Recovery and facets for deformation twins in minerals and metals.

Type II and IV twins with irrational twin boundaries are studied by high-resolution transmission electron microscopy in two plagioclase crystals. The twin boundaries in these and in NiTi are found to relax to form rational facets separated by disconnections. The topological model (TM), amending the classical model, is required for a precise theoretical prediction of the orientation of the Type II/IV twin plane. Theoretical predictions also are presented for types I, III, V, and VI twins. The relaxation process that forms a faceted structure entails a separate prediction from the TM. Hence, faceting provides a difficult test for the TM. Analysis of the faceting by the TM is in excellent agreement with the observations.

Catalytic-assembly of programmable atom equivalents.

Escape from metastable states in self-assembly of colloids is an intractable problem. Unlike the commonly adopted approach of thermal annealing, the recently developed enthalpy-mediated strategy provided a different option to address this dilemma in a dynamically controllable manner at room temperature. However, it required a complex catalytic-assembly DNA strand-displacement circuitry to mediate interaction between multiple components. In this work, we present a simple but effective way to achieve catalytic-assembly of DNA-functionalized colloidal nanoparticles, i.e., programmable atom equivalents, in a far-from-equilibrium system. A removable molecule named "catassembler" that acts as a catalyst was employed to rectify imperfect linkages and help the system escape from metastability without affecting the assembled framework. Notably, catalytic efficiency of the catassembler can be effectively improved by changing the seesaw catassembler in toehold length design or numbers of the repeat units. Leveraging this tractable catalytic-assembly approach, different ordered architectures were easily produced by directly mixing all reactants, as in chemical reactions. By switching bonding identities, solid-solid phase transformations between different colloidal crystals were achieved. This work opens up an avenue for programming colloid assembly in a far-from-equilibrium system.

Nanoscale Operando Imaging of Electrically Driven Charge-Density Wave Phase Transitions.

Structural transformations in strongly correlated materials promise efficient and fast control of materials' properties via electrical or optical stimulation. The desired functionality of devices operating based on phase transitions, however, will also be influenced by nanoscale heterogeneity. Experimentally characterizing the relationship between microstructure and phase switching remains challenging, as nanometer resolution and high sensitivity to subtle structural modifications are required. Here, we demonstrate nanoimaging of a current-induced phase transformation in the charge-density wave (CDW) material 1T-TaS2. Combining electrical characterizations with tailored contrast enhancement, we correlate macroscopic resistance changes with the nanoscale nucleation and growth of CDW phase domains. In particular, we locally determine the transformation barrier in the presence of dislocations and strain, underlining their non-negligible impact on future functional devices. Thereby, our results demonstrate the merit of tailored contrast enhancement and beam shaping for advanced operando microscopy of quantum materials and devices.

Laser-Printed Photoanode: Femtosecond Laser-Induced Crystalline Phase Transformation of WO3 Nanorods for Space-Efficient and Flexible Thin-Film Solar Water-Splitting Cells.

Despite its potential for clean hydrogen harvesting, photoelectrochemical (PEC) water-splitting cells face challenges in commercialization, particularly related its harvesting performance and productivity at an industrial scale. Herein, a facile fabrication method of flexible thin-film photoanode for PEC water-splitting to overcome these limitations, based on laser processing technologies, is proposed. Laser-induced graphene, a carbon structure produced through direct laser writing carbonization (DLWC), plays a dual role: a flexible and stable current collector and a substrate for the hydrothermal synthesis of tungsten trioxide (WO3) nanorods (NRs). To facilitate water-splitting, a femtosecond-pulsed laser (fs laser) is focused on the WO3 NRs, converting their crystalline phase from pristine orthorhombic to monoclinic structure without thermal damage. With NiFe layered double hydroxide (LDH) catalyst, the flexible thin-film photoanode exhibits good PEC performance (1.46 mA cm-2 at 1.23 VRHE) and retains ≈90% of its performance after 3000 bending cycles. With its excellent mechanical properties, the flexible photoanode can be operated in various shapes with different curvatures, enabling space-efficient PEC water-splitting by loading larger photoanode within a given space. This study is expected to contribute to the advancement of large-scale solar water-splitting cells, introducing a new approach to enhance H2/O2 production and expand its application range.

