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The crystallization of complex, concentrated alloys can result in atomic-level short-range order, composition gradients, and phase separation. These features govern the properties of the resulting alloy. While nucleation and growth in single-element metals are well understood, several open questions remain regarding the crystallization of multi-principal component alloys. We use molecular dynamics to model the crystallization of a five-element, equiatomic alloy modeled after CoCrCuFeNi upon cooling from the melt. Stochastic, homogeneous nucleation results in nuclei with a biased composition distribution, rich in Fe and Co. This deviation from the random sampling of the overall composition is driven by the internal energy and affects nuclei of a wide range of sizes, from tens of atoms all the way to super-critical sizes. This results in short-range order and compositional gradients at nanometer scales. [ABSTRACT FROM AUTHOR]

Advances in cryobiology techniques commonly target either the cooling or the warming cycle, while little thought has been given to ≪repair≫ protocols applicable during cold storage. In particular, crystallization is the dominant threat to cryopreserved samples but proceeds from small nuclei that are innocuous if further growth is forestalled. To this end, we propose a laser editing technique that locally heats individual crystals above their melting point by a focused nanosecond pulse, followed by amorphization during rapid resolidification. As a reference, we first apply the approach to ice crystals in cryoprotected solution and use Raman confocal mapping to study the deactivation of crystalline order. Then, we examine dimethyl sulfoxide trihydrate crystals that can germinate at low temperatures in maximally freeze concentrated regions, as commonly produced by equilibrium cooling protocols. We show how to uniquely identify this phase from Raman spectra and evidence retarded growth of laser-edited crystals during warming. [ABSTRACT FROM AUTHOR]

In this study, we conducted successful experiments on ethylenediamine sulfate (EDS), an organic compound, to investigate its enantioselectivity in chiral crystallization. We employed optical trapping with circularly polarized laser beams, using a continuous wave laser at 1064 nm. By focusing the laser at the air–solution interface of a heavy water-saturated EDS solution, the formation of sub-micrometer-sized chiral EDS crystals was verified. Two generated enantiomorphs (d-crystal and l-crystal) were identified by the rotating analyzer method. The enantioselectivity in the chiral crystallization of EDS was assessed through 30 to 60 times experiments conducted under various conditions of laser powers and polarization modes, utilizing the count of generated crystals for each enantiomorph in the evaluation. Circularly polarized lasers at a specific power created an imbalance in the generation probability of the enantiomorphs, resulting in crystal enantiomeric excess values of 23% and −30%. The enantioselectivity mechanism was explored from two perspectives: refractive index differences of two enantiomorphs and 3D helical optical forces. Study of the thermodynamic mechanism was insufficient to explain the outcomes. Conversely, the 3D helical optical force mechanism revealed that the forces acting on EDS clusters in solution induced helical fluid motion, driving EDS nucleation, with the helicity of fluid motion determining the crystal's chirality. This approach will present new insights into chirality in industrial and research fields, with potential applications in regard to improving optical resolution and addressing the origin of homochirality. [ABSTRACT FROM AUTHOR]

We demonstrate modulation of insulator metal transition (IMT) of VO2 films grown on single crystalline substrates through the effect of in-plane compression with crystallization of capping chalcogenide layer on the targeted VO2 films. Chalcogenide germanium–antimony–telluride (Ge2Sb2Te5: GST), which shows large volume reduction of 6.8% with its phase change from amorphous to crystal, was deposited on VO2 films grown on Al2O3 (001) and TiO2 (001) substrates, where V–V atoms along the cR-axis in the tetragonal VO2 phase align parallel and perpendicular to the substrate surfaces, respectively. As a result, counter shifts in temperature-dependence of resistance characteristics, to lower and higher directions, were observed for VO2 films on Al2O3 (001) and TiO2 (001), consistent with the lattice modulation of VO2 films by the in-plane compression introduced by GST crystallization. The obtained results open a way to realize large resistance change of IMT under constant temperature by controlling GST phases. [ABSTRACT FROM AUTHOR]

The use of flashlamp annealing as a low-temperature alternative or supplement to thermal annealing is investigated. Flashlamp annealing and thermal annealing were conducted on 100 nm thick indium tin oxide (ITO) films deposited on glass to compare the properties of films under different annealing methods. The ITO samples had an average initial sheet resistance of 50 Ω/sq. After flashlamp annealing, the sheet resistance was reduced to 33 Ω/sq only, while by thermal annealing at 210 °C for 30 min, a sheet resistance of 29 Ω/sq was achieved. Using a combination of flashlamp annealing and thermal annealing at 155 °C for 5 min, a sheet resistance of 29 Ω/sq was achieved. X-ray diffraction analysis confirmed that flashlamp annealing can be used to crystallize ITO. Flashlamp annealing allows for low-temperature crystallization of ITO on a time scale of 1–3 min. Through electrical and optical characterizations, it was determined that flashlamp annealing can achieve similar electrical and optical properties as thermal annealing. Flashlamp offers the method of low-temperature annealing, which is particularly suitable for temperature sensitive substrates. [ABSTRACT FROM AUTHOR]

Using colloids effectively confined in two dimensions by a cell with a thickness comparable to the particle size, we investigate the nucleation and growth of crystallites induced by locally heating the solvent with a near-infrared laser beam. The particles, which are "thermophilic," move towards the laser spot solely because of thermophoresis with no convection effects, forming dense clusters whose structure is monitored using two order parameters that gauge the local density and the orientational ordering. We find that ordering takes place when the cluster reaches an average surface density that is still below the upper equilibrium limit for the fluid phase of hard disks, meaning that we do not detect any sign of a proper "two-stage" nucleation from a glass or a polymorphic crystal structure. The crystal obtained at late growth stage displays a remarkable uniformity with a negligible amount of defects, arguably because the incoming particles diffuse, bounce, and displace other particles before settling at the crystal interface. This "fluidization" of the outer crystal edge may resemble the surface enhanced mobility giving rise to ultra-stable glasses by physical vapor deposition. [ABSTRACT FROM AUTHOR]

Freezing of water under nanoconfinement exhibits physical peculiarities with respect to the bulk water. However, experimental observations are extremely challenging at this scale, which limits our understanding of the effect of confinement on water properties upon freezing. In this study, we use molecular dynamic simulations to investigate how confinement affects the kinetics of growth of ice and the thermodynamic equilibrium of ice-liquid coexistence. TIP4P/Ice water model and CSH-FF model were applied to simulate ice crystallization in a confined cement system at temperatures down to 220 K. We adapted an interface detection algorithm and reparameterized the CHILL/CHILL+ algorithm to capture ice growth. The confinement leads to a shift of the maximum growth rate of ice to a higher temperature than for bulk water. Both the confinement and surface impurities contribute to slowing down the ice growth. For the ice-liquid coexistence at equilibrium, we derive a formulation of Thomson's equation adapted to statistical physics quantities accessible by molecular simulation, and we show that this adapted equation predicts accurately the melting line of bulk and confined ice Ih as a function of pressure. The confinement decreases systematically the melting temperature of ice of about 5 K compared with bulk ice Ih. A premelted water film about 1 nm thick is observed between the solid wall and ice, and its thickness is found to decrease continuously as temperature is lowered. We note that the surface impurities are key to the formation of the premelted water nanofilm when the temperature is lower than 250 K. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations are performed to study the crystallization of formamidinium lead iodide. From all-atom simulations of the crystal growth process and the δ-α-phase transitions, we try to reveal the formation of various stack-faulted intermediate defected structures and report various polytypes of formamidinium lead iodide that are observed from simulations. [ABSTRACT FROM AUTHOR]

