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 has a positive heat of mixing, and in $CuZr$, characterized by a large negative heat of mixing. Our results allow us to identify that this unusual behavior is directly correlated with a non-monotonic temperature dependence for the formation energy of connected icosahedral structures, which are incompatible with crystalline order and impede the development of the crystal nucleus, leading to an unexpectedly larger free energy barrier at low temperature. This, in turn, promotes the formation of a predominantly closed-packed critical nucleus, with fewer defects, thereby suggesting a new way to control the structure of the crystal nucleus, which is of key importance in catalysis.
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…
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…
We report the results of the Ni-based bulk metallic glass structural evolution and crystallization behavior in situ investigation. The X-ray diffraction (XRD), transmission electron microscopy (TEM), nano-beam diffraction (NBD), differential scanning calorimetry (DSC), radial distribution function (RDF) and scanning probe microscopy/spectroscopy (STM/STS) techniques were applied to analyze the structure and electronic properties of Ni63.5Nb36.5 glasses before and after crystallization. It was proved that partial surface crystallization of Ni63.5Nb36.5 can occur at the temperature lower than fo…
A complex rare-earth rich aluminoborosilicate glass has been proved to be a good candidate for the immobilization of new high level radioactive wastes. A simplified seven-oxides composition of this glass was selected for this study. In this system, sodium and calcium cations were supposed in other works to simulate respectively all the other alkali (R+=Li+, Rb+, Cs+) and alkaline-earth (R'2+=Sr2+, Ba2+) cations present in the complex glass composition. Moreover, neodymium or lanthanum are used here to simulate all the rare-earths and actinides occurring in waste solutions. In order to study th…
Transparent glasses of BaNaB9O15 (BNBO) were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were respectively, confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC). The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. The correlation between the heating rate dependent glass transition and the crystallization temperatures was discussed and deduced the Kauzmann temperature for BNBO glass-plates and powdered samples. The values of th…
Abrupt crystallization from shock-compressed CaSiO3 glass
Graduate School of Engineering, The University of Osaka（大阪大学研究生院工学研究科）；School of Science, Wuhan University of Technology（武汉理工大学理学院）；Institute of Laser Engineering, The University of Osaka（大阪大学激光工程研究所）；Nevada Extreme Conditions Laboratory, University of Nevada, Las Vegas（内华达大学拉斯维加斯分校极端条件实验室）；RIKEN SPring-8 Center（理化学研究所SPring-8中心）；Graduate School of Science, Osaka Metropolitan University（大阪公立大学理学研究科）
Poly(ethylene terephthalate) (PET) is a semi--crystalline polymer that can be crystallized to different degrees heating from the amorphous state. Even when primary crystallization has been completed, secondary crystallization can take place with further annealing and modify the characteristics of the amorphous interlamellar phase. In this work we study the glass transition of highly crystallized PET and in which way it is modified by secondary crystallization. Amorphous PET samples were annealed for 4 hours at temperatures between 140C and 180C. The secondary crystallization process was monito…
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.
Upcycling solar glass into Ce-doped oxyfluorides: spectroscopic and crystallization properties
Universidade Tecnológica Federal do Paraná（巴西联邦技术大学巴拉那分校）；Universidade Estadual de Maringá（马里纳加州立大学）；Laboratoire CEMHTI, UPR 3079-CNRS（法国国家科学研究中心CEMHTI实验室）
Li1.5Al0.5Ge1.5(PO4)3 (LAGP) is among the most promising solid electrolytes for the next generation all-solid-state lithium batteries. However, preparing LAGP electrolytes is timeand energy-intensive. In this work, LAGP glassy powders were sintered and crystallized in 180 seconds by ultrafast high-temperature sintering (UHS) under conditions attractive for continuous industrial processes (i.e., ambient pressure and atmosphere). The fast heating rates characteristic of UHS significantly delay crystallization, potentially decoupling crystallization and sintering. Furthermore, EIS characterizatio…
Engineering phase change materials (PCM) to realize superior data storage devices requires a detailed understanding of crystallization kinetics and its temperature dependence. The temperature dependence of crystallization differs distinctly between crystallizing from the glassy phase and the undercooled liquid (UCL). Hence, knowing the phase from which crystallization occurs is necessary for predicting the switching ability. Here, we measure the glassy dynamics and crystallization kinetics using calorimetry for heating rates spanning over six orders of magnitude. Our results show that the prom…
Crystallization of metallic glass as a grain-boundary nucleated process: experimental and theoretical evidence for the grain structure of metallic glasses
A comparative study on as cast and annealed rare earth bulk metallic glass (BMG) with composition Tb36Sm20Al24Co20 has been carried out by magnetization measurements. The as cast amorphous sample shows non-ergodic magnetization but does not show the behavior expected from magnetic glass. After annealing, the partially crystallized BMG shows this magnetic glass behavior. This is confirmed by the established measurement protocol of cooling and heating in unequal fields (CHUF).