Classification and Simulation of Structural Phase Transformation-Induced Interfacial Defects in Group VI Transition-Metal Dichalcogenide Monolayers.

Polymorphic 2D materials have recently emerged as promising candidates for use in nanoelectronic devices by way of their ability to undergo structural phase transformations induced by external fields. Under cyclic transformations, however, induced interfacial defects may proliferate and compromise the system properties. Herein, we first employ geometric analysis to classify such defects generated during the 2H ↔ 1T and 2H ↔ 1T' transformations in group VI transition-metal dichalcogenide monolayers. Then, simulations of a mesoscale model with atomistic spatial resolution are conducted to assess the proliferation of such defects during cyclic 2H ↔ 1T transformations. It is shown that defect densities reach a steady state, with the 2H phase remaining more pristine than the 1T and 1T' states. We expect that the effects of these defects on the device performance are application-dependent and will require further inquiry.

Laser-Driven Transient Phase Oscillations in Individual Spin Crossover Particles.

An unusual expansion dynamics of individual spin crossover nanoparticles is studied by ultrafast transmission electron microscopy. After exposure to nanosecond laser pulses, the particles exhibit considerable length oscillations during and after their expansion. The vibration period of 50-100 ns is of the same order of magnitude as the time that the particles need for a transition from the low-spin to the high-spin state. The observations are explained in Monte Carlo calculations using a model where elastic and thermal coupling between the molecules within a crystalline spin crossover particle govern the phase transition between the two spin states. The experimentally observed length oscillations are in agreement with the calculations, and it is shown that the system undergoes repeated transitions between the two spin states until relaxation in the high-spin state occurs due to energy dissipation. Spin crossover particles are therefore a unique system where a resonant transition between two phases occurs in a phase transformation of first order.

Redox phase transformations in magnetite nanoparticles: impact on their composition, structure and biomedical applications.

Magnetite nanoparticles (NPs) are one of the most investigated nanomaterials so far and modern synthesis methods currently provide an exceptional control of their size, shape, crystallinity and surface functionalization. These advances have enabled their use in different fields ranging from environmental applications to biomedicine. However, several studies have shown that the precise composition and crystal structure of magnetite NPs depend on their redox phase transformations, which have a profound impact on their physicochemical properties and, ultimately, on their technological applications. Although the physical mechanisms behind such chemical transformations in bulk materials have been known for a long time, experiments on NPs with large surface-to-volume ratios have revealed intriguing results. This article is focused on reviewing the current status of the field. Following an introduction on the fundamental properties of magnetite and other related iron oxides (including maghemite and wüstite), some basic concepts on the chemical routes to prepare iron oxide nanomaterials are presented. The key experimental techniques available to study phase transformations in iron oxides, their advantages and drawbacks to the study of nanomaterials are then discussed. The major section of this work is devoted to the topotactic oxidation of magnetite NPs and, in this regard, the cation diffusion model that accounts for the experimental results on the kinetics of the process is critically examined. Since many synthesis routes rely on the formation of monodisperse magnetite NPs via oxidation of wüstite counterparts, the modulation of their physical properties by crystal defects arising from the oxidation process is also described. Finally, the importance of a precise control of the composition and structure of magnetite-based NPs is discussed and its role in their biomedical applications is highlighted.

Localized Soft Vibrational Modes and Coherent Structural Phase Transformations in Rutile TiO2 Nanoparticles under Negative Pressure.

We study the effect of size on the vibrational modes and frequencies of nanoparticles, by applying a newly developed, robust, and efficient first-principles-based method that we present in outline. We focus on rutile TiO2, a technologically important material whose bulk exhibits a softening of a transverse acoustic mode close to q=(12,12,14), which becomes unstable with the application of negative pressure. We demonstrate that, under these conditions, nanoparticles above a critical size exhibit unstable localized modes and we calculate their characteristic localization length and decomposition with respect to bulk phonons. We propose that such localized soft modes could initiate coherent structural phase transformations in small nanoparticles above a critical size.

Lanthanide Contraction in LnF3 (Ln = Ce-Lu) and Its Chemical and Structural Consequences: Part 1: Location of YF3 in the LnF3 Series According to Its Chemical and Structural Characteristics.