The performance of sustainable polymers can be modified and enhanced by incorporating functional groups in the backbone of the polymer chain that increases intermolecular interactions, thus impacting the thermal properties of the material. However, in-depth studies on the role of intermolecular interactions on the crystallization of these polymers are still needed. This work aims to ascertain whether incorporating functional groups able to induce intermolecular interactions can be used as a suitable systematic strategy to modify the polymer thermal properties and crystallization kinetics. Thus, amide and additional ester groups have been incorporated into aliphatic polyesters (PEs). The impact of intermolecular interactions on the melting and crystallization behavior, crystallization kinetics, and crystalline structure has been determined. Functional groups that form strong intermolecular interactions increase both melting and crystallization temperatures but retard the crystallization kinetics. Selecting appropriate functional groups allows tuning the crystallinity degree, which can potentially improve the mechanical properties and degradability in semicrystalline materials. The results demonstrate that it is possible to tune the thermal transitions and the crystallization kinetics of PEs independently by varying their chemical structure. [ABSTRACT FROM AUTHOR]

Spontaneous crystallization of metals under extreme conditions is a unique phenomenon occurring under far-from-equilibrium conditions that could enable the development of revolutionary and disruptive metastable metals with unusual properties. In this work, the formation of the hexagonal close-packed nickel (hcp-Ni) metastable phase during spontaneous crystallization is studied using non-equilibrium molecular dynamics (MD) simulations, with the goal of maximizing the fraction of this metastable phase in the final state. We employ Bayesian optimization (BO) with the Gaussian processes (GPs) regression as the surrogate model to maximize the hcp-Ni phase fraction, where temperature and pressure are control variables. MD simulations provide data for training the GP model, which is then used with BO to predict the next simulation condition. Such BO-guided active learning leads to a maximum hcp-Ni fraction of 43.38% in the final crystallized phase within 40 iterations when a face-centered cubic crystallite serves as the seed for crystallization from the amorphous phase. When an hcp seed is used, the maximum hcp-Ni fraction in the final crystal increases to 58.25% with 13 iterations. This study shows the promise of using BO to identify the process conditions that can maximize the rare phases. This method can also be generally applicable to process optimization to achieve target material properties. [ABSTRACT FROM AUTHOR]

The morphology of dodecane in a nanopore at temperatures typical in exploited or depleted oil reservoirs is investigated using molecular dynamics simulation. The dodecane morphology is found to be determined by interactions between interfacial crystallization and surface wetting of the simplified oil, while "evaporation" only plays a minor role. The morphology changes from an isolated, solidified dodecane droplet to a film with orderly lamellae structures remaining within, and finally to a film containing randomly distributed dodecane molecules, as the system temperature increases. In a nanoslit under the impact of water, since water wins against oil in surface wetting on the silica surface due to electrostatic interaction induced hydrogen bonding between water and the silanol group of silica, the spreading of dodecane molecules over the silica surface is impeded by this water confinement mechanism. Meanwhile, interfacial crystallization is enhanced, leading to always an isolated dodecane "droplet," with crystallization weakening as the temperature increases. Since dodecane is immiscible to water, there is no mechanism for dodecane to escape the silica surface, and the competition of surface wetting between water and oil determines the morphology of the crystallized dodecane droplet. For the CO2–dodecane system in a nanoslit, CO2 is an efficient solvent for dodecane at all temperatures. Therefore, interfacial crystallization rapidly disappears. The competition of surface adsorption between CO2 and dodecane is secondary for all cases. The dissolution mechanism is a clear clue for the fact that CO2 is more effective than water flooding in oil recovery for a depleted oil reservoir. [ABSTRACT FROM AUTHOR]

Much effort has been expended to obtain thin films of metastable solid solutions of germanium (Ge) that contain as high tin (Sn) content as possible because of their excellent electronic and optoelectronic properties. On the basis of our previous study on amorphous Ge, we demonstrated in this study that irradiation of substrate-free films of amorphous Ge100−xSnx (x = 8, 11, and 19 at. %) with a low-energy electron beam of 3 keV at ambient temperature can induce instantaneous wide-area crystallization (explosive crystallization). Characteristic spiral crystal growth associated with explosive crystallization occurred with areas exceeding 50 μm in diameter around a scanned area of the electron beam of 8 × 8 μm2. As a result, solid solutions of GeSn with Sn concentration up to 19 at. % were obtained with the suppression of precipitation of β-Sn. The region of explosive crystallization reduced in size with increasing Sn content. In addition, thermal analyses revealed that the heat released during crystallization of amorphous GeSn films decreased with increasing Sn content. This relationship indicates that the heat release at the growth front plays a key role in the propagation of explosive crystallization of a-GeSn. [ABSTRACT FROM AUTHOR]

Leveraging the anisotropic shape of DNA-functionalized nanoparticles holds potential for shape-directed crystallization of a wide collection of superlattice structures. Using coarse-grained molecular dynamics simulations, we study the self-assembly of a binary mixture of cubic gold nanoparticles, which are functionalized by complementary DNA strands. We observe the spontaneous self-assembly of simple cubic (SC), plastic body-centered tetragonal (pBCT), and compositionally disordered plastic body-centered tetragonal (d-pBCT) phases due to hybridization of the DNA strands. We systematically investigate the effect of length, grafting density, as well as rigidity of the DNA strands on the self-assembly behavior of cubic nanoparticles. We measure the potential of mean force between DNA-functionalized nanocubes for varying rigidity of the DNA strands and DNA lengths. Using free-energy calculations, we find that longer and flexible DNA strands can lead to a phase transformation from SC to the pBCT phase due to a gain in entropy arising from the orientational degrees of freedom of the nanocubes in the pBCT phase. Our results may serve as a guide for self-assembly experiments on DNA-functionalized cubic nanoparticles. [ABSTRACT FROM AUTHOR]

