Deformation Of Crystals Research Articles

Multilevel gradient framework of Ce/Mo co-substituted Na3V2(PO4)3/C–CeO2@CNTs system with ultralong cyclic stability for half and full sodium ion cells

Na3V2(PO4)3 (NVP) has attracted much attention due to its excellent potential for sodium storage property. However, low electronic and ionic conductivities severely limit further development. Herein, a dimensional gradient structure of Ce/Mo co-doped and carbon nanotubes (CNTs) enwrapped Na3V2(PO4)3/C–CeO2@CNTs system is constructed by a facile sol-gel method for the first time. The much larger Ce3+ can be used as the pillar ions to buffer the crystal deformation and enhance the structural stability. Moreover, the high charge and strong self-polarization ability of Ce can suppress the increase of charge transfer resistance during the charge/discharge process, which is beneficial to improve the electrochemical performance. Meanwhile, the doping of high-valent Mo6+ generates beneficial vacancies to elevate the Na + diffusion kinetics. The presence of encapsulated CNTs inhibits particle growth, optimizing particle size and shortening ion delivery paths. Significantly, a new conductive CeO2 phase is clearly identified combining with carbon layers to construct favorable bilayer conductive networks, which effectively facilitate electronic transport. Thus, the modified Na3V1.79Ce0.07Mo0.07(PO4)3/C@CNTs (CeMo0.07@CNTs) exhibits a reversible capacity of 110.3 mAh g−1 at 1C, with 91% retention after 1000 cycles. It releases a capacity of 74.9 mAh g−1 at 30C and maintains at 73.9 mAh g−1 after 12000 cycles with a high retention rate of 98.7%. Furthermore, a high retention rate of 83.2% can be obtained after cycling 15000 cycles at 80C, corresponding to a low decay rate of 0.0011% each cycle. In addition, the CHC//CeMo0.07@CNTs asymmetric full cell reveals high specific capacity of 91.59 mAh g−1, demonstrating its excellent practical prospects.

Superplastic deformation inside the knife-sharp shear bands in mid-crustal granites

We examined the microstructures of three ductile shear bands of granitic composition that deformed under mid-to-upper greenschist facies. These shear bands, from the Bundelkhand Craton, India, are 0.8–4.4 mm thick with 20–30 μm median grain sizes and share sharp contacts with the host granite. Comminution of the rheologically stronger feldspars increased permeability, promoted fluid influx, and allowed strain localisation in the incipient shear bands. The major components, quartz and feldspars, deformed via phase-specific crystal plastic deformation mechanisms. Quartz in the monomineralic bands deformed predominantly via dislocation creep, while the feldspars deformed via diffusion creep. Finer quartz grains, which occur at plagioclase triple junctions, resulted from myrmekitisation – also evident from the anti-clustered distribution of quartz-plagioclase phase boundaries and CPO inheritance. The weak CPOs and high mean misorientation angles of the fine plagioclase and K-feldspar grains and yet a high shear strain (γ = 16–37) suggest a significant contribution of grain boundary sliding (GBS) in strain localisation inside the ductile shear bands. Since intracrystalline slip alone cannot explain the high ductile strain in the shear bands, we suggest that GBS controlled the deformation and maturation of the shear bands and promoted superplasticity to accommodate further shearing.

Structural and Thermal Diffusivity Analysis of an Organoferroelastic Crystal Showing Scissor-Like Two-Directional Deformation Induced by Uniaxial Compression.

A two-directional ferroelastic deformation in organic crystals is unprecedented owing to its anisotropic crystal packing, in contrast to isotropic symmetrical packing in inorganic compounds and polymers. Thereby, finding and constructing multidirectional ferroelastic deformations in organic compounds is undoubtedly complex and at once calls for deep comprehension. Herein, we demonstrate the first example of a two-directional ferroelastic deformation with a unique scissor-like movement in single crystals of trans-3-hexenedioic acid by the application of uniaxial compression stress. A detailed structural investigation of the mechanical deformation at the macroscopic and microscopic levels by three distinct force measurement techniques (including shear and three-point bending test), single crystal X-ray diffraction techniques, and polarized synchrotron-FTIR microspectroscopy highlighted that mechanical twinning promoted the deformation. The presence of two crystallographically equivalent faces and the herringbone arrangement promoted the two-directional ferroelastic deformation. In addition, anisotropic heat transfer properties in the parent and the deformed domains were investigated by thermal diffusivity measurement on all three axes using microscale temperature-wave analysis (μ-TWA). A correlation between the anisotropic structural arrangement and the difference in thermal diffusivity and mechanical behavior in the two-directional organoferroelastic deformation could be established. The structural and molecular level information from this two-directional ferroelastic deformation would lead to a more profound understanding of the structure-property relationship in multidirectional deformation in organic crystals.