A lanthanide contraction(LC) of 14 lanthanides (Ln) from 58Ce to 71Lu consists of the interaction of Ln nucleus with 4f-electrons. Rare earth elements (REEs-R) include Sc, Y, La, and 14 Ln. They are located in 4-6th periods of the subgroup of group III. The electronic structure divides R into short (d- Sc, Y, La) and long (14 f-elements Ce-Lu) homologous series. The most important chemical consequence of LC is the creation of a new conglomerate of 16 RF3 by mixing fluorides of d- (Y, La) and f-elements. This determines the location of YF3 among LnF3. The location of YF3 depends on the structural (formula volumes-Vform) and thermochemical (temperatures and heats of phase transformations, phase diagrams) properties. The location of YF3 between HoF3 and ErF3 was determined by Vform at a standard pressure (Pst) and temperature (Tst). The location of YF3 according to heats of phase transformations ΔHfus and ΔHtrans is in a dimorphic structural subgroup (SSGr) D (Ln = Er-Lu), but without the exact "pseudo ZY". According to the temperatures of phase transformations (Ttrans) in LnF3 (Ln = Dy-Lu), YF3 is located in the SSGr D between ErF3 and TmF3. The ErF3-YF3 and YF3-TmF3 phase diagrams show it to be between ErF3 and TmF3. The crystals of five ß-LnF3 (Ln = Ho-Lu) and ß-YF3 were obtained in identical conditions and their crystal structures were studied. Vform (at Pst and Tst) with "pseudo" atomic numberZY = 67.42 was calculated from the unit cell parameters, which were defined with ±5 × 10-4 Å accuracy. It determines the location of YF3 between HoF3 and ErF3.

Antioxidant Triggered Metallic 1T' Phase Transformations of Chemically Exfoliated Tungsten Disulfide (WS2 ) Nanosheets.

Developing facile methods for inducing phase transformation between metallic and semiconducting 2D transition metal dichalcogenide (TMDC) materials is crucial toward leveraging their use in cutting-edge energy devices. Herein, 2H-to-1T' phase transformations in chemically exfoliated Tungsten Disulfide (WS2 ) nanosheet films, triggered by antioxidants toward highly conductive 2D TMDC electrode materials, are introduced. It is found that antioxidants cause residual LiOx compounds to reduce to Li metal, subsequently inducing 1T' phase transformations in layered WS2 nanosheets, resulting in significantly enhanced conductivity across the overall films. Both thermoelectric devices and supercapacitors are fabricated utilizing the highly conductive 1T' phase WS2 nanosheet films as a working electrode, allowing for outstanding performance due to the increased conductivity of the WS2 nanosheet films. The method constitutes a facile approach toward the use of chemically exfoliated 1T' TMDC nanosheets for highly efficient energy device applications.

Dual Responsive Molecular-Arm Modified Single Enzyme Molecules for Efficient Cellulose Hydrolysis.

Immobilizing cellulase for improving its hydrolysis activity and recyclability is critical for a cost-effective and environment-friendly conversion of cellulosic biomass. However, developing a strategy for achieving a high mass-transfer rate and good separation efficiency between an insoluble cellulose substrate and cellulase remains difficult. Instead of the traditional method, a single-enzyme molecular modification method is used in this study. To modify cellulase and provide it with a temperature-pH dual responsive property, systemized poly(acrylic-acrylonitrile) (PAA-PAN) molecular arms are used. The modified cellulase can reversibly transform between liquid and solid phases. In the liquid phase, the modified cellulase can adjust its active center, increasing its hydrolysis efficiency and separation efficiency. Cellulase and glucose products can be easily separated in the solid phase, allowing the reuse of cellulase. The results show that the modified cellulase's hydrolysis efficiency is comparable to that of free cellulase and that the modified enzyme preserves more than 60% of its initial activity after 15 batches of efficient hydrolysis. Thus, the proposed modification route considerably lowers the cost of cellulose enzymatic hydrolysis.

Induced side-branching in smooth and faceted dendrites: theory and phase-field simulations.

