Size-dependent Transition Research Articles

An Amorphous-to-Anatase Phase Transition Study of TiO2 Nanotubes by Temperature-Dependent Synchrotron-Based In Situ X-ray Diffraction.

TiO2 nanotubes (NTs) with amorphous and crystalline structures have attracted interest due to their wide range of applications, particularly black TiO2, which addresses the limitations of conventional TiO2 (a wide band gap of 3.0-3.2 eV). Understanding the amorphous-to-anatase phase transition is crucial for phase control of crystalline TiO2. This study investigates the size-dependent phase transition behavior of TiO2 and black TiO2 NTs using temperature-dependent synchrotron-based X-ray diffraction. Thermal treatments reveal that phase transitions occur in the ranges of 210-240 °C for normal NTs and 270-300 °C for black NTs. The onset temperature and crystallization growth are dependent on size, especially NT length, at least in the system under investigation. We observe anisotropic crystallization in quantum confinement, with the unit cell undergoing compression in the a-axis and expansion in the c-axis during crystallization. The longest black NTs (BV50T4) show a significant difference in the c/a ratio. Defects, such as oxygen vacancies, localize on specific NT planes.

Stable many-body localization under random continuous measurements in the no-click limit

In this work, we investigate the localization properties of a paradigmatic model, coupled to a monitoring environment and possessing a many-body localized (MBL) phase. We focus on the postselected no-click limit with quench random rates, i.e., random gains and losses. In this limit, the system is modeled by adding an imaginary random potential, rendering non-Hermiticity in the system. Numerically, we provide evidence that the system is localized for any finite amount of disorder. To analytically understand our results, we extend the quantum random energy model (QREM) to the non-Hermitian scenario. The Hermitian QREM has been used previously as a benchmark model for MBL. The QREM exhibits a size-dependent MBL transition, where the critical value scales as Wc∼LlnL with system size and presenting many-body mobility edges. We reveal that the non-Hermitian QREM with random gain-loss offers a significantly stronger form of localization, evident in the nature of the many-body mobility edges and the value for the transition, which scales as Wc∼ln1/2L with the system size. Published by the American Physical Society 2024

Mechanism of chip segmentation transition from shear slip to shear fracture of Zirconium-based bulk metallic glass in mechanical machining

An in-depth understanding of material cutting deformation forms the foundation for manufacturing Zirconium-based bulk metallic glass (Zr-based BMG) parts. This study explores the transition in chip segmentation mode from shear slip to shear fracture in Zr-based BMG during mechanical machining. The investigation covers chip micromorphology, cyclic cutting force, machined surface quality, and the themo-mechanical properties under various chip segmentation modes linked to cutting conditions. A size-dependent transition in chip segmentation has been observed in the cutting of Zr-based BMG. At a specific cutting speed, a smaller uncut chip thickness favors chip formation via shear slip, resulting in a smooth primary shear zone (PSZ). Conversely, a larger uncut chip thickness leads to chip shear fracture, with the PSZ displaying fishbone-like and dimple patterns. The integration of the modified cutting kinematic model with the free volume-dependent shear transformation zone (STZ) model suggests that the transition from shear slip to fracture is due to an increase in uncut chip thickness, which causes a greater STZ volume in the PSZ. When the STZ volume surpasses a threshold, the intrinsic structural recovery of material from shearing cannot fully compensate for the free volume softening, leading to excessive free volume that ultimately triggers shear fracture. During the chip shear fracture process, the evolution from fishbone-like patterns to dimples in the PSZ is attributed to faster crack propagation at greater uncut chip thickness or higher cutting speeds. In practical applications, it is advisable to avoid chip shear fracture during machining to maintain high-quality machined surface quality.

