X-ray structural and spectral analyses, X-ray diffraction topography and metallography were used to study dendrite structure of Al-4 wt % Cu single crystals grown by the Bridgman technique at a rate of 1 mm/min and on seeds with <001> orientation. The single crystals were obtained upon the crystallization of the melt under the action of a pressure and the gravitational-field component directed along the surface of the crystallization front. Non-uniform distribution of copper in the solid solution and the eutectic content has been found in transverse section of single crystals and strong increase in their concentration was observed at the lateral side of the samples in the direction of the gravitational-field component action. Distribution of copper and the eutectic phase depend on pressure.
The present study reports Al induced crystallization (AIC) of amorphous (a)-SiGe in Al-Ge-Si ternary system at low temperature ~ 350 degree C. In addition to crystallization, the isothermal annealing of a-SiGe/AlOx/Al/corning-glass (CG) structure was found to be accompanied by an Al induced layer exchange (ALILE) phenomenon. The evolution of residual stress in the Al layer during isothermal annealing is evaluated using X-ray diffraction based technique to ascertain the role of stress in the ALILE process. A corroboration of the stress with the growth kinetics, analyzed using Avrami theory of p…
Crystallization pressure drives deformation and damage in monuments, buildings and the Earth's crust. Even though the phenomenon has been known for 170 years there is no agreement between theoretical calculations of the maximum attainable pressure and that found experimentally. We have therefore developed a novel experimental technique to image the nano-confined crystallization process while controlling the pressure and applied it to calcite. The results show that displacement by crystallization pressure is arrested at pressures well below the thermodynamic limit. We use existing molecular dyn…
We report observation of crystallization of the glass-forming binary Lennard-Jones liquid first used by Wahnström [G. Wahnström, Phys. Rev. A 44, 3752 (1991)]. Molecular dynamics simulations of the metastable liquid on a timescale of microseconds were performed. The liquid crystallized spontaneously. The crystal structure was identified as MgZn_2. Formation of transient crystallites is observed in the liquid. The crystallization is investigate at different temperatures and compositions. At high temperature the rate of crystallite formation is the limiting factor, while at low temperature the l…
Crystallization from an amorphous atomic structure is usually seen as a spontaneous process in pursuit of a lower energy state, but for alloy systems it is often hard to elucidate because of the intrinsic structural and compositional complexity. Here, by means of electron beam irradiation, we found surface-limited, and thus size-dependent crystallization in a system of monoatomic Pd metallic glass, which is ascribed to the structural differences between the surface and the interior. The equilibrium thickness of the surface crystallization is controllable, presenting a promising approach to fab…
Using molecular simulations, we shed light on the mechanism underlying crystal nucleation in metal alloys and unravel the interplay between crystal nucleation and glass transition, as the conditions of crystallization lie close to this transition. While decreasing the temperature of crystallization usually results in a lower free energy barrier, we find an unexpected reversal of behavior for glass-forming alloys as the temperature of crystallization approaches the glass transition. For this purpose, we simulate the crystallization process in two glass-forming Copper alloys, $Ag_6Cu_4$, which h…
Salt crystallization is a major cause of weathering of artworks, monuments and rocks. Damage will occur if crystals continue to grow in confinement, i.e. within the pore space of these materials generating mechanical stresses. We report on a novel method that allows to directly measure, at the microscale, the resulting pressure while visualizing the spontaneous nucleation and growth of alkali halide salts. The experiments reveal the crucial role of the wetting films between the growing crystal and the confining walls for the development of the pressure. The results suggest that the pressure or…
We present a derivation of the recently proposed eighth order phase field crystal model [Jaatinen et al., Phys. Rev. E 80, 031602 (2009)] for the crystallization of a solid from an undercooled melt. The model is used to study the planar growth of a two dimensional hexagonal crystal, and the results are compared against similar results from dynamical density functional theory of Marconi and Tarazona, as well as other phase field crystal models. We find that among the phase field crystal models studied, the eighth order fitting scheme gives results in good agreement with the density functional t…
We focus our attention on Monte Carlo simulations of crystallization, which is one of the most important processes occurring in nature and technology of materials. Special attention is paid to the crystallization shrinkage and its consequences onto the growth of the new crystalline phase. We show that crystallization shrinkage stops after reaching the percolation threshold and that this is not the final stage of the crystallization process. Based on experimental evidences on sintering of diopside-albite systems and computer simulations we argue that crystallization continues inside the grains …