In a recent article, Schmelzer and Tropin [Entropy 20 [2] 103 (2018)] presented an unfounded, confusing critique of several aspects of modern glass science. Relying on pre-Socratic Greek philosophy and state-of-the-art scientific understanding from the 1920s-1930s, Schmelzer and Tropin propagate an antiquated view of glass physics that is at odds with well-accepted knowledge in the field from both theory and experiments conducted in the post-World War II era. The objective of this short letter is to elucidate and extinguish their critique. This rebuttal is directed to our colleagues and especi…
A bulk metallic glass forming alloy is subjected to shear flow in its supercooled state by compression of a short rod to produce a flat disc. The resulting material exhibits enhanced crystallization kinetics during isothermal annealing as reflected in the decrease of the crystallization time relative to the non-deformed case. The transition from quiescent to shear-accelerated crystallization is linked to strain accumulated during shear flow above a critical shear rate $\dotγ_c\approx 0.3$ s$^{-1}$ which corresponds to Péclet number, $Pe\sim\mathcal{O}(1)$. The observation of shear accelerated …
Nucleation and growth of crystal in an oxide glass was studied in a Si B Al Zr Nd Ca Na O system. The nucleation and growth process was monitored by thermal analysis and isothermal experiments. For the Ca sample the crystallization is homogeneous in the bulk showing a slow increase of crystallinity as temperature increases. The Na rich sample on the other hand go through several crystallization process in the bulk or from the surface, leading to bigger crystals. The activation energy of the viscous flow and the glass transition are of same magnitude when that of crystallization is a lot smalle…
Nuclear spent fuel reprocessing generates high level radioactive waste with high Mo concentration that are currently immobilized in borosilicate glass matrices containing both alkali and alkaline-earth elements [1]. Because of its high field strength, Mo6+ ion has a limited solubility in silicate and borosilicate glasses and crystallization of alkali or alkaline-earth molybdates can be observed during melt cooling or heat treatment of glasses [2-4]. Glass composition changes can significantly modify the nature and the relative proportions of molybdate crystals that may form during natural cool…
The rheological properties of highly concentrated suspensions of hard-sphere particles are studied with particular reference to the rheological response of shear induced crystals. Using practically monodisperse hard spheres, we prepare shear induced crystals under oscillatory shear and examine their linear and non-linear mechanical response in comparison with their glassy counterparts at the same volume fraction. It is evident, that shear-induced crystallization causes a significant drop in the elastic and viscous moduli due to structural rearrangements that ease flow. For the same reason the …
Study of condensed matter in certain extreme conditions allows one to better understand the mechanisms of microscopic structural transformations and to develop materials with completely new mechanical properties. In the present work, we study the structure and crystallization kinetics of bulk metallic glass (BMG) Ni$_{62}$Nb$_{38}$. We show that this BMG is rapidly crystallized under the combined effect of shear deformation and ultrahigh pressure. A threshold pressure required to initiate the formation of a stable crystalline phase is revealed. Shear deformation and pressure lead to the phase …
The local organisation of a simulated glass-forming mixture due to Kob and Andersen is analysed. Evidence is presented for a structural transition from triangulated coordination polyhedra to cubic as the number fraction of the smaller species B increases towards equimolar. The impact of the change on the partial radial distribution function g-{BB}(r) is established. The dependence of the crystallisation rate on the composition is determined and the related to the observed structural changes.