Crystallization of amorphous materials by thermal annealing has been investigated for numerous applications in the fields of nanotechnology, such as thin-film transistors and thermoelectric devices. The phase transition and shape evolution of amorphous germanium (Ge) and Ag@Ge core–shell nanoparticles with average diameters of 10 and 12 nm, respectively, were investigated by high-energy electron beam irradiation and in situ heating within a transmission electron microscope. The transition of a single Ge amorphous nanoparticle to the crystalline diamond cubic structure at the atomic scale was clearly demonstrated. Depending on the heating temperature, a hollow Ge structure can be maintained or transformed into a solid Ge nanocrystal through a diffusive process during the amorphous to crystalline phase transition. Selected area diffraction patterns were obtained to confirm the crystallization process. In addition, the thermal stability of Ag@Ge core–shell nanoparticles with an average core of 7.4 and a 2.1 nm Ge shell was studied by applying the same beam conditions and temperatures. The results show that at a moderate temperature (e.g., 385 °C), the amorphous Ge shell can completely crystallize while maintaining the well-defined core–shell structure, while at a high temperature (e.g., 545 °C), the high thermal energy enables a freely diffusive process of both Ag and Ge atoms on the carbon support film and leads to transformation into a phase segregated Ag–Ge Janus nanoparticle with a clear interface between the Ag and Ge domains. This study provides a protocol as well as insight into the thermal stability and strain relief mechanism of complex nanostructures at the single nanoparticle level with atomic resolution. [ABSTRACT FROM AUTHOR]

A Gaussian approximation machine learning interatomic potential for platinum is presented. It has been trained on density-functional theory (DFT) data computed for bulk, surfaces, and nanostructured platinum, in particular nanoparticles. Across the range of tested properties, which include bulk elasticity, surface energetics, and nanoparticle stability, this potential shows excellent transferability and agreement with DFT, providing state-of-the-art accuracy at a low computational cost. We showcase the possibilities for modeling of Pt systems enabled by this potential with two examples: the pressure–temperature phase diagram of Pt calculated using nested sampling and a study of the spontaneous crystallization of a large Pt nanoparticle based on classical dynamics simulations over several nanoseconds. [ABSTRACT FROM AUTHOR]

Computational predictions of the polymorphic outcomes of a crystallization process, referred to as polymorph selection, can accelerate the process development for manufacturing solid products with targeted properties. Polymorph selection requires understanding the interplay between the thermodynamic and kinetic factors that drive nucleation. Moreover, post-nucleation events, such as crystal growth and polymorphic transformation, can affect the resulting crystal structures. Here, the nucleation kinetics of the Lennard-Jones (LJ) fluid from the melt is investigated with a focus on the competition between FCC and HCP crystal structures. Both molecular dynamics (MD) simulations and 2D free energy calculations reveal that polymorph selection occurs not during nucleation but when the cluster sizes exceed the critical cluster size. This result contrasts with the classical nucleation mechanism, where each polymorph is assumed to nucleate independently as an ideal bulk-like cluster, comprised only of its given structure. Using the 2D free energy surface and the MD simulation-derived diffusion coefficients, a structure-dependent nucleation rate is estimated, which agrees with the rate obtained from brute force MD simulations. Furthermore, a comprehensive population balance modeling (PBM) approach for polymorph selection is proposed. The PBM combines the calculated nucleation rate with post-nucleation kinetics while accounting for the structural changes of the clusters after nucleation. When applied to the LJ system, the PBM predicts with high accuracy the polymorphic distribution found in a population of crystals generated from MD simulations. Due to the non-classical nucleation mechanism of the LJ system, post-nucleation kinetic events are crucial in determining the structures of the grown crystals. [ABSTRACT FROM AUTHOR]

A series of experimental and numerical studies were carried out on the mechanical and geometric performance of an aerostructural part produced by a material out-of-autoclave stamp forming process using unidirectional (UD) carbon fiber (CF) reinforced polyetherketoneketone (PEKK), which provides advantages like reshaping, recycling, welding, and low serial manufacturing costs. As a novelty, initial part geometry, different types of springs, and their attachment type were examined experimentally and compared with simulations. Compression tests were performed to determine mechanical strengths which reach levels up to 550 MPa. In addition, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were conducted to determine the crystallinity which occurs depending on the cooling regimes of the material. The crystallinity has been observed to vary regionally ranging from 16 to 21%. However, the crystallinity of the part towards the cold mold region decreased from 20 to 17%. In addition, simulations were performed to observe and control the occurrence of wrinkles and other defects. [ABSTRACT FROM AUTHOR]

• Rapid cooling is effective for the anti-crystallization of rice husk silica ash. • Cooling pathway patterns are drawn in a uniform temperature-time diagram. • On the diagram, the border zone between the crystalline and amorphous phases is drawn. • The phase diagram is applicable for finding a cooling condition for anti-crystallization. • The border zone is different depending on the inorganic components of rice husk. Rice husk (RH), which is an abundant agricultural waste, consists of ca. 20 % silica (SiO 2 · n H 2 O). Upon RH combustion, a large amount of silica ash is generated. RH silica is originally amorphous; however, the ash is crystalized depending on the conditions of the combustion. Crystallization of RH occurs at a much lower temperature than that of pure SiO 2 due to the eutectic effects of minerals, such as Na and K, that are initially present in RH. Controlling for anti-crystallization is required for expanding the possibility of using RH ash that is abundantly generated by combustion. Here, RH is combusted, followed by a highly thermocontrolled investigation, and the time and temperature dependency of RH ash crystallization are studied. Crystallization is avoidable when the ash is rapidly cooled; for instance, 20 °C/min cooling can avoid crystallization even if the combustion temperature reaches 950 °C. Various pathway patterns for achieving temperature and cooling ratio are plotted on a uniform diagram of temperature vs. time. Furthermore, a border zone, indicating the regions in which RH ash becomes amorphous and crystals, is successfully drawn into the diagram by using the data maintained at a constant temperature. A comparison with a few different types of RH showed that the border zone on the diagram can move depending on their ratios of inorganic elements, causing a eutectic effect. [ABSTRACT FROM AUTHOR]

β-CaSiO 3 with a low dielectric constant and low dielectric loss is one of the decisive components of commercial calcium borosilicate (CBS) low-temperature co-fired ceramic substrate. However, achieving a high degree of crystallization of β-CaSiO 3 is difficult in CBS glass ceramics because of the competitive multiphase crystallization during sintering. We have shown that six-coordinated magnesium can be used to weaken the silicate network to achieve a high degree of crystallization of β-CaSiO 3 in CBS glass ceramics. The appropriate MgO content to ensure a large amount of MgO 6 production gradually destroys the [SiO 4 ] tetrahedral network as the temperature increases, resulting in a β-CaSiO 3 content of 76.2 vol%, when the MgO content is 2.71 mol%. The resulting material has the lowest dielectric constant (4.95@15 GHz) and dielectric loss (8 × 10−4@15 GHz), and the best three-point bend strength (77.43 MPa). Our work provides an effective method of changing the crystallization by modifying the glass network in silicate-based glass ceramics with a low dielectric constant. [ABSTRACT FROM AUTHOR]

The coexistence of two fragments, a chiral isosteviol moiety and an achiral pyridinoyl-hydrazone moiety, in the molecules of pyridinoyl-hydrazone derivatives of isosteviol results in the realization of two distinct supramolecular motifs in their crystals, namely, a true homochiral motif and a pseudosymmetric homochiral motif. [ABSTRACT FROM AUTHOR]