The effect of crystalline structure on the mechanical behavior in Zr-based amorphous materials: A molecular dynamics simulation

The structure relaxation in the Zr-based amorphous phase affects the microstructure and mechanical properties of metallic glasses. To clarify the mechanical properties and deformation mechanism of amorphous crystallization, the compression and tensile deformation of the Zr90Cu10 amorphous model with different levels of ordered lattice structure were studied by molecular dynamics simulation. The influence mechanism of crystals on the deformation and mechanical properties of amorphous alloys was investigated using atomic-scale stress‒strain curves, atomic structures, and dislocation line distributions. The results show that the in situ crystallization of amorphous alloys has a positive effect on enhancing the elastic modulus and yield strength of amorphous metals. The high-stress regions in the model are predominantly concentrated within the amorphous phase. The phase dislocation entanglement under stress will improve the plasticity of the amorphous state. This work also discusses the deformation mechanism of nanocrystalline amorphous alloys at the atomic level.

Non-Local Q-Tensor Approach for Description of Elastic Deformations of Nematic Liquid Crystals at Sub-Micron Scale

Within the framework of phenomenological approach, a generalized concept of a non-local order parameter, that have the form of a traceless correlation tensor function or a tensor integral operator, is introduced. The main relationships, which determine the equilibrium orientational states and the phase transitions of a deformed nematic liquid crystal, are described. The resulting expression for the free energy is quadratic with respect to the gradients of the order parameter tensor. The limiting transition of the non-local order parameter to the local one leads to an expression that complements the classical Oseen–Frank theory of elasticity. The considered model includes eight independent elastic constants. Three of them relate to "bulk" constants analogous to Frank constants, another three ones relate to "surface" constants, and the remaining two constants determine the anisotropic effect of the gradient of the scalar order parameter on the director field. The constants are necessary for the consideration of a liquid crystal state near defects, as well as for the description of orientation effects caused by the inhomogeneity of order parameter. It is shown that in the free energy expression, the "surface" terms contribute to the director orientation in the case of a non-constant scalar order parameter, even in the approximation of rigid boundary conditions.

Anisotropic Deformation Behavior and Indentation Size Effect of Monocrystalline BaF2 Using Nanoindentation.

In this study, our objective is to investigate the anisotropic deformation behavior and the indentation size effect (ISE) of monocrystalline barium fluoride (BaF2) using nanoindentation experiments with a diamond Berkovich indenter. BaF2 is known for its anisotropy, which results in significant variations in its mechanical properties. This anisotropy poses challenges in achieving high processing quality in ultra-precision machining. Through our experiments, we observed numerous pop-in events in the load-displacement curves, indicating the occurrence of plastic deformation in BaF2 crystals, specifically in the (100), (110), and (111) orientations; these pop-in events were observed as the indentation depth increased to 56.9 nm, 58.2 nm, and 57.8 nm, respectively. The hardness-displacement and elastic modulus-displacement curves were obtained from the tests exhibiting the ISE. The nanoindentation hardness of BaF2 is found to be highly dependent on its crystallographic orientation. Similarly, for BaF2 in the (100) orientation, the range is from 2.43 ± 0.74 and 1.24 ± 0.12 GPa. For BaF2 in the (110) orientation, the values range from 2.15 ± 0.66 to 1.18 ± 0.15 GPa. For BaF2 in the (111) orientation, the values range from 2.12 ± 0.53 GPa to 1.19 ± 0.12 GPa. These results highlight the significant influence of crystallographic orientation on the mechanical properties of BaF2. To better understand the ISE, we employed several models including Meyer's law, the Nix-Gao model, the proportional specimen resistance (PSR) model, and the modified PSR (mPSR) model, and compared them with our experimental results. Among these models, the mPSR model demonstrated the best level of correlation (R2>0.9999) with the experimental measurements, providing a reliable description of the ISE observed in BaF2. Our reports provide valuable insights into the anisotropic mechanical characteristics of BaF2 materials and serve as a theoretical guide for the ultra-precision machining of BaF2.

