Order-disorder Transition Research Articles

Computational studies of the order-disorder transition in block copolymer topological blends

Block copolymer (BCP) nanolithography provides an economical way to pattern nanoscale features for the semiconductor industry. Molecular cyclization can reduce feature sizes, but like linear BCPs, cyclic BCP nanostructure size is limited by the order-disorder transition (ODT). Although the ODTs of pure linear and cyclic BCPs have been studied extensively, there is little information on binary blends of these BCPs. Here, we use dissipative particle dynamic simulations to study the impact of size mismatch and molecular architecture of component BCPs on the ODT for various blends. We see that the blend ODT always occurs at higher segregation strength than one would predict from linear interpolation between pure-component ODTs. The deviation from this simple prediction is greater for blends with greater size mismatch between components. We find clustering of like components (i.e., linear BCPs with linear BCPs and cyclic BCPs with cyclic BCPs) in the disordered phase, and the characteristic lengths of the component clusters correlate with molecular size. Because the ordered state consists of uniformly spaced lamellae, which requires interdigitation of linear and cyclic components of the blend, resolution of the size mismatch between clusters seen in the disordered state can be thought of as a barrier to ordering. Published by the American Physical Society 2024

THz spectroscopy on the amino acids L-serine and L-cysteine.

We present a detailed study on the temperature-dependent THz spectra of the polycrystalline amino acids, L-serine and L-cysteine, for wavenumbers from 20 to 120cm-1 and temperatures from 4 to 300K. Even though the structure of these two amino acids is very similar, with a sulfur atom in the side chain of cysteine instead of an oxygen atom in serine, the excitation spectra are drastically different. Obviously, the vibrational dynamics strongly depend on the ability of cysteine to form sulfur-hydrogen bonds. In addition, cysteine undergoes an order-disorder type phase transition close to 80K, documented by additional specific heat experiments, with accompanying anomalies in the THz results. On increasing temperatures, well-defined vibrational excitations exhibit significant shifts in the eigenfrequencies with concomitant line-broadening yielding partly overlapping modes. Interestingly, several modes completely lose all their dipolar strength and are unobservable under ambient conditions. Comparing the recent results to the published work utilizing THz, Raman, and neutron-scattering techniques, as well as with abinitio simulations, we aim at a consistent analysis of the results ascribing certain eigenfrequencies to distinct collective lattice modes. We document that THz spectra can be used to fine-tune the parameters of model calculations and as fingerprint properties of certain amino acids. In addition, we analyzed the low-temperature heat capacity of both the compounds and detected strong excess contributions compared to the canonical Debye behavior of crystalline solids, indicating soft excitations and a strongly enhanced phonon-density of states at low frequencies.

Critical behavior of the dimerized Si(001) surface: Continuous order-disorder phase transition in the two-dimensional Ising universality class

Critical behavior of the dimerized Si(001) surface: Continuous order-disorder phase transition in the two-dimensional Ising universality class

Phase transition and universality of the majority-rule model on complex networks

In this paper, we investigate the phenomena of order-disorder phase transition and the universality of the majority-rule model defined on three complex networks, namely the Barabási–Albert, Watts–Strogatz and Erdős–Rényi networks. Assume each agent holds two possible opinions randomly distributed across the networks’ nodes. Agents adopt anticonformity and independence behaviors, represented by the probability p, where with a probability p, agents adopt anticonformity or independence behavior. Based on our numerical simulation results and finite-size scaling analysis, it is found that the model undergoes a continuous phase transition for all networks, with critical points for the independence model greater than those for the anticonformity model in all three networks. We obtain critical exponents identical to the opinion dynamics model defined on a complete graph, indicating that the model exhibits the same universality class as the mean-field Ising model.

Influence of vanadium and dysprosium co-doping on phase stability, microstructure, and electrical properties of Bi2O3

Herein, we report the synthesis of Dy–V co-doped Bi2O3 ceramics using the solid–state processing technique under atmospheric conditions. The X-ray diffraction (XRD) patterns demonstrate the stability of the cubic fluorite δ-Bi2O3 in the V-rich ceramics. However, in Dy-rich ceramics, a mixture of phases, including α and δ, gradually diminishes with increased mutual dopant concentrations, suggesting a transition to the single fcc δ-phase with Fm-3 m space group. According to the Rietveld analysis and electron density representation, it is evident that there are no impure peaks present in α-Bi2O3, which highlights the clear transition to the δ-phase polymorphs. The DTA curves for samples M4 and M7 display a distinct endothermic peak at temperatures around 724.5 and 744.5 °C, indicating a phase transition from the monoclinic α-phase to the cubic δ-phase. These peaks are also attributed to an order-disorder transition (ODT). The FESEM micrographs consistently revealed the existence of irregular and aggregated grains, with an average grain size ranging from 0.80 to 5.57 μm. The level of aggregation became more apparent with the escalation of Dy3+ doping, as opposed to the 5–20 wt% V loading. Moreover, the as-sintered pellets M2 demonstrated the absence of any pore formation compared to other samples, confirming a remarkably high degree of densification. As a result, the as-sintered pellets have a low level of void space, with an apparent porosity of no more than 2.5%. Based on the conductivity measurements and electrochemical impedance spectroscopy (EIS), Bi0.85V0.10Dy0.05O1.5 exhibits the highest electrical conductivity of 0.965 (Ω cm)−1 and an optimal activation energy of 0.537 eV at 627 °C compared to other prepared compositions. This remarkable performance is attributed to the high polarizability and mixed valence cations, especially in V5+-rich ceramics, compared to the Dy3+-rich compositions with a reduced conductivity of 0.010 to 0.097 (Ω cm)−1. The Nyquist plots indicate that impedance decreases with vanadium doping increases until it reaches Bi0.85V0.10Dy0.05O1.5. Higher Dy3+ content increases impedance, leading to lower cell performance. The typical composition can be a solid electrolyte in SOFCs operating at moderate temperatures.