Vanillin crystals undergo needle-like morphology that results in poor flowability, crystal breakage, and low packing density. The spherical crystallization technology can produce particles with improved flowability and stability. A reverse antisolvent crystallization based on liquid-liquid phase separation is proposed in this work to produce vanillin spherical agglomerates. Hansen Solubility Parameters are applied to explain the liquid-liquid phase separation (LLPS) phenomenon. The Pixact Crystallization Monitoring system is applied to in-situ monitor the whole process. A six-step spherical crystallization mechanism is revealed based on the recorded photos, including the generation of oil droplets, nucleation inside oil droplets, the coalescence and split of oil droplets, crystal growth and agglomeration, breakage of oil droplets, and attrition of agglomerates. Different working conditions are tested to explore the best operation parameters and a frequency-conversion stirring strategy is proposed to improve the production of spherical crystals. [ABSTRACT FROM AUTHOR]

For a polymer/polymer dismissible blend with two crystallizable components, the crystallization behavior of different components and the reciprocal influences between different crystals are interesting and important, but did not investigate in detail. In this study, the L-poly(lactic acid)/polypropylene (PLLA/PP) blends with different weight ratios were prepared by melt mixing and the crystallization behavior of the blends were investigated. Results showed that the crystalline structures of PLLA and PP were not altered by the composition. For the crystallization of PLLA, both the diffusion of chain segments and crystallization rate were enhanced under the existence of PP crystals. For the crystallization of PP, its crystallization rate was depressed under the existence of amorphous PLLA molecular chains. When the PP crystallized from the existence of PLLA crystals, although the diffusion rate of PP was reduced by PLLA crystals, the nucleation positions were obviously enhanced, which accelerated the formation of PP crystals. This investigation would supply more basic data for the application of PLLA/PP blend. [ABSTRACT FROM AUTHOR]

The loading of nanoparticle in the polymer matrix affects their response to shear flows applied during the fabrication process. With this in mind, in the present study, the concurrent effect of carbon nanotube (CNT) presence and shear application on the rheological and electrical properties as well as on the crystallization behavior of polypropylene (PP) based nanocomposites has been investigated. The results of rheological analyses showed that the solid-like behavior increases in proportion to the CNT content, and a remarkable increase in the solid-like behavior is obtained at a CNT content of 2 wt%. The isothermal crystallization results corroborated that crystallization temperature increases proportionally with the CNT content, however does not change with shearing. The non-isothermal crystallization findings confirmed that crystallization kinetics promotes with increasing CNT content, and this effect becomes more pronounced with shearing. The results of thermal analysis confirmed that the melting temperature decreases slightly, and the crystallinity remains almost unchanged with increasing CNT content up to 2%. However, when the CNT content rose up to 4%, the crystallinity decreased significantly due to confined crystallization. When this nanocomposite was subjected to shearing, the crystallinity increased. The results of electrical conductivity measurement revealed that the conductivity increases with increasing CNT content, while it decreases with shearing and the vulnerability of nanocomposites to shearing decreases with increasing CNT content. [ABSTRACT FROM AUTHOR]

The surface gap of tephriphonolite compositions in the Passa Quatro alkaline complex, in SE Brazil, is attributed to non-buoyancy of these high viscosity intermediate compositions during magmatic fractional crystallization at different depths. Thermodynamic and Rayleigh models for three alkaline suites of a strongly silica-undersaturated series were integrated to demonstrate that parental (basanite, nephelinite and alkaline basalt) and residual (phonolites) magmas are cogenetic by fractional crystallization at pressures of 10 kbar and 5 kbar, i.e. at magma chambers located above and below the Conrad discontinuity within the Upper Cretaceous-Palaeogene 40 km-thick continental crust in SE Brazil. The fractional crystallization of the parental magmas produced an ultramafic residual solid (wehrlite, olivine-bearing clinopyroxenite and clinopyroxenite) and residual liquids (evolved basanite and alkaline basalt, and phonotephrite). The latter moved up and built magma chambers at lower depths in the continental crust where those magmas initially crystallized clinopyroxenite extracts and high viscosity residual liquid that was entrapped and prevented to ascent towards the surface. Then, an abrupt change in the extract mineralogy produced a feldspathic-rich extract (leucocratic leucite monzosyenite, mesocratic syenite or leucocratic monzodiorite) and a residual phonolitic liquid with low viscosity. Following the feldspar crystallization, the magma viscosity decreased, acquiring adequate buoyancy that resulted in shallow-crust magma chambers in which phonolite diversification took place. These processes occurred due to the existence of a transcrustal, plumbing architecture where the high viscosity intermediate tephriphonolites were prevented to reach shallower depths, resulting in the Daly gap observed in the Passa Quatro Alkaline Complex. [ABSTRACT FROM AUTHOR]

Two new zinc azole complexes incorporated Strandberg-type cluster-based solids, namely (Hpz)6{Zn(pz)4(H2O)2}[{Zn(pz)2P2Mo5O23}2]·8H2O (1) and (Himi)4{Zn(imi)3P2Mo5O23}·7H2O (2) were crystallized using isomeric azole ligands, i.e., pyrazole (pz) and imidazole (imi), respectively. While solid 1 crystallized in triclinic system with space group P-1 with cell parameters a = 9.5647(15), b = 12.558(2), c = 20.340(3) Å, α = 75.907(7), β = 84.727(6), γ = 87.525(7)°, Z = 1; 2 crystallized in orthorhombic system with space group P212121 having cell parameters a = 12.048(3), b = 19.561(5), c = 20.732(5) Å, Z = 4. Both pyrazole and imidazole can form a complex with zinc centres to form an extended solid in 1 and a derivatized Strandberg-type cluster in 2. Interestingly, 1 is a new supramolecular isomer of previously reported solid viz., (pz)[{Zn(pz)3}3{P2Mo5O23}]·2H2O and 2 is the only example wherein a zinc imidazole complex has derivatized a Strandberg-type cluster. Detailed structure analysis of 1 and 2 was carried out, and the role of tectons in dictating the self-assembly of these solids was evaluated. In addition, a solid-state photoluminescence study was carried out for 1 and 2 at room temperature. Two zinc azole complexes incorporated Strandberg-type cluster-based solids and have been crystallized. While 1 is a new supramolecular isomer of (pz)[{Zn(pz)3}3{P2Mo5O23}]·2H2O; 2 is the only example wherein a zinc imidazole complex has derivatized a Strandberg-type cluster. Apart from detailed structural analysis, solid-state photoluminescence of solids has also been investigated. [ABSTRACT FROM AUTHOR]

Amorphous silica has numerous high temperature applications due to its inherent thermal shock resistance and low coefficient of thermal expansion (CTE). However, at the high temperatures required for processing (>1200 °C), the metastable β-cristobalite phase preferentially forms and is accompanied by a volume change, and potential cracking, upon conversion to the low temperature α-cristobalite phase. The CTE of the final crystalline phase is an order of magnitude higher than its amorphous counterpart. Here experimental results demonstrate that small additions of B 4 C (3.5 wt%) effectively inhibit silica crystallization in powder and sintered gel-cast forms up to 22 h at temperatures as high as 1500 °C as confirmed via x-ray diffraction. The oxidation of B 4 C to B 2 O 3 and its subsequent melt and evaporation disrupts the nucleation and growth of the cristobalite phase. The mechanism for crystallization inhibition is further explored through optical microscopy to probe changes in surface morphology. [Display omitted] [ABSTRACT FROM AUTHOR]