Extreme Spontaneous Deformations of Active Crystals.

We demonstrate that two-dimensional crystals made of active particles can experience extremely large spontaneous deformations without melting. Using particles mostly interacting via pairwise repulsive forces, we show that such active crystals maintain long-range bond order and algebraically decaying positional order, but with an exponent η not limited by the 1/3 bound given by the (equilibrium) KTHNY theory. We rationalize our findings using linear elastic theory and show the existence of two well-defined effective temperatures quantifying respectively large-scale deformations and bond-order fluctuations. The root of these phenomena lies in the sole time-persistence of the intrinsic axes of particles, and they should thus be observed in many different situations.

Room-temperature deformation of single crystals of WC investigated by micropillar compression

The room temperature deformation behavior of single crystals of WC has been investigated as a function of crystal orientation and specimen size by micropillar compression tests. Plastic flow is successfully observed at room temperature by the operation of slip on {011¯0}〈21¯1¯3〉 when the specimen size is reduced to micrometer orders. This slip system is the only operative slip system in WC at room temperature, and thus plastic flow is not observed for crystal orientations close to the c-axis orientation. The bulk critical resolve shear stress (CRSS) is estimated to be 1.2 ± 0.3 GPa from the extrapolation of the size-dependent CRSS. The 1/3〈21¯1¯3〉 dislocation carrying slip on {011¯0} dissociates into two identical collinear partial dislocations separated by a stacking fault with the energy of 211∼264 mJ/m2. The preference of slip along 〈21¯1¯3〉 among possible directions (such as 〈21¯1¯0〉 and [0001]) on the {011¯0} prism plane is discussed in terms of dislocation self-energy based on anisotropic elasticity, stacking fault energy, dislocation dissociation and Peierls stress for dislocation motion. The lowest Peierls stress arising from the shorter Burgers vector (1/6〈21¯1¯3〉) of dislocations as a result of collinear dissociation of dislocations with b = 1/3〈21¯1¯3〉 on the {011¯0} slip plane is considered to be the main reason for the preference of the {011¯0}〈21¯1¯3〉 slip system.

In situ observation of crystal reorientation in polygranular graphite by synchrotron X-ray diffraction and neutron imaging

The capacity of polygranular graphite to accommodate strain is important to its use within structural components. This study has used in situ neutron and synchrotron X-ray experiments to demonstrate that reorientation of crystal domains accompanies the accommodation of applied mechanical strain in unirradiated Gilsocarbon (GCMB/IM24) graphite. Orientation changes were observed using 3D X-ray Diffraction, and local changes in neutron scattering were also observed with energy-resolved Bragg-edge neutron imaging. In both cases, this behaviour at the crystal level was partially recovered when the load was removed. This study provides new evidence for crystal deformation mechanisms that contribute to polycrystalline graphite's elastic non-linearity and the development of permanent set, which may also explain the effects of fast neutron irradiation on graphite elastic behaviour.

Determination of Light-Induced Deformation Characteristics of the Director Field of Nematic Liquid Crystal by Combining the Methods of Aberrational Self-Action of Light Beam and Polarization Microscopy.

Light-induced director field deformation of a nematic liquid crystal in the field of an obliquely incident laser beam is experimentally studied with aberrational self-action and polarization microscopy. Each of the methods has features associated with the geometry of the light interaction with the director. The combination of methods significantly expands the possibilities of reconstructing the light-induced nonlinear phase shift profile and the director field deformation.