Germanium is an extremely important material used for numerous functional applications in many fields of nanotechnology. In this paper, we study the crystallization of amorphous Ge using atomistic simulations of critical nano-metric nuclei at high temperatures. We find that crystallization occurs by the recurrent transfer of atoms via a diffusive process from the amorphous phase into suitably-oriented crystalline layers. We accompany our simulations with a comprehensive thermodynamic and kinetic analysis of the growth process, which explains the energy balance and the interfacial growth veloci…
Piezoelectric quartz SiO2 crystals are widely used in industry as oscillators. As a natural mineral, quartz and its relevant silicates are also of interest of geoscience and mineralogy. However, the nucleation and growth of quartz crystals is difficult to control and not fully understood. Here we report successful solid state crystallization of thin film of amorphous GeO2 into quartz on various substrates including Al2O3, MgAl2O4, MgO, LaAlO3 and SrTiO3. At relatively low annealing temperatures, the crystallization process is spherulitic: with fibers growing radially from the nucleation center…
An aluminoborosilicate glass, containing high amount of rare earth (RE) accordingly to the following composition 50.68 SiO2 - 4.25 Al2O3 - 8.50 B2O3 - 12.19 Na2O - 4.84 CaO - 3.19 ZrO2 - 16.35 RE2O3 (wt.%), is currently under study for the immobilization of nuclear waste solutions. In this work, we wanted to investigate the effect of changing the RE cation type on the glass structure and on its crystallization behavior. For this purpose, a glass series was elaborated in which the nature of the RE is varying from lanthanum to lutetium. In this glass series, only little effect was observed on th…
Vortex crystals are commonly observed in ultra-thin ferroelectrics. However, a clear physical picture of origin of this topological state is currently lacking. Here, we show that vortex crystallization in ultra-thin Pb(Zr0.4,Ti0.6)O3 films stems from the softening of a phonon mode and can be thus described as a SU(2) symmetry-breaking transition. This result sheds light on the topology of the polar vortex patterns and bridges polar vortices with smectic phases, spin spirals, and other modulated states. Finally, we predict an ac-field driven resonant switching of the vortex tube orientation whi…
Competing crystallization pathways and cold crystallization kinetics in 10OS5 liquid crystal
Institute of Nuclear Physics, Polish Academy of Sciences（波兰科学院核物理研究所）；Faculty of Science, University of Siedlce（谢德尔采大学理学院）；Research Center for Thermal and Entropic Science, Graduate School of Science, Osaka University（大阪大学理学研究科热与熵科学研究中心）
Using Monte Carlo simulations we study crystallization in the three-dimensional Ising model with four-spin interaction. We monitor the morphology of crystals which grow after placing crystallization seeds in a supercooled liquid. Defects in such crystals constitute an intricate and very stable network which separate various domains by tensionless domain walls. We also show that the crystallization which occurs during the continuous heating of the glassy phase takes place at a heating-rate dependent temperature.
According to classical nucleation theory, a crystal grows from a small nucleus that already bears the symmetry of its end phase - but experiments with colloids now reveal that, from an amorphous precursor, crystallites with different structures can develop.
Attempts to grow terbium aluminium garnet (Tb3Al5O12, TAG) by the Czochralski method lead to crystals of millimeter scale. Larger crystals could not be obtained. DTA measurements within the binary system showed that TAG melts incongruently at 1840 deg. C. The perovskite (TbAlO3, TAP) with a congruent melting point of 1930 deg. C is the most stable phase in this system. The region for primary crystallization of TAP covers the chemical composition of TAG and suppresses the primary crystallization of the terbium aluminium garnet.
The kinetic mechanisms underlying bottom-up assembly of colloidal particles have been widely investigated in efforts to control crystallization pathways and to direct growth into targeted superstructures for applications including photonic crystals. Current work builds on recent progress in the development of kinetic theories for crystal growth of body-centered-cubic crystals in systems with short-range inter-particle interactions, accounting for a greater diversity of crystal structures and the role of the longer-ranged interactions and orientational degrees of freedom arising in polar system…
We investigate salt crystallization in porous media that can lead to their disintegration. For sodium sulfate we show for the first time experimentally that when anhydrous crystals are wetted with water, there is very rapid growth of the hydrated form of sulfate in clusters that nucleate on anhydrous salt micro crystals. The molar volume of the hydrated crystals being four times bigger, the growth of these clusters can generate stresses in excess of the tensile strength of the stone and lead therefore to damage.