Atomic-scale observation of nucleation- and growth-controlled deformation twinning in body-centered cubic nanocrystals

Twinning is an essential mode of plastic deformation for achieving superior strength and ductility in metallic nanostructures. It has been generally believed that twinning-induced plasticity in body-centered cubic (BCC) metals is controlled by twin nucleation, but facilitated by rapid twin growth once the nucleation energy barrier is overcome. By performing in situ atomic-scale transmission electron microscopy straining experiments and atomistic simulations, we find that deformation twinning in BCC Ta nanocrystals larger than 15 nm in diameter proceeds by reluctant twin growth, resulting from slow advancement of twinning partials along the boundaries of finite-sized twin structures. In contrast, reluctant twin growth can be obviated by reducing the nanocrystal diameter to below 15 nm. As a result, the nucleated twin structure penetrates quickly through the cross section of nanocrystals, enabling fast twin growth via facile migration of twin boundaries leading to large uniform plastic deformation. The present work reveals a size-dependent transition in the nucleation- and growth-controlled twinning mechanism in BCC metals, and provides insights for exploiting twinning-induced plasticity and breaking strength-ductility limits in nanostructured BCC metals.

Amorphous Sb2Te3 nanowires: Synthesis, characterization and size-dependent phase transition behavior

Understanding the phase transition behavior of phase-change (PC) material with respect to the scaling effect is essential for the application of PC materials. Among all the PC materials, SbTe binary plays a significant role in the well-known Ge-Sb-Te system. Here we have used an unconventional and cost-effective method to fabricate a wide range of prototypical Sb2Te3amorphous nanowires (18–220 nm in diameter) using templated electrodeposition. Compositional, morphological, and structural characterization of the amorphous nanowires were performed, and the crystallization temperature of in-template nanowires was measured using a four-probe resistivity meter. We report that the crystallization temperature of amorphous Sb2Te3 nanowires can be tuned with respect to the diameter of the nanowires and a significant increase was observed for the nanowires with diameters ≤35 nm. Our study sheds light on the size-dependent phase transition behavior of PC NWs with implications for further advancement of the PC memory technology.

Size-dependent transition from steady contraction to waves in actomyosin networks with turnover

Size-dependent transition from steady contraction to waves in actomyosin networks with turnover

Elucidating the particle size-dependent guest-induced structural transition of flexible metal–organic frameworks by exploring cooperative nature

Flexible metal–organic frameworks (MOFs) show S-shaped adsorption isotherms due to their structural transition. This behavior changes depending on their particle size. This paper elucidates the size effect using a multi-scale simulation model.

(Invited) Coupling of Electrochemistry with Surface Science and Computational Modeling to Understand Nanoparticle Electrocatalysts

We investigated nanoparticle electrocatalysts in oxygen evolution reaction (OER) and CO2 reduction reaction (CO2RR) via an approach coupling electrochemistry with ultra-high vacuum (UHV) surface science and computational modeling. Well-defined nanoparticle electrocatalysts such as Fe2O3, NiFeOx, and Ag, were prepared in the UHV chamber via physical vapor deposition (PVD) and characterized with surface science techniques including X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), followed by electrochemistry measurements to establish the structure-property relationships in OER and CO2RR. Calculations based on density functional theory (DFT) and microkinetic modeling (MKM) were then implemented to gain fundamental insight into these systems. We observed the edge-enhanced OER activity of Au-supported, ultra-thin Fe2O3 electrocatalysts and revealed incorporation of Ni at the edge sites (NiFeOx) further boosting their OER activity. We also resolved the size-dependent transition between CO2RR and H2 evolution reaction (HER) selectivity in sub-5 nm Ag electrocatalysts and identified an effective minimum size limit of ∼4 nm for active and selective Ag catalysts: particle diameters below this range experienced increased H2 evolutions due to a high population of Ag edge sites; and larger diameter particles favored CO2RR as the population of Ag(100) surface sites grew but will begin to lose catalyst utilization based on total metal masses.