Determining the fundamental failure modes in Ni-rich lithium ion battery cathodes

Challenges associated with in-service mechanical degradation of Li-ion battery cathodes has prompted a transition from polycrystalline to single crystal cathode materials. Whilst for single crystal materials, dislocation-assisted crack formation is assumed to be the dominating failure mechanism throughout battery life, there is little direct information about their mechanical behaviour, and mechanistic understanding remains elusive. Here, we demonstrated, using in situ micromechanical testing, direct measurement of local mechanical properties within LiNi0.8Mn0.1Co0.1O2 single crystalline domains. We elucidated the dislocation slip systems, their critical stresses, and how slip facilitate cracking. We then compared single crystal and polycrystal deformation behaviour. Our findings answer two fundamental questions critical to understanding cathode degradation: What dislocation slip systems operate in Ni-rich cathode materials? And how does slip cause fracture? This knowledge unlocks our ability to develop tools for lifetime prediction and failure risk assessment, as well as in designing novel cathode materials with increased toughness in-service.

Plastic deformation of single crystals of the equiatomic Cr-Fe-Co-Ni medium entropy alloy – A comparison with Cr-Mn-Fe-Co-Ni and Cr-Co-Ni alloys

The plastic deformation behavior of single crystals of the equiatomic Cr-Fe-Co-Ni medium-entropy alloy was investigated in compression and tension from 9 K to 1373 K. The critical resolved shear stress (CRSS) for {111}<11¯0> slip is 44–45 MPa at room temperature and does not exhibit significant tension-compression asymmetry. It increases rapidly with decreasing temperature but exhibits a dulling of the temperature dependence below 77 K due to the inertia effect. The 0 K CRSS was determined to be 200 MPa by extrapolating the temperature dependence of CRSS from above 77 K to lower temperatures. This CRSS value is higher than that of the equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy, 174 MPa, but lower than that of the equiatomic Cr-Co-Ni medium-entropy alloy, 225 MPa. The rank of CRSS at 0 K of the three equiatomic alloys is consistent with the prediction of some solid solution strengthening models. The stacking fault energy (SFE) of the Cr-Fe-Co-Ni is about 20 mJ/m2, which falls between those of the Cr-Mn-Fe-Co-Ni and Cr-Co-Ni alloys. Deformation twinning in the Cr-Fe-Co-Ni MEA occurs at a shear stress of 249 MPa on conjugate (1¯1¯1) planes in the form of Lüders deformation at 77 K. The relationship between twinning stress and SFE is not monotonic as previously believed, but displays a concave with a minimum twinning stress at an intermediate SFE value.

Microstructural Insights into the Evolution of Ophiolitic Chromite from Luobusha

The podiform chromitite found within the Luobusha ophiolite comprises characteristic nodules and massive chromitites. However, the exact origin of these formations remains a topic of ongoing debate. In this study, the microstructures of olivine and chromite are investigated to unravel their formation processes and shed light on the associated geodynamic mechanisms. EBSD analysis provides insights into chromitite and host peridotite deformation mechanisms. Olivine grains in the host dunite and nodular chromite exhibit crystallographic preferred orientations (CPOs) with D-type fabrics, which show a girdle distribution in the [010] and [001] axes, normal to the foliation plane of the sample. The massive and disseminated chromitite displays B-type and C-type olivine fabric, with a concentration of [001] axes parallel to the lineation of the sample. Crystal plastic deformation can be observed in the Luobusha chromite grains, highlighting intercrystalline deformation processes. Small grains lacking misorientation observed in the massive chromitite are likely attributed to heterogeneous nucleation. Chromite nodules are found to be a patchwork of subgrains with various orientations and high-angle boundary misorientation. The formation of Luobusha chromitite involves deep-seated crystallization, followed by amalgamation, and subsequent deformation within the mantle peridotite. These findings distinguish Luobusha chromitite from other ophiolitic chromite deposits, offering valuable insights into the deformation history and formation processes.