Motivated by old experiments on colloidal suspensions, we report molecular dynamics simulations of assemblies of hard spheres, addressing crystallization and glass formation. The simulations cover wide ranges of polydispersity s (standard deviation of the particle size distribution divided by its mean) and particle concentration. No crystallization is observed for s > 0.07. For 0.02 < s < 0.07, we find that increasing the polydispersity at a given concentration slows down crystal nucleation. The main effect here is that polydispersity reduces the supersaturation since it tends to stabilise the…
December 1991 legislation in France has spurred research on enhanced separation and conditioning or transmutation of long-lived radionuclides from high level radioactive wastes (HLW). In this field, we have studied zirconolite-based glass-ceramics in which the crystalline phase (zirconolite: CaZrTi2O7) aimed to preferentially incorporate minor actinides is embedded in a glassy calcium aluminosilicate matrix. At the laboratory scale, the crystallization of the parent glass is carried out thanks to a two-step thermal treatment: a nucleation stage followed by a growth stage. This paper presents t…
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 …
Solid-phase epitaxial crystallization of amorphous Si layers on a crystalline Si substrate during B-ion irradiation is investigated over the temperature range 293 - 573 K. Regrowth occurs at all measured temperatures, with activation energy 0.07 eV and prefactor 2.36 nm / 10^14 B cm-2 The low activation energy suggests that free interstitial point defects are involved and the unusually large prefactor indicates that each interstitial crystallizes about 50 host Si atoms. We propose that interstitial annihilation at the a/c interface sets off a shock-like process that drives c-Si island nucleati…
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…
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…
Metals in amorphous state are promising for the use as structural materials due to their superior properties related to the absence of grain boundaries and dislocations.Obtaining the amorphous state requires quenching with a high cooling rate.In conventional technologies,this is the reason for a considerable size limitation hindering application of amorphous alloys.Additive manufacturing (AM) is free of the size limitation.The so-called bulk metallic glass (BMG) alloys have extremely low critical cooling rates and can be used in AM. Recent studies on AM from Zr-based BMGs by selective laser me…
Transparent glasses in the system 3BaO-3TiO2-B2O3 (BTBO) were fabricated via the conventional melt-quenching technique. The as-quenched samples were confirmed to be glassy by differential thermal analysis (DTA) technique. The thermal parameters were evaluated using non-isothermal DTA experiments. Kauzmann temperature was found to be 759 K based on heating rate dependent glass transition and crystallization temperatures. Theoretical relation for temperature dependent viscosity was proposed for these glasses and glass-ceramics.
Crystal nucleation and growth processes induced by an externally applied shear strain in a model metallic glass are studied by means of nonequilibrium molecular dynamics simulations, in a range of temperatures. We observe that the nucleation-growth process takes place after a transient, induction regime. The critical cluster size and the lag-time associated with this induction period are determined from a mean first-passage time analysis. The laws that describe the cluster growth process are studied as a function of temperature and strain rate. A theoretical model for crystallization kinetics …
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）
This work concerns glasses belonging to SiO2-Al2O3-CaO-ZrO2-TiO2-Nd2O3 system that lead to zirconolite crystallization in their bulk after nucleation + crystal growth thermal treatments and that could find application as nuclear waste form. The understanding of crystallization processes in glasses implied to investigate their structure. The environment around Ti, Zr (nucleating agents) and Nd was characterized for various Nd2O3 loadings. Electron spin resonance study of the small amount of Ti3+ occurring in glasses enabled to identify two types of sites for titanium. EXAFS showed that Zr occup…
A quinary (La0.5Ce0.5)65Al10(Co0.6Cu0.4)25 alloy with superior glass-forming ability (GFA), identified by the formation of fully glassy rod of 32 mm in diameter by tilt-pour casting, was reported. By comparing with the GFA of quarternary (La0.5Ce0.5)65Al10TM25 and ternary Ln65Al10TM25 alloys (Ln = La or Ce; TM = Co or Cu), we suggest that the strong frustration of crystallization by utilizing the coexistence of La-Ce and Co-Cu to complicate competing crystalline phases is helpful to construct BMG component with superior GFA.