Crown‐Ether‐Ring Size Dependent Crystal Structures, Phase Transition and Dielectric Properties of [M(crown)]BF4⋅xH2O (M+=Na+, K+; crown=15‐crown‐5, 18‐crown‐6; x=0 or 1)

AbstractCrown ethers demonstrate significant conformational flexibility and rotational symmetry, rendering them invaluable in the realms of supramolecular chemistry and crystal engineering. These unique natures facilitate the construction of supramolecular crystals of crown ethers, characterized by disorder‐order phase transitions, imparts unique properties that hold promise for diverse applications across multiple fields. In this study, four supramolecular compounds, namely [Na(15‐crown‐5)]BF4 (1), [Na(18‐crown‐6)]BF4⋅H2O (2), [K(15‐crown‐5)]BF4 (3) and [K(18‐crown‐6)]BF4⋅H2O (4) were synthesized and characterized by microanalysis, thermogravimetric analysis, differential scanning calorimetry and powder X‐ray diffraction techniques. Herein, 15‐crown‐5 and 18‐crown‐6 correspond to 1,4,7,10,13‐pentaoxacyclopentadecane and 1,4,7,10,13,16‐hexaoxacyclooctadecane, respectively. It was observed that the crystal structure, phase transition, and dielectric properties of these supramolecular compounds are significantly influenced by the size of the crown‐ether rings. The research extensively discussed the correlation between the coordination mode of metal ions of K+ or Na+ with crown ethers, the compatibility between metal ions and crown‐ether rings in terms of size, and the effects of crown‐ether disorder on dielectric permittivity during phase transitions. Our discoveries hold significant implications for the design and development of crown‐ether supramolecular functional materials.

Size-Dependent Phase Transition in Ultrathin Ga2O3 Nanowires.

Gallium oxide (Ga2O3) has attracted extensive attention as a potential candidate for low-dimensional metal-oxide-semiconductor field-effect transistors (MOSFETs) due to its wide bandgap, controllable doping, and low cost. The structural stability of nanoscale Ga2O3 is the key parameter for designing and constructing a MOSFET, which however remains unexplored. Using in situ transmission electron microscopy, we reveal the size-dependent phase transition of sub-2 nm Ga2O3 nanowires. Based on theoretical calculations, the transformation pathways from the initial monoclinic β-phase to an intermediate cubic γ-phase and then back to the β-phase have been mapped and identified as a sequence of Ga cation migrations. Our results provide fundamental insights into the Ga2O3 phase stability within the nanoscale, which is crucial for advancing the miniaturization, light weight, and integration of wide-bandgap semiconductor devices.

Universal window size-dependent transition of correlations in complex systems.

Correlation analysis serves as an easy-to-implement estimation approach for the quantification of the interaction or connectivity between different units. Often, pairwise correlations estimated by sliding windows are time-varying (on different window segments) and window size-dependent (on different window sizes). Still, how to choose an appropriate window size remains unclear. This paper offers a framework for studying this fundamental question by observing a critical transition from a chaotic-like state to a nonchaotic state. Specifically, given two time series and a fixed window size, we create a correlation-based series based on nonlinear correlation measurement and sliding windows as an approximation of the time-varying correlations between the original time series. We find that the varying correlations yield a state transition from a chaotic-like state to a nonchaotic state with increasing window size. This window size-dependent transition is analyzed as a universal phenomenon in both model and real-world systems (e.g., climate, financial, and neural systems). More importantly, the transition point provides a quantitative rule for the selection of window sizes. That is, the nonchaotic correlation better allows for many regression-based predictions.

Direct Observation of Size-Dependent Phase Transition in Methylammonium Lead Bromide Perovskite Microcrystals and Nanocrystals.

Methylammonium (MA) lead halide perovskites have been widely studied as active materials for advanced optoelectronics. As crystalline semiconductor materials, their properties are strongly affected by their crystal structure. Depending on their applications, the size of MA lead halide perovskite crystals varies by several orders of magnitude. The particle size can lead to different structural phase transitions and optoelectronic properties. Herein, we investigate the size effect for phase transition of MA lead bromide (MAPbBr3) by comparing the temperature-dependent neutron powder diffraction patterns of microcrystals and nanocrystals. The orthorhombic-to-tetragonal phase transition occurs in MAPbBr3 microcrystals within the temperature range from 100 to 310 K. However, the phase transition is absent in nanocrystals in this temperature range. In this work, we offer a persuasive and direct evidence of the relationship between the particle size and the phase transition in perovskite crystals.