Artificial neural network potentials for mechanics and fracture dynamics of two-dimensional crystals ** ** Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide license

Understanding the mechanics and failure of materials at the nanoscale is critical for their engineering and applications. The accurate atomistic modeling of brittle failure with crack propagation in covalent crystals requires a quantum mechanics-based description of individual bond-breaking events. Artificial neural network potentials (NNPs) have emerged to overcome the traditional, physics-based modeling tradeoff between accuracy and accessible time and length scales. Previous studies have shown successful applications of NNPs for describing the structure and dynamics of molecular systems and amorphous or liquid phases of materials. However, their application to deformation and failure processes in materials is still uncommon. In this study, we discuss the apparent limitations of NNPs for the description of deformation and fracture under loadings and propose a way to generate and select training data for their employment in simulations of deformation and fracture simulations of crystals. We applied the proposed approach to 2D crystalline graphene, utilizing the density-functional tight-binding method for more efficient and extensive data generation in place of density functional theory. Then, we explored how the data selection affects the accuracy of the developed artificial NNPs. It revealed that NNP’s reliability should not only be measured based on the total energy and atomic force comparisons for reference structures but also utilize comparisons for physical properties, e.g. stress–strain curves and geometric deformation. In sharp contrast to popular reactive bond order potentials, our optimized NNP predicts straight crack propagation in graphene along both armchair and zigzag (ZZ) lattice directions, as well as higher fracture toughness of ZZ edge direction. Our study provides significant insight into crack propagation mechanisms on atomic scales and highlights strategies for NNP developments of broader materials.

Spin moment cancelation of high Curie temperature Ir doped ZrO2 gradual atomic change

This paper presents the structural, magnetic properties, and spin moment cancelation phenomenon of the zirconium oxide with a gradual change of zirconium for Iridium. The density functional theory (DFT) is shown to be a key feature of magnetic properties of solid materials treatment. It is shown that a small adjustment of the spin moment (less than 6%) is allowed. The Zr1-xIrxO2 crystal structure deformation leads to a magnetic compensation that occurs at x=0.06. Spin and orbital moments behaviors are discussed. The stability of the alloy compounds is confirmed by energy calculations. The material presents ferromagnetic stability and an indirect exchange coupling with a hybridization effect that permitted the evolution from a non-magnetic to a host material with magnetic properties. The Ir orbitals are set at the Fermi level and are spin polarized which indicates a half metallic behavior then makes the material a good candidate for spintronics’ applications.

Universal Piezo-Photocatalytic Wastewater Treatment on Realistic Pollutant Feedstocks by Bi4TaO8Cl: Origin of High Efficiency and Adjustable Synergy.

Clean water is a fundamental human right but millions struggle for it daily. Herein, we demonstrate a new piezo-photocatalyst with immense structural diversity for universal wastewater decontamination. Single-crystalline Bi4TaO8Cl nanoplates with exposed piezoelectric facets exhibit visible-light response, piezoelectric behavior with coercive voltages of ±5 V yielding 0.35% crystal deformation, and pressure-induced band-bending of >2.5 eV. Using five common contaminants of textile and pharmaceutical industries, we show that the nanoplates can mineralize them in all piezocatalytic, photocatalytic, and piezo-photocatalytic approaches with efficiencies higher than most catalysts developed for just one contaminant. Their efficiencies for feedstocks differing over 2 orders of magnitude in concentrations, the highest to date, are also demonstrated to simulate real-life situations. These extensive studies established that combining piezocatalytic and photocatalytic approaches can lead to a tremendous synergy exceeding >45%. The origin of synergy has been illustrated for the first time using band-bending models and improved charge transfer from valence and conduction band electronic surfaces. We further quantified synergy across reactants, concentrations, and ultrasonic frequency and power to demonstrate their versatility and unpredictability. Finally, seven parameters that contribute to synergy but create unpredictability have been identified for the rational design of piezo-photocatalysts for wastewater treatment.

Cylindrical void growth vs. grain fragmentation in FCC single crystals: CPFEM study for two types of loading conditions

The crystal plasticity finite element method (CPFEM) is used to investigate the coupling between the cylindrical void growth or collapse and grain refinement in face-centred cubic (FCC) single crystals. A 2D plane strain model with one void is used. The effect of the initial lattice orientation, similarities, and differences between stress- and strain-driven loading scenarios are explored. To this end, boundary conditions are enforced in two different ways. The first one is based on maintaining constant in-plane stress biaxiality via a dedicated truss element, while the second one is imposing a constant displacement biaxiality factor. Uniaxial and biaxial loading cases are studied. For the uniaxial loading case a special configuration, which enforces an equivalent pattern of plastic deformation in the pristine crystal, is selected in order to investigate the mutual interactions between the evolving void and the developed lattice rotation heterogeneity. Next, biaxial loading cases are considered for three crystal orientations, one of which is not symmetric with respect to loading directions. It is analysed how stress or strain biaxility factors and initial lattice orientation influence the void evolution in terms of its size and shape. Moreover, the consequences of variations in the resulting heterogeneity of lattice rotation are studied in the context of the grain refinement phenomenon accompanying the void evolution. Scenarios that may lead to more advanced grain fragmentation are identified.