In this article, we introduce a framework to investigate the growth of nano-crystallites in a polymer matrix numerically. This framework combines the Flory theory of entropic elasticity with phase-field approaches commonly used to model crystal growth. We investigate in particular the growth kinetics of a crystallite in the presence of topological constraints such as entanglements or cross-links, and show that depending on the coupling between the topological constraints and the growth kinetics various structures can be observed: branched structures looking like spherulites or stable nano-crys…
We have studied the structure and free energy landscape of a semi-flexible lattice-polymer in the presence of a surface. At low temperatures coexistence of two-dimensional integer-folded crystals is observed. As the temperature is increased there is a transition from these crystalline configurations to a disordered coil adsorbed onto the surface. The polymer then gradually develops three-dimensional character at higher temperatures. We compute the free energy as a function of increasing crystallinity and compare with the free energy profiles assumed by the Lauritizen-Hoffman surface nucleation…
A solution for the most important problems in 3D printing technology (long print times, small build volumes and limited material properties) is proposed. Method is based on the fact that temperature of melts crystallization can be shifted up by pressure. Required pressure can be created by Ampere force caused by electric current in the melt flow. Magnetohydrodynamical model (with heat taken into account) is developed. It has been shown that additional heating of melt by this current can be overcome by appropriate choice of tunable parameters and introduction of some additional magnetic field. …
The use of laser with a Gaussian-beam profile is frequently adopted in attempts of crystallizing non-single-crystal thin films; however, it merely results in the formation of poly-crystal thin films. In this paper, selective area crystallization of non-single-crystal copper(II) oxide (CuO) is described. The crystallization is induced by laser, laser-induced crystallization, with a beam profile in the shape of chevron. The crystallization is verified by the exhibition of a transition from a non-single-crystal phase consisting of small 100 nm x 100 nm grains of CuO to a single-crystal phase of c…
Crystal growth and crystal coalescence processes in supercooled systems strongly depend on the concentration of crystallization centers. We perform atomistic dynamics simulations of the crystallization process in the ultrathin metallic film at different supercooling levels corresponding to supercooled liquid and amorphous solid states. Scaled relations are applied to identify the characteristic regimes in the time-dependent crystalline nuclei concentration: steady-state nucleation regime, saturation regime and coalescence regime. We show that the crystal growth at the saturation regime appears…
Core optics components for high precision measurements are made of stable materials, having small optical and mechanical dissipation. The natural choice in many cases is glass, in particular fused silica. Glass is a solid amorphous state of material that couldn't become a crystal due to high viscosity. However thermodynamically or externally activated stimulated local processes of spontaneous crystallization (known as devitrification) are still possible. Being random, these processes can produce an additional noise, and influence the performance of such experiments as laser gravitational wave …
We present an isothermal fluctuating nonlinear hydrodynamic theory of crystallization in molecular liquids. A dynamic coarse-graining technique is used to derive the velocity field, a phenomenology, which allows a direct coupling between the free energy functional of the classical Density Functional Theory and the Navier-Stokes equation. Contrary to the Ginzburg-Landau type amplitude theories, the dynamic response to elastic deformations is described by parameter-free kinetic equations. Employing our approach to the free energy functional of the Phase-Field Crystal model, we recover the classi…
Crystallization of metallic glass as a grain-boundary nucleated process: experimental and theoretical evidence for the grain structure of metallic glasses
Below the melting temperature $T_m$ crystals are the stable phase of typical elemental or molecular systems. However, cooling down a liquid below $T_m$, crystallization is anything but inevitable. The liquid can be supercooled, eventually forming a glass below the glass transition temperature $T_g$. Despite their long lifetimes and the presence of strong barriers that produces an apparent stability, supercooled liquids and glasses remain intrinsically metastable state and thermodynamically unstable towards the crystal. Here we investigated the isothermal crystallization kinetics of the prototy…
Development of reliable interatomic potentials is crucial for theoretical studies of relationship between chemical composition, structure and observable properties in glass-forming metallic alloys. Due to ambiguity of potential parametrization procedure, some crucial properties of the system, such as crystallization stability or symmetry of the ground state crystal phase, may not be correctly reproduced in computer simulations. Here we address this issue for ${\rm Cu_{64.5}Zr_{35.5}}$ alloy described by two modifications of embedded atom model potential as well as by \textit{ab initio} molecul…
DNA-coated colloids can self-assemble into an incredible diversity of crystal structures, but applications of this technology are limited by poor understanding and control over the dynamical crystallization pathways. To address this challenge, we use microfluidics to quantify the self-assembly dynamics of DNA-programmed colloidal crystals, from thermally-activated nucleation through reaction-limited and diffusion-limited phases of crystal growth. Our detailed measurements of the temperature and concentration dependence of the kinetics at all stages along the crystallization pathway provide a s…