Designing hetero-structured ultra-strong and ductile Zr-2.5Nb alloys: Utilizing the grain size-dependent martensite transformation during quenching

• A heterogeneous structured Zr-2.5Nb alloys were fabricated successfully utilizing the grain size-dependent martensite transformation. • The present Zr-2.5Nb alloys manifest the highest yield strength (∼710 MPa), together with a high ultimate tensile strength (∼844 MPa) and good ductility (∼17.1%). • A model based on the grain-size-dependent critical resolved shear stress for dislocation slip and twinning has been proposed to explain the α' martensite substructures transition at a critical grain size d c = 3.3 μm. To further improve the service performance of Zr-2.5Nb alloy worked as pressure tubes in pressurized heavy water reactors, more investigation about the microstructure and thermomechanical processing route of Zr-2.5Nb alloy need to be conducted. In this work, a hetero-structured Zr-2.5Nb alloy was prepared by applying a novel technique. Microstructure analysis reveals that the alloy exhibits a grain size-dependent martensite substructure transition during post-rolling quenching. The hetero-structure consists of equiaxed primary α grains and the lamellae groups containing both parallel α' dislocation martensite and α' twin martensite. Compared with the previously reported Zr-Nb alloys, the present Zr-2.5Nb alloys manifest the highest yield strength (∼710 MPa), together with a high ultimate tensile strength (∼844 MPa) and good ductility (∼17.1%). The enhanced mechanical properties are found to arise from the properly controlled fraction/size of the two types of martensite, which not only significantly strengthens the alloy but also contributes to a stronger strain hardening. A model based on the grain-size-dependent critical resolved shear stress for dislocation slip and twinning has been proposed to explain the α' martensite substructures transition at a critical grain size d c = 3.3 μm. Below this size, the critical resolved shear stress (CRSS) for twinning is higher than that for the <c + a> slip. Thus, the α' dislocation martensite is more favorable to form. Otherwise, the α' twin martensite would exhibit a high activity. The present work indicates that making use of the grain size-dependent martensite transformation to tailor the hetero-structure in Zr alloys is an effective strategy to overcome the strength–ductility trade-off in the material.

Evidence of a glassy magnetic transition driven by structural disorder in BiFeO3 nanoparticles

Important effects appear in low and high temperature magnetometry of multiferroic BiFeO3 (BFO) nanoparticles as sizes are reduced from 105 nm to 18 nm. In these particles, a magnetic transition appears close to 200 K probably associated with a spin reorientation which is absent in bigger particles. At higher temperatures and up to the bulk ferroelectric Curie temperature (1000 K), two additional magnetic transitions can be identified. Around TN 600 K, a size-dependent magnetic transition appears, associated with an antiferromagnetic transition. A model based on atomic vibration instability can describe the variation of TN with nanoparticle size. Furthermore, for certain sizes, the properties are dominated by the glassy state arising from the disorder produced by the formation of a core-shell structure. This implies that the magnetic behavior of nanoparticles is strongly affected by their crystal structure close to the transition temperature. The structural disorder which couples to the magnetic properties add control to the magnetic and ferroelectric properties of BFO nanoparticles.

Size-Dependent Microwave Heating and Catalytic Activity of Fine Iron Particles in the Deep Dehydrogenation of Hexadecane.

Knowledge of the electromagnetic microwave radiation–solid matter interaction and ensuing mechanisms at active catalytic sites will enable a deeper understanding of microwave-initiated chemical interactions and processes, and will lead to further optimization of this class of heterogeneous catalysis. Here, we study the fundamental mechanism of the interaction between microwave radiation and solid Fe catalysts and the deep dehydrogenation of a model hydrocarbon, hexadecane. We find that the size-dependent electronic transition of particulate Fe metal from a microwave “reflector” to a microwave “absorber” lies at the heart of efficient metal catalysis in these heterogeneous processes. In this regard, the optimal particle size of a Fe metal catalyst for highly effective microwave-initiated dehydrogenation reactions is approximately 80–120 nm, and the catalytic performance is strongly dependent on the ratio of the mean radius of Fe particles to the microwave skin depth (r/δ) at the operating frequency. Importantly, the particle size of selected Fe catalysts will ultimately affect the basic heating properties of the catalysts and decisively influence their catalytic performance under microwave initiation. In addition, we have found that when two or more materials—present as a mechanical mixture—are simultaneously exposed to microwave irradiation, each constituent material will respond to the microwaves independently. Thus, the interaction between the two materials has been found to have synergistic effects, subsequently contributing to heating and improving the overall catalytic performance.

