phases, the low field magnetic properties are strongly direction dependent, showing considerably higher magnetization values perpendicular than parallel to the c-axis. Magnetic relaxation experiments show that both the ferromagnetic and the re-entrant spin-glass phases are non-equilibrium states, where the system exhibits magnetic aging …
Nanocrystalline metals contain a large fraction of high-energy grain boundaries, which may be considered as glassy phases. Consequently, with decreasing grain size, a crossover in the deformation behaviour of nanocrystals to that of metallic glasses has been proposed. Here, we study this crossover using molecular dynamics simulations on bulk glasses, glass-crystal nanocomposites, and nanocrystals of Cu64Zr36 with varying crystalline volume fractions induced by long-time thermal annealing. We find that the grain boundary phase behaves like a metallic glass under constraint from the abutting cry…
There has been growing interest in structural quantum phase transitions and quantum fluctuations of phonons in the research area of condensed matter physics. Here, we report the observation of glass-like features in the lattice heat capacity of a stuffed tridymite-type crystal, Ba1-xSrxAl2O4, a candidate compound of quantum paraelectrics. Substitutional chemical suppression of the ferroelectric phase transition temperature (TC) of Ba1-xSrxAl2O4 results in the disappearance of the TC at x=0.07. For the compositional window of x=0.2-0.5, the lattice heat capacity is enhanced below approximately …
Self-induced crystalline fluctuation spin-glass state in Mn7C3 binary compounds
State Key Laboratory of Superhard Materials, College of Physics, Jilin University（吉林大学物理学院超硬材料国家重点实验室）；Center for Optics Research and Engineering, Shandong University（山东大学光电研究中心）；State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University（吉林大学化学学院无机合成与制备化学国家重点实验室）；Institute of High Pressure Physics, School of Physical Science and Technology, Ningbo University（宁波大学物理科学与技术学院高压物理研究所）
We report low temperature (1.8-15 K) ac magnetic susceptibility and isothermal remanent magnetization behavior for the single crystalline form of Dy2PdSi3, crystallizing in a AlB2-derived hexagonal structure, for two orientations. The results, while confirming the existence of two magnetic transitions, one at 8 K and the other at 2.5 K, as inferred from previous dc magnetization studies, suggest that the 2.5K-transition is spin-glass-like, with an interesting sensitivity to the application of an external dc magnetic field. Thus, this compound appears to undergo a transition from antiferromagne…
The thermal conductivity of polycrystalline semiconductors with type-I clathrate hydrate crystal structure is reported. Ge clathrates (doped with Sr and/or Eu) exhibit lattice thermal conductivities typical of amorphous materials. Remarkably, this behavior occurs in spite of the well-defined crystalline structure and relatively high electron mobility ($\sim 100 cm^2/Vs$). The dynamics of dopant ions and their interaction with the polyhedral cages of the structure are a likely source of the strong phonon scattering.
Quantitative density measurements from electron scattering show that shear bands in deformed Al_{88}Y_{7}Fe_{5} metallic glass exhibit alternating high and low density regions, ranging from -9 % to +6 % relative to the un-deformed matrix. Small deections of the shear band from the main propagation direction coincide with switches in density from higher to lower than the matrix and vice versa, indicating that faster and slower motion (stick-slip) occurs during the propagation. Nano-beam diffraction analyses provides clear evidence that the density changes are accompanied by structural changes s…
We have computed second and third nonlinear optical susceptibilities of two crystalline bulk tellurium oxide polymorphs: $α$-TeO$_{2}$ (the most stable crystalline bulk phase) and $γ$-TeO$_{2}$ (the crystalline phase that ressembles the more to the glass phase. Third order nonlinear susceptibilities of the crystalline phases are two orders of magnitude larger than $α$-SiO$_{2}$ cristoballite, thus extending the experimental observations on glasses to the case of crystalline compounds. While the electronic lone pairs of Te contribute to those large values, a full explanation of the anisotropy o…
Molecular dynamics simulations using an interatomic potential developed by artificial neural network deep machine learning are performed to study the local structural order in Al90Tb10 metallic glass. We show that more than 80% of the Tb-centered clusters in Al90Tb10 glass have short-range order (SRO) with their 17 first coordination shell atoms stacked in a '3661' or '15551' sequence. Medium-range order (MRO) in Bergman-type packing extended out to the second and third coordination shells is also clearly observed. Analysis of the network formed by the '3661' and '15551' clusters show that ~82…
Metallic glasses have attracted considerable interest in recent years due to their unique combination of superb properties and processability. Predicting bulk metallic glass formers from known parameters remains a challenge and the search for new systems is still performed by trial and error. It has been speculated that some sort of "confusion" during crystallization of the crystalline phases competing with glass formation could play a key role. Here, we propose a heuristic descriptor quantifying confusion and demonstrate its validity by detailed experiments on two well-known glass forming all…
Raman micro/macro-spectroscopy allows for a non-destructive remote analysis: body and glaze, crystalline and amorphous phases can be identified, including the nanosized pigments colouring the glaze. Last generation instruments are portable which allows for examination in museum, on sites, etc. This paper gives an overview on the potential of Raman spectrometry technique to analyze ancient ceramics and glasses. Selected glasses as well as glazes of various porcelains, celadon, faiences and potteries, representative of the different production technologies used in the Antique, European, Mediterr…
To describe structural peculiarities in inhomogeneous media caused by the tendency to the close packing of atoms a formalism based on the using of the Riemann geometry methods (which were successfully applied lately to the description of structures of quasicrystals and glasses) is developed. Basing on this formalism we find in particular the criterion of stability of precipitates of the Frank-Kasper phases in metallic systems. The nature of the ''rhenium effect'' in W-Re alloys is discussed.