Study of the Kinetics of Radiation Damage in CeO2 Ceramics upon Irradiation with Heavy Ions

In this work, the effect of irradiation with heavy Kr15+ and Xe22+ ions on the change in the structural and strength properties of CeO2 microstructural ceramics, which is one of the candidates for inert matrix materials for dispersed nuclear fuel, is considered. Irradiation with heavy Kr15+ and Xe22+ ions was chosen to determine the possibility of simulation of radiation damage comparable to the action of fission fragments, as well as neutron radiation, considering damage accumulation at a given depth of the near-surface layer. During the research, it was found that the main changes in the structural properties with an increase in the irradiation fluence are associated with the crystal lattice deformation distortions and the consequent radiation damage accumulation in the surface layer, and its swelling. Evaluation of the effect of gaseous swelling caused by the radiation damage accumulation showed that a variation in the ion type during irradiation results in a growth in the value of swelling and destruction of the near-surface layer with the accumulation of deformation distortions. Results of the strength variation demonstrated that the most intense decrease in the near-surface layer hardness is observed when the fluence reaches more than 1013–1014 ion/cm2, which is typical for the effect of overlapping radiation damage in the material.

Mechanism of High-Rate Cycling Stability of Anthraquinone Cathode for Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries (ZIBs) are an appealing rechargeable battery technology for next-generation energy storage devices, known for their low cost and high safety. Among the promising cathode materials used for aqueous ZIBs, anthraquinone (AQ) stands out due to its high theoretical specific capacity, low cost, and environmental friendliness. In this study, we investigate the cyclic stability of AQ in aqueous ZIBs. We demonstrate that AQ exhibits a good capacity retention at a high current density even after 1000 charge–discharge cycles, while more obvious capacity fading is observed at a low current density. Density functional theory calculations reveal that the mechanism of the rapid capacity fading under a low current density is due to the significant structural deformation of AQ crystal during Zn insertion into the AQ bulk. Furthermore, the energy barrier of Zn ions that diffuse into the AQ bulk is much higher than the diffuse on the AQ surface, leading to an irreversible Zn insertion. However, under a high current density, Zn ions prefer to adsorb and diffuse on the AQ surface without bulk insertion and structural deformation, rending a higher cycling stability. These insights into the factors influencing the cycling stability of AQ-based electrodes offer a guidance to improve their performance for practical applications.

Evaluations of atomic-resolution strain fields using molecular dynamics simulations combined with corrected smoothed particle hydrodynamics

Deformation analyses of polymeric materials using molecular dynamics (MD) simulations are very useful in evaluating the physical properties based on the atomic features. Generally, the average responses of a system, such as the stress–strain response, are evaluated, but a molecular chain around a solid should deform in an unusual manner in a composite system, such as a solid/polymer system. This may lead to damage and a microscopic inelastic deformation, ultimately affecting the macroscopic behavior of the material. In this study, we propose a technique for use in evaluating the local pseudo-continuum deformation quantities, such as strain and stretch, during MD simulations by introducing deformation analysis via corrected smoothed particle hydrodynamics in a total Lagrangian formulation. Three different types of systems (uniform deformation of an Au crystal, cured resin sandwiched between silica walls, and cured resin containing a nanofiller) are considered, and the unique local deformations in the composite systems are quantitatively evaluated. In particular, local constitutive behavior can be evaluated using this technique, and in the sandwiched system, a high correlation is observed between the local stiffness inhomogeneity and the cohesive failure point. In the filler-containing system, a highly rigid epoxy resin layer is observed around the filler, and local deformation at the poles of the filler is confirmed owing to elongation. The observed trends are consistent with the experimental results. The insights obtained should contribute to the evaluation and understanding of microscopic deformation and damage, which is the beginning of macroscopic failure in a composite material.