During the blast furnace (BF) smelting process, the viscosity of BF slag affects greatly the quality of molten iron, slag-iron separation, gas flow distribution, etc. After discharged from BF, the crystallization of molten slag at low cooling rate will decrease the glass content and hydration activity of slag, which occurs more easily in the tempting heat recover system of molten slag for energy saving and emission reduction. The glassy slag at quite cooling rate is the valuable resource to replace virgin raw material to conserve the natural resource for producing the value-added materials, which facilitates the circular economy and sustainable development. This paper firstly describes the generation of BF slag, and discusses the research methods of viscosity-structure of the slag and detailed effects of basic oxides, acidic oxides and amphoteric oxides. Then, the characterization methods for crystallization of slag, determination of critical cooling rate, precipitated phases and the effect of chemical components are summarized. With regard to the preparation of glass-ceramics from BF slag, the effects of heat treatment, nucleation agent, addition amount of the slag and main chemical components are expounded. At last, the future challenges and attentions on the viscosity, crystallization and glass-ceramics preparation of BF slag are scrutinized. [ABSTRACT FROM AUTHOR]

In recent years, researchers have prepared glass-ceramics using a mixture of multiple solid waste materials, which is an effective and resourceful way to use and store solid waste. However, solid waste usually contains multiple heavy metals, which presents challenges during the mixing and co-solidification processes. In this study, high-performance glass-ceramics with low leaching were prepared from blast furnace slag (BFS). The synergistic curing mechanism of BFS glass-ceramics for heavy metals Cr, Mn, Cu, Zn, Ni, and Co was investigated in detail, as well as the migration pattern and storage state of heavy metals under different heat treatment stages and different Cr contents. The results show that the increases in temperature and Cr 2 O 3 content contribute to the incorporation of heavy metals into the crystal lattice and promote crystal growth. Excessive crystallization of spinel causes aggregation, which further curtails the leaching of heavy metals. The leaching concentration of heavy metals mainly depends on the heavy metal content in the glass network and the degree of network polymerization. Thus, spinel acts as a crystal core for the solidification of heavy metals, while augite and glass phases act as a double barrier to physically encapsulate them, which is effective for the storage of a wide range of heavy metals. Furthermore, the physical and chemical properties of BFS glass-ceramics are consistent with the Chinese industry standard "Glass-ceramics plate for industrial application" (JC/T 2097-2011). This study provides important theoretical support for the synergistic solidification of multiple heavy metals in glass-ceramics, as well as insights into the preparation of glass-ceramics by mixing BFS with other solid wastes. [Display omitted] [ABSTRACT FROM AUTHOR]

Anthraquinone-induced asymmetric N 3 −Sb−O coordination was constructed on C 3 N 4 matrix by a rapid and simple explosive crystallization approach, which contributes to selective O 2 photoreduction to H 2 O 2. [Display omitted] Achieving O 2 photoreduction to H 2 O 2 with high selectivity control and durability while using easily accessible catalyst requires new synthesis strategies. Herein, we propose an asymmteric Sb coordination active center strategy of introducing anthraquinone (AQ) and heptazine to form local N 3 − Sb − O coordination by a rapid and simple explosive crystallization approach, resulting in a mesoporous conjugated heptazine-amide-AQ polymer coordinated Sb (HAAQ-Sb). It is demonstrated that the N 3 − Sb − O coordination effectively suppresses the charge recombination and acts as the highly active site for O 2 adsorption. Moreover, as-introduced AQ units initiate low-barrier hydrogen transfer through a reversible redox process that triggers highly-efficient H 2 O 2 production. A superior apparent quantum yield of 20.2 % at 400 nm and a remarkable solar-to-chemical conversion efficiency of 0.71 % are achieved on the optimal HAAQ-Sb, which is the highest among C 3 N 4 -based photocatalysts at present. This asymmetric coordination concept and material design method provide new perspectives for the research of novel catalysts toward artificial photosynthesis. [ABSTRACT FROM AUTHOR]

Applicability of the Johnson-Mehl-Avrami (JMA) model beyond the typical range of the negative asymmetries of the crystallization peak was tested by means of theoretical simulations. Using the solid-state kinetic equation with implemented temperature dependences of either activation energy E or pre-exponential factor A, it was shown that the originally monotonically increasing transformation rate constant changes its evolution with temperature to a non-monotonous course, exhibiting a broad maximum. If the crystallization process following the non-isothermal JMA kinetics proceeds near this maximum, the asymmetry of the corresponding kinetic peak can gradually change to significantly positive values. Of particular interest are the cases with the JMA kinetic exponent m JMA ≥ 2, where the asymmetry of the JMA peaks changes with increasing heating rate from the typical negative values to largely positive values – such crystallization behavior was indeed observed for several chemically diverse materials (polymers, small organic molecules, chalcogenide and oxide glasses). [ABSTRACT FROM AUTHOR]

In this study, the theory of continuous crystallization from a supersaturated solution is developed, taking the concentration‐dependent fines dissolution, product removal, and feed supply rates into account. These rates make it possible to control the operation mode of the crystallizer and obtain the required supersaturation of the solution, the desired crystal‐size distribution in the supersaturated liquid, and the necessary crystal removal rate of the product. The steady‐ and unsteady‐state solutions of model equations are found analytically. It is shown that the non‐stationary crystal‐size distributions approach the stationary distribution with increasing time. The theory developed is the basis for investigating the linear and nonlinear stability of the crystallizer with allowance for the concentration‐dependent fines dissolution, product removal and feed supply rates. [ABSTRACT FROM AUTHOR]

Glass seals utilized in Solid Oxide Fuel Cells (SOFCs) can be subject to modification through the incorporation of oxide additives to bolster their mechanical strength. This research focuses on a novel class of additives, specifically protective coating materials designed for alloy interconnects. It is crucial to emphasize that the glass seal interfaces directly with the protective coating, bypassing direct contact with the alloy itself. The efficacy of this approach is exemplified through the utilization of Ni–Co spinel-based oxide, established as an effective protective substance for stainless steel interconnects. The introduction of a minute quantity of Ni–Co oxides does not induce alterations in the glass seal properties, encompassing phase structure, microstructure, thermal expansion coefficient (CTE), and softening behavior. The Ni–Co oxide additive serves to mitigate the glass devitrification tendency, leading to a substantial augmentation in shear strength at the seal-interconnect interface and a marked enhancement in sealing properties. The composite seal, enriched with 3.0 wt% Ni–Co oxide, showcases superior sealing performance, demonstrating exceptional stability throughout a rigorous 1200-h test. The average leakage rate during this test period stands at 0.0024 sccm⋅cm−1. The incorporation of Ni–Co oxide triggers the formation of needle-shaped crystals, playing a pivotal role in averting channel void formation and augmenting the bonding strength between the seal and interconnect. Consequently, this fortifies gas tightness, ensuring the maintenance of outstanding sealing performance over an extended duration. [Display omitted] • The Ni–Co spinel-based oxide was synthesized using the sol-gel method. • The additive significantly enhanced the bonding between seal & interconnect. • The sealing exhibited a very low leakage rate in gas-tightness experiments. • The stability of the sealing was observed to be excellent in long-term experiments. • This work provides a novel perspective for the selection of additives in seals. [ABSTRACT FROM AUTHOR]