Fe doped Ni$_2$Mn$_{1.5}$In$_{0.5}$, particularly, Ni$_2$Mn$_{1.4}$Fe$_{0.1}$In$_{0.5}$, despite having an incommensurate, modulated 7M martensitic structure at room temperature exhibits frequency dependent behavior of storage modulus and loss that obeys Vogel-Fulcher law as well as shows ergodicity breaking between zero field cooled and field cooled strain measurements just above the transition temperature. Both, frequency dependence and ergodicity breaking are characteristics of a strain glassy phase and occur due to presence of strain domains which are large enough to present signatures of …
We study the influence of the liquid-vapor surface on the crystallization kinetics of supercooled metal alloys. While a good glass former, $\rm{Cu}_{50}\rm{Zr}_{50}$, shows no evidence of surface enhancement of crystallization, $\rm{Ni}_{50}\rm{Al}_{50}$ exhibits an increased rate of crystallization due to heterogeneous nucleation at the free liquid surface. The difference in the compositional fluctuations at the interface is proposed as the explanation of the distinction between the two alloys. Specifically, we observe compositional ordering at the surface of $\rm{Ni}_{50}\rm{Al}_{50}$ while …
Differential scanning calorimetry (DSC) is one of the most versatile probes for silicate glasses, allowing determination of, e.g., transition temperatures (glass, crystallization, melting) and the temperature dependence of heat capacity. However, complications arise for glasses featuring overlapping transitions and low sensitivity, e.g., arising from SiO2-rich compositions with small change in heat capacity during glass transition or the low sensitivity of thermocouples at high temperature. These challenges might be overcome using temperature-modulated DSC (TM-DSC), which enables separation of…
The cohesive energies and structural properties of recently predicted, and never synthesized, B$_2$O$_3$ polymorphs are investigated from first principles using density functional theory and high-accuracy many-body methods, namely, the random phase approximation and quantum Monte Carlo. We demonstrate that the van der Waals forces play a key role in making the experimentally known polymorph (B$_2$O$_3$-I) the lowest in energy, with many competing metastable structures lying only a few kcal/mol above. Remarkably, all metastable crystals are comparable in energy and density to the glass, while h…
Crystallization kinetics has features that are universal and independent of the type of crystallized system. The possibility of using scaling relations to describe the temperature dependences of the surface self-diffusion coefficient $D_s$, which is one of the key characteristics of crystallization kinetics, has been demonstrated in application to various crystallized molecular glasses. It has been shown that the surface self-diffusion coefficient $D_s$ as a function of the dimensionless temperature is reproduced by a power law and is universally scaled for all considered systems. The analysis…
A correlation between the change in magnetic susceptibility (Δ\c{hi}exp) upon crystallization of Cu-Zr, Hf metallic glasses (MG) with their glass forming ability (GFA) observed recently is found to apply to Cu-Ti and Zr-Ni alloys, too. In particular, a small Δ\c{hi}exp , which reflects similar electronic structures, ES, of glassy and corresponding crystalline alloys, corresponds to high GFA. Here, we studied Δ\c{hi}exp in five Cu-Ti and four Cu-Zr and Ni-Zr MGs. The fully crystalline final state of all alloys was verified from X-ray diffraction patterns. The variation of GFA with composition i…
The lack of thermal stability, originating from their metastable nature, has been one of the paramount obstacles that hinder the wide range of applications of metallic glasses. We report that the stability of a metallic glass can be dramatically improved by slow deposition at high temperatures. The glass transition and crystallization temperatures of the ultrastable metallic glass can be increased by 51 K and 203 K, respectively, from its ordinary glass state. The ultrastable metallic glass also shows ultrahigh strength and hardness, over 30 % higher than its ordinary counterpart. Atomic struc…
The existence of a 'crossover region' in glass-forming liquids has long been considered as a general phenomenon that is as important as the glass transition. One potential origin for the crossover behavior is a liquid-to-liquid phase transition (LLPT). Although a LLPT is thought to exist in all forms of liquids, structural evidence for this, particularly in supercooled liquids, is scarce, elusive, and in many cases controversial. A key challenge to the search for a LLPT in a supercooled liquid is the interference of crystallization during cooling. Crystallization induces major structural chang…