The present work is devoted to the phenomenon of induced side branching stemming from the disruption of free dendrite growth. We postulate that the secondary branching instability can be triggered by the departure of the morphology of the dendrite from its steady state shape. Thence, the instability results from the thermodynamic trade-off between non monotonic variations of interface temperature, surface energy, kinetic anisotropy and interface velocity within the Gibbs-Thomson equation. For the purposes of illustration, the toy model of capillary anisotropy modulation is prospected both analytically and numerically by means of phase-field simulations. It is evidenced that side branching can befall both smooth and faceted dendrites, at a normal angle from the front tip which is specific to the nature of the capillary anisotropy shift applied. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Transport phenomena in complex systems (part 2).

This theme issue, in two parts, continues research studies of transport phenomena in complex media published in the first part (Alexandrov & Zubarev 2021 Phil. Trans. R. Soc. A 379, 20200301. (doi:10.1098/rsta.2020.0301)). The issue is concerned with theoretical, numerical and experimental investigations of nonlinear transport phenomena in heterogeneous and metastable materials of different nature, including biological systems. The papers are devoted to the new effects arising in such systems (e.g. pattern and microstructure formation in materials, impacts of external processes on their properties and evolution and so on). State-of-the-art methods of numerical simulations, stochastic analysis, nonlinear physics and experimental studies are presented in the collection of issue papers. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Thermal Conductivity of Solid Triphenyl Phosphite.

The thermal conductivity, κ, of solid triphenyl phosphite was measured by using the transient hot-wire method, and its temperature and pressure dependencies were analyzed to understand heat transfer processes in the solid polymorphic phases, as well as in the glass and the exotic glacial state. Phase transformations and the structural order of the phases are discussed, and a transitional pressure-temperature diagram of triphenyl phosphite is presented. The thermal conductivity of both the crystalline and disordered states is described within the theory of two-channel heat transfer by phonons and diffusons in dielectric solids. In the glass and glacial states, the weakly temperature-dependent (glass-like) κ is described well by the term associated with heat conduction of diffusons only, and it can be represented by an Arrhenius-type function. In the crystal phases, the strongly temperature-dependent (crystal-like) κ associated with heat transfer by phonons is weakened by significant heat transfer by diffusons, and the extent of the two contributions is reflected in the temperature dependence of κ. We find that the contribution of diffusons in the crystal phases depends on pressure in the same way as that in amorphous states, thus indicating that the same mechanism is responsible for this channel of heat transfer in crystals and amorphous states.

Origami and materials science.

Origami, the ancient art of folding thin sheets, has attracted increasing attention for its practical value in diverse fields: architectural design, therapeutics, deployable space structures, medical stent design, antenna design and robotics. In this survey article, we highlight its suggestive value for the design of materials. At continuum level, the rules for constructing origami have direct analogues in the analysis of the microstructure of materials. At atomistic level, the structure of crystals, nanostructures, viruses and quasi-crystals all link to simplified methods of constructing origami. Underlying these linkages are basic physical scaling laws, the role of isometries, and the simplifying role of group theory. Non-discrete isometry groups suggest an unexpected framework for the design of novel materials. This article is part of the theme issue 'Topics in mathematical design of complex materials'.

Transport phenomena in complex systems (part 1).

The issue, in two parts, is devoted to theoretical, computational and experimental studies of transport phenomena in various complex systems (in porous and composite media; systems with physical and chemical reactions and phase and structural transformations; in biological tissues and materials). Various types of these phenomena (heat and mass transfer; hydrodynamic and rheological effects; electromagnetic field propagation) are considered. Anomalous, relaxation and nonlinear transport, as well as transport induced by the impact of external fields and noise, is the focus of this issue. Modern methods of computational modelling, statistical physics and hydrodynamics, nonlinear dynamics and experimental methods are presented and discussed. Special attention is paid to transport phenomena in biological systems (such as haemodynamics in stenosed and thrombosed blood vessels magneto-induced heat generation and propagation in biological tissues, and anomalous transport in living cells) and to the development of a scientific background for progressive methods in cancer, heart attack and insult therapy (magnetic hyperthermia for cancer therapy, magnetically induced circulation flow in thrombosed blood vessels and non-contact determination of the local rate of blood flow in coronary arteries). The present issue includes works on the phenomenological study of transport processes, the derivation of a macroscopic governing equation on the basis of the analysis of a complicated internal reaction and the microscopic determination of macroscopic characteristics of the studied systems. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

Ostwald ripening in the presence of simultaneous occurrence of various mass transfer mechanisms: an extension of the Lifshitz-Slyozov theory.