Supramolecular self-assembly–directed two unique organogels were achieved by varying gel-immobilized solvents. One gel is comprised of adipic acid (ADP) and triethanolamine (TEA) in pure dimethylformamide medium (i.e., ADP-TEA-DMF), while the other is formed from the combination of adipic acid and triethanolamine in a 1 : 1 mixed solvent system of DMF and acetonitrile (i.e., ADP-TEA-DMF-MeCN). Furthermore, we observed robust crystallization behaviour under the different stoichiometric conditions of adipic acid with triethanolamine in pure dimethylformamide (i.e., Crystal-DMF) and in pure dimethyl sulfoxide (i.e., Crystal-DMSO). To evaluate the mechanical strength and viscoelastic attributes, rheological experiments were executed on these supramolecular organogels of ADP-TEA-DMF and ADP-TEA-DMF-MeCN. Additionally, comprehensive microstructural analyses were conducted in order to unravel the architectural variations arising from the involvement of different solvent-directed semi-solid gel-state. Scanning electron microscopy (FESEM) images of xerogel specimens obtained from the two organogels revealed distinctive morphological patterns. Notably, perceptible variations in the morphology were also observed in both the crystalline phases. The crystal structure of both the crystalline phases (i.e., Crystal-DMF and Crystal-DMSO) were explored using single crystal X-ray diffraction study at 296 K for Crystal-DMF and under liquid nitrogen atmosphere for Crystal-DMSO. Crystal-DMF and Crystal-DMSO have identical crystal structures that are composed of the adipate dianion (ADP2−) and the protonated triethanolamine (TEAH+). The crystal engineering pattern of Crystal-DMSO was elucidated through this study. These findings of versatile organogelation and robust crystallization emphasize the significance of solvent polarity and its diversity in attaining both the gel and crystalline phases. The organogel-formation strategy of ADP-TEA-DMF and ADP-TEA-DMF-MeCN was unravelled using infrared spectroscopic analyses. ESI-Mass spectral studies demonstrate the basic gel-constructing units, which are repeating to offer stable organogels. Thus, the solvent and the gelator concentration-directed organogelation process and the robust crystal-formation strategy are critically visualized in this study. [ABSTRACT FROM AUTHOR]

A novel one‐pot deracemization method using a bifunctional chiral agent (BCA) is proposed for the first time to convert a racemate to the desired enantiomer. Specifically, chiral α, (α‐diphenyl‐2‐pyrrolidinemethanol) formed enantiospecific cocrystals with racemic dihydromyricetin, and used its own alkaline catalysis to catalyze the racemization between the (2R,3R)‐enantiomer and (2S,3S)‐enantiomer in solution, achieving a one‐pot spontaneous deracemization. This strategy was also successfully extended to the deracemization of three other racemic compound drugs: (R,S)‐carprofen, (R,S)‐indoprofen, and (R,S)‐indobufen. The one‐pot deracemization method based on the BCA strategy provides a feasible approach to address the incompatibility between cocrystallization and racemization reactions that are commonly encountered in the cocrystallization‐induced deracemization process and opens a new window to develop essential enantiomerically pure pharmaceutical products with atom economy. [ABSTRACT FROM AUTHOR]

A novel one‐pot deracemization method using a bifunctional chiral agent (BCA) is proposed for the first time to convert a racemate to the desired enantiomer. Specifically, chiral α, (α‐diphenyl‐2‐pyrrolidinemethanol) formed enantiospecific cocrystals with racemic dihydromyricetin, and used its own alkaline catalysis to catalyze the racemization between the (2R,3R)‐enantiomer and (2S,3S)‐enantiomer in solution, achieving a one‐pot spontaneous deracemization. This strategy was also successfully extended to the deracemization of three other racemic compound drugs: (R,S)‐carprofen, (R,S)‐indoprofen, and (R,S)‐indobufen. The one‐pot deracemization method based on the BCA strategy provides a feasible approach to address the incompatibility between cocrystallization and racemization reactions that are commonly encountered in the cocrystallization‐induced deracemization process and opens a new window to develop essential enantiomerically pure pharmaceutical products with atom economy. [ABSTRACT FROM AUTHOR]

In a methylammonium‐free (MA‐free) composition, the uncontrollable crystallization process between Cs and formamidine (FA) currently hinders its efficiency enhancement, especially in inverted perovskite solar cells (PSCs). Here, a dual‐interface modification of perovskite films is proposed by simultaneously introducing additives and surface passivators. In particular, (aminomethyl)phosphonic acid (AMP) is introduced into the precursor solution to balance crystallization by inducing the preferential crystallization of FA through the specific formation of strong hydrogen bonds with FA. In addition, AMP spontaneously sinks and anchors to the buried interface to fill the voids of the self‐assembled monolayer (SAM) via the covalent bonds formed by ─PO3H2 and FTO. Subsequently, by the sequential modification of perovskite surface with 2‐(3‐fluorophenyl)ethylamine iodide (mF‐PEAI) and piperazine diiodide (PDI), a uniform surface potential is achieved and recombination losses at the interface are minimized. Notably, the dual‐interface‐modified inverted MA‐free PSCs achieve a state‐of‐the‐art power conversion efficiency (PCE) of 25.35% (certified: 24.87%) with a satisfactory Voc of 1.17 V based on the bandgap of 1.52 eV. Importantly, the unencapsulated devices maintain 92.8% and 91.7% of the initial efficiency after 1000 h of maximum power output (MPP) tracking and >800 h of heating at 85 °C, respectively, confirming excellent operational and thermal stability. [ABSTRACT FROM AUTHOR]

Metallic alloy fuels from fast reactors will be reprocessed by a non‐aqueous electrochemical technique known as electrorefining. Electrorefining of spent metal fuel results in the accumulation of heat‐generating fission products, especially 137Cs in the eutectic salt. These fission products need to be removed from the salt so as to reduce the decay heat load and contamination. The melt crystallization technique is a simple separation process being pursued for the separation of fission products. This is a single‐step process that utilizes the difference in solubility of fission products in the solid and liquid phase. This process is also less energy intensive. Crystallization involves the purification of a substance from a liquid mixture by solidification of the desired component. Since separation is based on selective solidification, which involves phase change, it is essential to evaluate the transient solidification pattern, liquid fraction distribution, solute distribution, and separation time and efficiency. Numerical modeling of the separation of CsCl from a LiCl‐KCl eutectic mixture has been carried out using Ansys Fluent (19.2). The effect of crystallizer geometry and cooling rates on the separation of CsCl has been numerically simulated. [ABSTRACT FROM AUTHOR]