Resolving the Size-Dependent Transition between CO2 Reduction Reaction and H2 Evolution Reaction Selectivity in Sub-5 nm Silver Nanoparticle Electrocatalysts

Resolving the Size-Dependent Transition between CO₂ Reduction Reaction and H₂ Evolution Reaction Selectivity in Sub-5 nm Silver Nanoparticle Electrocatalysts

Thickness dependence of magnetization structures in thin Permalloy rectangles

Abstract Zero-field magnetization states in Permalloy thin-film elements of rectangular shape are calculated by means of finite element micromagnetic modeling. The energies of several possible magnetization patterns are determined for different sizes and thicknesses of the specimen. Based on these data, a phase diagram of the lowest-energy configuration is set up for rectangles of edge lengths between 250 and 1000 nm. It is shown that a thickness- and size-dependent transition from quasi-homogeneous single-domain states to demagnetized flux-closure patterns occurs in that range. The regime of sizes and thickness of the phase diagram in which the lowest-energy configuration of the thin-film element is a single-domain state is particularly important, since in this case the sample is expected to show good stability with respect to thermal demagnetization, which is a required criterion to make it suitable for technological applications in magneto-electronic devices.

Multivalency-Induced Shape Deformation of Nanoscale Lipid Vesicles: Size-Dependent Membrane Bending Effects.

The size of membrane-enveloped virus particles, exosomes, and lipid vesicles strongly impacts functional properties in biological and applied contexts. Multivalent ligand-receptor interactions involving nanoparticle shape deformation are critical to such functions, yet the corresponding effect of nanoparticle size remains largely elusive. Herein, using an indirect nanoplasmonic sensing approach, we investigated how the nanoscale size properties of ligand-modified lipid vesicles affect real-time binding interactions, especially vesicle deformation processes, with a receptor-modified, cell membrane-mimicking platform. Together with theoretical analyses, our findings reveal a pronounced, size-dependent transition in the membrane bending properties of nanoscale lipid vesicles between 60 and 180 nm in diameter. For smaller vesicles, a large membrane bending energy enhanced vesicle stiffness while the osmotic pressure energy was the dominant modulating factor for larger, less stiff vesicles. These findings advance our fundamental understanding of how nanoparticle size affects multivalency-induced nanoparticle shape deformation and can provide guidance for the design of biomimetic nanoparticles with tailored nanomechanical properties.

The origin of enhanced {{{{{{{{rm{O}}}}}}}}}_{2}^{+} production from photoionized CO2 clusters

CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of {{{{{{{{rm{O}}}}}}}}}_{2}^{+} from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing {{{{{{{{rm{O}}}}}}}}}_{2}^{+}. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres.

Grain size altering yielding mechanisms in ultrafine grained high-Mn austenitic steel: Advanced TEM investigations

The underlying mechanism of discontinuous yielding behavior in an ultrafine-grained (UFG) Fe-31Mn-3Al-3Si (wt.%) austenitic TWIP steel was investigated by the use of advanced TEM technique with taking the plastic deformation mechanisms and their correlation with grains size near the macroscopic yield point into account. Typical yield drop mechanisms such as the dislocation locking by the Cottrell atmosphere due to the presence of interstitial impurities cannot explain the origin of this phenomenon in the UFG high-Mn austenitic TWIP steel. Here, we experimentally revealed that the plastic deformation mechanisms in the early stage of deformation, around the macroscopic yield point, show an obvious association with grain size. More specifically, the main mechanism shifts from the conventional slip in grain interior to twinning nucleated from grain boundaries with decreasing the grain size down to less than 1 μm. Our observation indicates that the grain size dependent deformation mechanisms transition is also deeply associated with the discontinuous yielding behavior as it could govern the changes in the grain interior dislocation density of mobile dislocations around the macroscopic yield point.