The underlying structural order that transcends the liquid, glass and crystalline states is identified using an efficient genetic algorithm (GA). GA identifies the most common energetically favorable packing motif in crystalline structures close to the alloy's Al-10 at.% Sm composition. These motifs are in turn compared to the observed packing motifs in the actual liquid structures using a cluster-alignment method which reveals the average topology. Conventional descriptions of the short-range order, such as Voronoi tessellation, are too rigid in their analysis of the configurational poly-type…
The requirement that packings of hard particles, arguably the simplest structural glass, cannot be compressed by rearranging their network of contacts is shown to yield a new constraint on their microscopic structure. This constraint takes the form a bound between the distribution of contact forces P(f) and the pair distribution function g(r): if P(f) \sim f^θ and g(r) \sim (r-σ)^(-γ), where σ is the particle diameter, one finds that γ \geq 1/(2+θ). This bound plays a role similar to those found in some glassy materials with long-range interactions, such as the Coulomb gap in Anderson insulato…
We report on a non-equilibrium phase of matter, the minimally disordered crystal phase, which we find exists between the maximally amorphous glasses and the ideal crystal. Even though these near crystals appear highly ordered, they display glassy and jamming features akin to those observed in amorphous solids. Structurally, they exhibit a power-law scaling in their probability distribution of weak forces and small interparticle gaps as well as a flat density of vibrational states. Dynamically, they display anomalous aging above a characteristic pressure. Quantitatively this disordered crystal …
We use a theoretical model to explore how fluid dynamics, in particular, the pressure gradient and wall shear stress in a channel, affect the deposition of particles flowing in a microfluidic network. Experiments on transport of colloidal particles in pressure-driven systems of packed beads have shown that at lower pressure drop, particles deposit locally at the inlet, while at higher pressure drop, they deposit uniformly along the direction of flow. We develop a mathematical model and use agent-based simulations to capture these essential qualitative features observed in experiments. We explo…
Polyhedra and their arrangements have intrigued humankind since the ancient Greeks and are today important motifs in condensed matter, with application to many classes of liquids and solids. Yet, little is known about the thermodynamically stable phases of polyhedrally-shaped building blocks, such as faceted nanoparticles and colloids. Although hard particles are known to organize due to entropy alone, and some unusual phases are reported in the literature, the role of entropic forces in connection with polyhedral shape is not well understood. Here, we study thermodynamic self-assembly of a fa…
Germanium dioxide ($GeO_2$) is a chemical analogue of $SiO_2$. Furthermore, it is also to some extent a structural analogue, as the low and high-pressure short-range order (tetrahedral and octahedral) is the same. However, a number of differences exist. For example, the $GeO_2$ phase diagram exhibits a smaller number of polymorphs, and all three $GeO_2$ phases (crystalline, glass, liquid) have an increased sensitivity to pressure, undergoing pressure induced changes at much lower pressures than their equivalent $SiO_2$ analogues. In addition, differences exist in $GeO_2$ glass in the medium ra…
When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate $R_c$, the crystalline state is bypassed and an amorphous glassy state forms instead. $R_c$ (or the corresponding critical casting thickness $d_c$) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small $R_c<10^{-2}$ K/s, pure metals and most alloys are poor glass-formers with large $R_c>10^{10}$ K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with $R_c$ approaching that for silica. Recent …
Liquids and solids are two fundamental states of matter. However, due to the lack of direct experimental determination, our understanding of the 3D atomic structure of liquids and amorphous solids remained speculative. Here we advance atomic electron tomography to determine for the first time the 3D atomic positions in monatomic amorphous materials, including a Ta thin film and two Pd nanoparticles. We observe that pentagonal bipyramids are the most abundant atomic motifs in these amorphous materials. Instead of forming icosahedra, the majority of pentagonal bipyramids arrange into networks th…
All hard, convex shapes are conjectured by Ulam to pack more densely than spheres, which have a maximum packing fraction of ϕ = π/\sqrt18 ~ 0.7405. For many shapes, simple lattice packings easily surpass this packing fraction. For regular tetrahedra, this conjecture was shown to be true only very recently; an ordered arrangement was obtained via geometric construction with ϕ = 0.7786, which was subsequently compressed numerically to ϕ = 0.7820. Here we show that tetrahedra pack much better than this, and in a completely unexpected way. Following a conceptually different approach, using thermod…