Recent techniques for forming thermoplastics, such as welding, automated fibre placement or additive manufacturing, generate successive rapid heating and cooling cycles that cause the partial melting of crystals during the process. The melting of an interface is essential to guarantee a good molecular diffusion across the welded parts. Nevertheless, no model can correctly predict the melting kinetics and consequently the evolution of the crystalline degree during the layers' deposition process. The purpose of this paper was to define the melting kinetics depending on the crystallization conditions for polyetheretherketone (PEEK). Firstly, a non-isothermal crystallization model was proposed over a wide range of cooling rates from 0.1 K.s−1 to 150 K.s−1. Experimental results have highlighted a dual-mode behaviour of melting and demonstrated the dependence of melting temperatures on crystallization conditions. Based on these observations, a model was developed to predict the melting behaviour after non-isothermal crystallization. The melting model revealed that after high cooling rates, primary and secondary crystals melt separately at low temperatures, while after slow cooling rates, both structures melt simultaneously at higher temperatures. Finally, the melting model was applied to the FFF thermal cycle to illustrate the influence of process parameters on the melting kinetics during deposition. [ABSTRACT FROM AUTHOR]

Self-assembly formation is a key research topic for realizing practical applications in swarm robotics. Due to its inherent complexity, designing high-performance self-assembly formation strategies and proposing corresponding macroscopic models remain formidable challenges and present an open research frontier. Taking inspiration from crystallization, this paper introduces a distributed self-assembly formation strategy by defining free, moving, growing, and solid states for robots. Robots in these states can spontaneously organize into user-specified two-dimensional shape formations with lattice structures through local interactions and communications. To address the challenges posed by complex spatial structures in modeling a macroscopic model, this work introduces the structural features estimation method. Subsequently, a corresponding non-spatial macroscopic model is developed to predict and analyze the self-assembly behavior, employing the proposed estimation method and a stock and flow diagram. Real-robot experiments and simulations validate the flexibility, scalability, and high efficiency of the proposed self-assembly formation strategy. Moreover, extensive experimental and simulation results demonstrate the model's accuracy in predicting the self-assembly process under different conditions. Model-based analysis indicates that the proposed self-assembly formation strategy can fully utilize the performance of individual robots and exhibits strong self-stability. [ABSTRACT FROM AUTHOR]

Organic photovoltaics (OPVs) have attracted widespread attention and became an important member of clean energy. Recently, their power conversion efficiency (PCE) has surpassed 19%. As is well known, the morphology of the active layer in OPVs crucially influences the PCE. In consideration of the intricate interactions between the donor molecules and acceptor molecules, the precise control of the morphology of the active layer is extremely challenging. Hence, it is urgent to develop effective methods to fabricate the hierarchical structure of the active layer. One significant driving force for the morphological evolution of the active layer is crystallization. Therefore, regulating the crystallization kinetics is an effective strategy for morphology control. In this review, we present the kinetic strategies recently developed to highlight their significance and effectiveness in morphology control. By applying these kinetic strategies, the hierarchical structure, including phase separation, domain size, crystallinity, and molecular orientation of the active layer can be optimized in different blend systems, leading to an improved PCE of OPVs. The outcomes set the stage for future advancements in device performance. [ABSTRACT FROM AUTHOR]

Large-Scale Material Extrusion (LS-MEX) is increasingly being used in small-scale production and prototyping due to its ability to create components in new temporal and spatial dimensions. However, the use of this manufacturing process poses microscopic and macroscopic challenges not encountered in previous small-scale production systems. These challenges arise primarily from the prolonged retention of heat in the material, which leads to insufficient strength in the extruded strands at the macrostructural level. As a result, the component can collapse, a phenomenon known as 'slumping'. Thermal energy also influences microstructural changes, such as crystallisation kinetics, which affect properties such as the strength and stiffness of the final product. The duration and dynamics of thermal energy are influenced by manufacturing parameters and the possible use of additional peripheral equipment, which affects component quality. In this study, the influence of thermal energy on structural processes through simulations of polyamide 6 with 40% carbon fibres (PA6 wt.%40 CF) is investigated. The results show that by adjusting the process parameters and using modification units, the thermal profile of the material can be accurately controlled, which allows the microstructural processes to be precisely controlled. This leads to the targeted modification of the macroscopic material properties. The focus of this work is on the combination of numerical simulations of the LS-MEX process with semi-empirical methods for the analysis of crystallisation processes. The application of the Nakamura model, which is used throughout similar investigations, allows a detailed description and prediction of the crystallisation kinetics during the manufacturing process. The study shows that the absolute degree of crystallisation can be determined with simplified assumptions using a combination of thermal simulations and semi-empirical approaches. It was found that the absolute degree of crystallisation increases from the outer interface of the strand to the print bed across the cross-section. This can be attributed to the specific thermal boundary conditions and the resulting temperature profiles at different points. [ABSTRACT FROM AUTHOR]

The crystallization of paramagnetic species in a magnetic field gradient under microgravity-like conditions is an area of interest for both fundamental and applied science. In this paper, a setup for the crystallization of paramagnetic species in the magnetic field up to 7 T generated by a superconducting magnet is described. The research includes calculations of the conditions necessary to compensate for the gravitational force for several types of paramagnetic substances using the magnetic field of superconducting magnets (4.7 T, 7 T, 9.4 T, and 16.4 T). Additionally, for the first time, the crystallization of copper sulfate and cobalt sulfate, as well as a mixture of copper sulfate and cobalt sulfate under gravitational force compensation in a superconducting magnet, was performed. This paper experimentally demonstrates the feasibility of growing paramagnetic crystals within the volume of a test tube on the example of copper and cobalt sulfate crystals. A comparison of crystals grown from the solution of a mixture of copper and cobalt sulfates under the same conditions, with and without the presence of a magnetic field, showed changes in both the number and size of crystals. [ABSTRACT FROM AUTHOR]

Mounting experimental evidence supports the existence of a liquid--liquid transition (LLT) in high-pressure supercooled water. However, fast crystallization of supercooled water has impeded identification of the LLT line TLL(p) in experiments. While the most accurate all-atom (AA) water models display a LLT, their computational cost limits investigations of its interplay with ice formation. Coarse-grained (CG) models provide over 100-fold computational efficiency gain over AA models, enabling the study of water crystallization, but have not yet shown to have a LLT. Here, we demonstrate that the CG machine-learned water model Machine-Learned Bond-Order Potential (ML-BOP) has a LLT that ends in a critical point at Pc = 170 ± 10 MPa and Tc = 181 ± 3 K. The TLL(p) of ML-BOP is almost identical to the one of TIP4P/2005, adding to the similarity in the equation of state of liquid water in both models. Cooling simulations reveal that ice crystallization is fastest at the LLT and its supercritical continuation of maximum heat capacity, supporting a mechanistic relationship between the structural transformation of water to a low-density liquid (LDL) and ice formation. We find no signature of liquid-liquid criticality in the ice crystallization temperatures. ML-BOP replicates the competition between formation of LDL and ice observed in ultrafast experiments of decompression of the high-density liquid (HDL) into the region of stability of LDL. The simulations reveal that crystallization occurs prior to the coarsening of the HDL and LDL domains, obscuring the distinction between the highly metastable first-order LLT and pronounced structural fluctuations along its supercritical continuation. [ABSTRACT FROM AUTHOR]