The Ostwald ripening stage of a phase transformation process with allowance for synchronous operation of various mass transfer mechanisms (volume diffusion and diffusion along the block boundaries and dislocations) and the initial condition for the particle-radius distribution function is theoretically studied. The initial condition is taken from the analytical solution describing the intermediate stage of a phase transition process. The present theory focuses on relaxation dynamics from the beginning of the ripening process to its final asymptotic state, which is described by the previously constructed theories (Slezov VV. et al. 1978 J. Phys. Chem. Solids 39, 705-709. (doi:10.1016/0022-3697(78)90002-1) and Alexandrov & Alexandrova 2020 Phil. Trans. R. Soc. A 378, 20190247. (doi:10.1098/rsta.2019.0247)). An evolutionary behaviour of particle growth rates dependent on various mass transfer mechanisms and time is analytically described. The boundaries of the transition layer, which surround the blocking point, are found. The fundamental and relaxation contributions to the particle-radius distribution function are derived for the simultaneous occurrence of various mass transfer mechanisms. The left branch of this function is shifted to smaller particle radii whereas its right branch extends to the right of the blocking point as compared with the asymptotic universal distribution function. The theory under consideration well agrees with experimental data. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

The shape of dendritic tips: a test of theory with computations and experiments.

This article is devoted to the study of the tip shape of dendritic crystals grown from a supercooled liquid. The recently developed theory (Alexandrov & Galenko 2020 Phil. Trans. R. Soc. A 378, 20190243. (doi:10.1098/rsta.2019.0243)), which defines the shape function of dendrites, was tested against computational simulations and experimental data. For a detailed comparison, we performed calculations using two computational methods (phase-field and enthalpy-based methods), and also made a comparison with experimental data from various research groups. As a result, it is shown that the recently found shape function describes the tip region of dendritic crystals (at the crystal vertex and some distance from it) well. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

A review on the theory of stable dendritic growth.

This review article summarizes the main outcomes following from recently developed theories of stable dendritic growth in undercooled one-component and binary melts. The nonlinear heat and mass transfer mechanisms that control the crystal growth process are connected with hydrodynamic flows (forced and natural convection), as well as with the non-local diffusion transport of dissolved impurities in the undercooled liquid phase. The main conclusions following from stability analysis, solvability and selection theories are presented. The sharp interface model and stability criteria for various crystallization conditions and crystalline symmetries met in actual practice are formulated and discussed. The review is also focused on the determination of the main process parameters-the tip velocity and diameter of dendritic crystals as functions of the melt undercooling, which define the structural states and transitions in materials science (e.g. monocrystalline-polycrystalline structures). Selection criteria of stable dendritic growth mode for conductive and convective heat and mass fluxes at the crystal surface are stitched together into a single criterion valid for an arbitrary undercooling. This article is part of the theme issue 'Transport phenomena in complex systems (part 1)'.

Fe2O3 Nanoparticles Doped with Gd: Phase Transformations as a Result of Thermal Annealing.

The aim of this work is to study the effect of the phase composition of the synthesized Fe2O3-Gd2O3 nanoparticles on the efficiency of using magnetic hyperthermia as a basis for experiments. This class of structures is one of the most promising materials for biomedical applications and magnetic resonance imaging. In the course of the study, the dynamics of phase transformations of nanoparticles Fe2O3 → Fe2O3/GdFeO3 → GdFeO3 were established depending on the annealing temperature. It has been determined that the predominance of the GdFeO3 phase in the structure of nanoparticles leads to an increase in their size from 15 to 40 nm. However, during experiments to determine the resistance to degradation and corrosion, it was found that GdFeO3 nanoparticles have the highest corrosion resistance. During the hyperthermal tests, it was found that a change in the phase composition of nanoparticles, as well as their size, leads to an increase in the heating rate of nanoparticles, which can be further used for practical purposes.