Energy storage technologies that can meet the unprecedented demands of a sustainable energy system based on intermittent energy sources require new battery materials. We investigate high ionic conductors, Li$_3$ClO glasses. In the present work we use a first principles method to model the amorphous structure of the glass. We characterize the structure by means of radial distribution functions, radial disctributions functions and coordination numbers. We compare to their crystalline counterparts. The electronic structure of the glass is compared to that of the crystalline material. The band gap…
In this article, a theoretical description of the "ideal glass transition" is approached upon the adoption of a quaternion orientational order parameter. Unlike first-order phase transitions of liquids into crystalline solid states, glass transitions are entirely different phenomena that are non-equilibrium and that are highly dependent on the applied cooling rate. Herein, the "ideal glass transition" that occurs at the finite Kauzmann temperature at which point the configurational entropy of an undercooled liquid matches that of its crystalline counterpart is identified as a first-order quant…
The magnetic susceptibilities and specific heats of the crystalline garnet and glass forms of Mn3Al2Si3O12 are reported. This allows a direct comparison of the degree of magnetic frustration of the triangle-based garnet lattice and the structurally disordered solid at the same composition for isotropic spin 5/2 Mn^2+ (3d^5). The results show that the glass phase shows more pronounced signs of magnetic frustration than the crystalline phase. Through comparison of the specific heats of Ca3Al2Si3O12 (grossular) and Mn3Al2Si3O12 (spessartine) garnets, information is provided concerning the anomalo…
The spin glass behavior of Y2Mo2O7 has puzzled physicists for nearly three decades. Free of bulk disorder within the resolution of powder diffraction methods, it is thought that this material is a rare realization of a spin glass resulting from weak disorder such as bond disorder or local lattice distortions. Here, we report on the single crystal growth of Y2Mo2O7. Using neutron scattering, we present unique isotropic magnetic diffuse scattering arising beneath the spin glass transition despite having a well-ordered structure at the bulk level. Despite our attempts to model the diffuse scatter…
The original electronic structure of the Pb$^{2+}$ ion explains its particular structural role in crystalline phases and silicate glasses. After a description of the structural role of lead in crystalline phases (PbO, silicates), this chapter presents a summary of the main structural studies carried out on glasses from the SiO$_2$-PbO, SiO$_2$-PbO-R$_2$O (R: alkaline) and SiO$_2$-PbO-Al$_2$O$_3$ systems, using various spectroscopic and simulation techniques.
The nature of Calcium--Silicate--Hydrate (C--S--H), the binding phase of cement, remains a controversial question. In particular, contrary to the former crystalline model, it was recently proposed that its nanoscale structure was actually amorphous. To elucidate this issue, we analyzed the structure of a realistic simulation of C--S--H, and compared the latter to crystalline tobermorite, a natural analogue to cement, and to an artificial ideal glass. Results clearly support that C--S--H is amorphous. However, its structure shows an intermediate degree of order, retaining some characteristics o…
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal …
We present results of molecular simulations that predict the phases formed by the self-assembly of model nanospheres functionalized with a single polymer "tether", including double gyroid, perforated lamella and crystalline bilayer phases. We show that microphase separation of the immiscible tethers and nanospheres causes confinement of the nanoparticles, which promotes local icosahedral packing that stabilizes the gyroid and perforated lamella phases. We present a new metric for determining the local arrangement of particles based on spherical harmonic "fingerprints", which we use to quantify…
Physics-Informed Glass-Structure Descriptors for Assessing the Intrinsic Reactivity of Mixed Amorphous-Crystalline Precursors in Alkali-Activated Materials
Hebei University of Technology（河北工业大学）；Rice University（莱斯大学）；Rice Advanced Materials Institute, Rice University（莱斯大学先进材料研究所）；Ken Kennedy Institute, Rice University（莱斯大学肯·肯尼迪研究所）
We measure shear response in packings of glass beads by pulling a thin, rough, metal plate vertically through a bed of volume fraction phi, which is set, before the plate is pulled, in the range 0.575 to 0.628. The yield stress is velocity independent over 4 decades and increases exponentially with phi, with a transition at phi approximately 0.595. An analysis of the measured force fluctuations indicates that the shear modulus is significantly smaller than the bulk modulus.
Physics-Informed Symbolic Regression for Predicting the Glass Transition Temperature of Alkali Borate Glasses
Federal University of Sergipe（塞尔希培联邦大学）；Federal University of Lavras (UFLA)（拉夫拉斯联邦大学）；Federal University of Bahia（巴伊亚联邦大学）；Brazilian Center for Research in Energy and Materials (CNPEM)（巴西能源与材料研究中心）