Zero field cooled spontaneous exchange bias (SEB) is observed in epitaxial La0.7Sr0.3MnO3 (LSMO):NiO self-assembled nanocomposite thin films grown on (001) SrTiO3 single crystal substrate by pulsed laser deposition. SEB is displayed by the novel asymmetry in the hysteresis loop of the composite film along with the field cooled conventional exchange bias (CEB) effect. The training effect shows that exchange bias relaxation is disorder mediated. It is revealed from DC magnetization results that such nanocomposite film divulges spin glass like behaviour, which is arising due to competing ferromag…
The results of ac susceptibility (chi) measurements for Ca3CoXO6 (X = Rh, Ir and Co) compounds, containing spin-chains separated by Ca ions, are presented. All these compounds exhibit an unusually large frequency dependence of ac chi, in the vicinity of respective magnetic ordering temperatures, which is normally not encountered in conventional spin-glasses. The frequency dependence of ac chi, peak temperature is however found to obey Vogel-Fulcher relationship. The results thus establish that these compounds are unusual spin-glasses, that too among stoichiometric compounds presumably due to g…
The structural and magnetic properties of double perovskiteTb2CoMnO6 have been investigated. Electronic structure analysis by XPS study reveals the presence of mixed oxidation state (Mn4+/Mn3+ and Co2+/Co3+) of B-site ions. The dc and ac magnetization measurements reveal different interesting phases such as Griffith phase, re-entrant spin glass, metamagnetic steps, Hopkinson like peak and also unusual slow relaxation. The M-H curve indicates the presence of competing AFM/FM interactions. The disorder in Tb2CoMnO6 leads to spin frustration at low temperature giving rise to the re-entrant spin g…
There are at least three fundamental states of matter, depending upon temperature and pressure: gas, liquid, and solid (crystal). These states are separated by first-order phase transitions between them. In both gas and liquid phases the complete translational and rotational symmetry exist, whereas in a solid phase both symmetries are broken. In intermediate phases between liquid and solid, which include liquid crystal and plastic crystal phases, only one of the two symmetries is preserved. Among the fundamental states of matter, the liquid state is most poorly understood. We argue that it is …
We report the results of magnetic measurements for the solid solution Ce$_2$Au$_{1-x}$Co$_x$Si$_3$. The results reveal that this solid solution is characterized by a magnetic phase diagram (plot of magnetic transition temperature versus $x$) unusual for Kondo lattices. In particular, the spin-glass freezing induced by disorder is observed only for the compositions at the weak coupling limit; as one approaches the quantum critical point by a gradual replacement of Au by Co, this disorder effect is surprisingly suppressed in favor of long range antiferro-magnetic ordering in contrast to expectat…
We report for the first time real time in situ and quantitative measurements of the mutarotation reaction of lactose in the solid state. The experiments have been performed by 13C NMR. We show that mutarotation is initiated on heating the amorphous state, and reaches chemical equilibrium close above the glass transition temperature Tg. We do not observe this transformation when starting from stable crystalline states. The final ratio of <alfa> and <beta> anomers is 1:1, which suggests that the energy profile of the mutarotation reaction pathway in the solid state is actually different from the…
From pore collapse to crystal growth: ultrafast laser-induced stishovite formation in nanoporous silica
Université Jean Monnet, CNRS, Institut d’Optique Graduate School, Laboratoire Hubert Curien UMR 5516（让·莫兰大学，法国国家科学研究中心，高等光学研究院，于贝尔·居里实验室）；Department of Materials Science and Engineering, The Ohio State University（俄亥俄州立大学材料科学与工程系）
The process of homogeneous crystal nucleation has been considered in a model liquid, where the interparticle interaction is described by a short-range spherical oscillatory potential. Mechanisms of initiating structural ordering in the liquid at various supercooling levels, including those corresponding to an amorphous state, have been determined. The sizes and shapes of formed crystal grains have been estimated statistically. The results indicate that the mechanisms of nucleation occurs throughout the entire considered temperature range. The crystallization of the system at low supercooling l…