Currently, narrowband light‐convertor is critically urgent for preeminent color representation in lighting and display fields, however, the development of target materials still remains challenging. Herein, glass ceramic (GC) composite based on in situ glass crystallization, where the condense glass network structure acts as effective obstructors for long distance ion diffusion, is elaborately designed to inhibit activators' multi‐sites occupation for acquiring narrowband emitting. Following this strategy, an unprecedented narrowband blue emission of Eu2+‐activators with a peak at 447 nm and full‐width of half maximum (FWHM) of ≈30 nm is developed in a new type of Sr5(PO4)3Cl (SPOCl) GC composite. The Eu2+‐activators' hindered diffusion inside the GC composite makes preferential and limit occupation of the [Sr1O9] sites, enabling narrowband blue luminescence. Furthermore, the GC composite highlights remarkable performance in high‐power violet‐excitable full‐spectrum lighting and transparent display (TD) prototype fields, due to its high color purity (≈98.1%), photoluminescence quantum field (PLQY, ≈80.5%) and thermal stability (≈82.1%@150 °C). This work not only promotes the profound understanding of the relationship between light manipulation and glass crystallization, but also paves the way toward the implementation of high‐quality lighting and display of GC composites. [ABSTRACT FROM AUTHOR]

In this study, Gd 2 O 3 –Ga 2 O 3 -GeO 2 -Nd 2 O 3 glasses and glass ceramics were synthesized, and their structural, thermal, and crystallization characteristics were analyzed. Our findings indicate that substituting Gd 2 O 3 for Ga 2 O 3 positively influences the enhancement of bridge oxygen content and network structure stability. Heat treatments at different temperatures showed no significant impact on the crystal phase type but did alter the crystallization rate. Optimal conditions were identified: a Gd 2 O 3 /Ga 2 O 3 ratio of 0.6 facilitated the production of transparent glass ceramics containing a single-phase GdGaGe 2 O 7 nano-crystal. Notably, the glass ceramic nucleated at 780 °C for 24 h and crystallized at 840 °C for 5 min exhibited superior performance. Despite a 6% reduction in transmission rate, the emission intensity at 1060 nm increased by 1.5 times. This material holds promise for various applications in solid-state lasers operating within the 1.06 μm region. [ABSTRACT FROM AUTHOR]

The tetracyanamidometallates Li4[T(CN2)4] with T=Si, Ge were prepared by solid‐state metathesis (SSM) reactions between TI4 and Li2(CN2). The new compounds Li4[T(CN2)4] are obtained as crystalline phases in high yields and represent the most basic examples of the family of tetracyanamidometallates. The formation of these compounds, via SiI4 and Li2(CN2), is analyzed by means of differential scanning calorimetry (DSC). The [Si(CN2)4]4− ion in the structure of Li4[Si(CN2)4] can be considered an analogue to the [SiO4]4− ion in Li4SiO4. The crystal structures of Li4[T(CN2)4] were solved and refined isotypically on the basis of single‐crystal X‐ray diffraction data in the space group C2/c, and further characterized by infrared and solid‐state NMR techniques. [ABSTRACT FROM AUTHOR]

Meniscus‐guided coating (MGC) is a promising method that offers predictable fabrication of highly crystalline thin films. For the integration of molecular semiconductors into large‐area electronic devices with high efficiency and reliability, homogeneous and highly ordered film morphologies are required. The solution processing of such defect‐free film structures requires comprehensive understanding of the complex relationship between molecular crystallization, fluid dynamics, and meniscus shape. In this work, the role of the meniscus shape on fluid dynamics in the coating bead and the crystallization process of the low molecular weight semiconductor 6,13‐bis(triisopropylsilylethynyl)pentacene (TIPS‐pentacene) during zone‐casting is systematically investigated. Depending on meniscus shape and coating velocity, four morphological subregimes are found: stick‐slip morphology, unidirectional homogenous crystal stripes, spherulitic morphology, and directional branched morphology; of which the second exhibits the highest crystallinity with a reduced trap density in the thin film, resulting in improved saturation and effective mobilities in field‐effect transistors (FET). Numerical simulation of fluid dynamics explains the observed morphological trends, which are correlated with the electrical behavior of the devices. This work provides a fundamental basis for upscaling MGC methods for the application of functional thin films. [ABSTRACT FROM AUTHOR]

Crystallizing molecules with long flexible chains is a challenge, making it difficult to perform X‐ray crystallography. Chaperones can assist in the crystallization of compounds that do not crystallize by themselves by producing solvate crystals that contain the analyte in their three‐dimensional lattices. Among the most versatile chaperones for liquid analytes are tetraaryladamantanes (TAAs), but the size of the compounds that can be encapsulated is limited, and attempts to surpass this limit with known TAAs were unsuccessful. Here we report that 1,3,5,7‐tetrakis(2‐fluoro‐4‐methoxyphenyl)adamantane (TFM) is a crystallization chaperone for acyclic molecules up to the molecular weight of phytyl acetate (338 g/mol). Encapsulation of such a large acyclic compound was achieved when the analyte was esterified and when a two‐step temperature protocol was used for crystallization. Exploratory work indicates that a drop to −20 °C allows for encapsulation of squalene (Mr 411 g/mol), albeit with positional disorder of the analyte. Our X‐ray crystal structures of solvates with flexible analytes shed light on how crystalline order can be imposed on large acyclic analytes. The new, fluorinated TAA gives access to crystal structures that were inaccessible thus far. [ABSTRACT FROM AUTHOR]

This communication reports an effective strategy helping address the long‐troubling melt processing issue of isotactic polybutene‐1 (i‐PB) caused by its extremely slow II‐I crystal phase transition. The solution lies in a facile synthesis of i‐PB containing H‐shape long‐chain‐branching structures (LCB‐i‐PB) by applying a so‐called ω‐alkenylmethyldichlorosilane copolymerization‐hydrolysis (ACH) chemistry to butene‐1 polymerization with Ziegler–Natta or metallocene catalysts. It is evident that the H‐shape LCB structures effectively enhance chain entanglements of i‐PB and induce an over‐the‐board acceleration of the overall melt crystallization process including nucleation, form II crystallization, and form II‐form I phase transition. As i‐PB usually requires up to a week to reach equilibrium of the II‐I phase transition, it is found that with LCB‐i‐PB such a transition is almost finished within as short as 24 h to even higher degrees. [ABSTRACT FROM AUTHOR]