Understanding variations of thermal hysteresis in barocaloric plastic crystal neopentyl glycol using correlative microscopy and calorimetry

Plastic crystals (PCs) exhibit solid–solid order-disorder first-order phase transitions that are accompanied by large correlated thermal and volume changes. These characteristics make PCs promising barocaloric solid-state working bodies for heating and cooling applications. However, understanding the variation of transition temperatures and thermal hysteresis in PCs with cycling is critical if these materials are to replace traditional gaseous refrigerants. Here, for the archetypal barocaloric PC neopentyl glycol (NPG), we correlate microstructure obtained from scanning electron microscopy with local and total thermal changes at the phase transition from infra-red imaging and calorimetry, respectively. We outline an evolution in microstructure as NPG recrystallises during repeated thermal cycling through its solid–solid phase transition. The observed microstructural changes are correlated with spatially inhomogeneous heat transfer, yielding direct insight into the kinetics of the phase transition. Our results suggest that the interplay of these processes affects the undesirable thermal hysteresis and the nature of the kinetic steady-state microstructures that are stabilised during cycling between the ordered and disordered phases. These observations have implications for using NPG and other PCs as technologically relevant barocaloric materials and suggest ways in which the hysteresis in these types of materials may be modified.

Lamellar Microphase Separation and Phase Transition of Hydrogen-Bonding/Crystalline Statistical Copolymers: Amide Functionalization at the Interface.

Microphase separation of random copolymers, as well as that of high χ-low N block copolymers, is promising to construct sub-10-nm structures into materials. Herein, we designed statistical copolymers consisting of 2-hydroxyethyl acrylate (HEA) and N-octadecylacrylamide (ODAAm) to produce crystallization and hydrogen bond-assisted lamellar structure materials. The copolymers not only formed a crystalline lamellar structure with 3-4 nm domain spacing but also maintained an amorphous lamellar structure via phase transition above the melting temperature up to approximately 100 °C. The key is to introduce hydrogen-bonding amide junctions between the octadecyl groups and the polymer backbones, by which the polymer chains are physically fixed at the interface of lamellar structures even above the melting temperature. The stabilization of the lamellar structure by the amide units is also supported by the fact that the lamellar structure of all-acrylate random copolymers bearing hydroxyethyl and crystalline octadecyl groups is disordered above the melting temperature. By spin-coating on a silicon substrate, the HEA/ODAAm copolymer formed a multilayered lamellar thin film consisting of a hydrophilic hydroxyethyl/main chain phase and a hydrophobic octadecyl phase. The structure and order-disorder transition were analyzed by neutron reflectivity.

Cryo-EM of the Nucleosome Core Particle Bound to Ran-RCC1 Reveals a Dynamic Complex.

Ras-related nuclear protein (Ran) is a member of the Ras superfamily of small guanosine triphosphatases (GTPases) and a regulator of multiple cellular processes. In healthy cells, the GTP-bound form of Ran is concentrated at chromatin, creating a Ran•GTP gradient that provides the driving force for nucleocytoplasmic transport, mitotic spindle assembly, and nuclear envelope formation. The Ran•GTP gradient is maintained by the regulator of chromatin condensation 1 (RCC1), a guanine nucleotide exchange factor that accelerates GDP/GTP exchange in Ran. RCC1 interacts with nucleosomes, which are the fundamental repeating units of eukaryotic chromatin. Here, we present a cryo-EM analysis of a trimeric complex composed of the nucleosome core particle (NCP), RCC1, and Ran. While the contacts between RCC1 and Ran in the complex are preserved compared with a previously determined structure of RCC1-Ran, our study reveals that RCC1 and Ran interact dynamically with the NCP and undergo rocking motions on the nucleosome surface. Furthermore, the switch 1 region of Ran, which plays an important role in mediating conformational changes associated with the substitution of GDP and GTP nucleotides in Ras family members, appears to undergo disorder-order transitions and forms transient contacts with the C-terminal helix of histone H2B. Nucleotide exchange assays performed in the presence and absence of NCPs are not consistent with an active role for nucleosomes in nucleotide exchange, at least in vitro. Instead, the nucleosome stabilizes RCC1 and serves as a hub that concentrates RCC1 and Ran to promote efficient Ran•GDP to Ran•GTP conversion.

Origin of Interfacial Orbital Reconstruction in Perovskite Superlattices.

The competition between on-site electronic correlation and local crystal field stands out as a captivating topic in research. However, its physical ramifications often get overshadowed by influences of strong periodic potential and orbital hybridization. The present study reveals this competition may become more pronounced or even dominant in two-dimensional systems, driven by the combined effects of dimensional confinement and orbital anisotropy. This leads to electronic orbital reconstruction in certain perovskite superlattices or thin films. To explore the emerging physics, we investigate the interfacial orbital disorder-order transition with an effective Hamiltonian and how to modulate this transition through strains.

Qualitative ab initio theory of magnetic and atomic ordering in FeNi

Magnetic and atomic ordering in equiatomic FeNi alloy is studied by different techniques and methods based on density functional theory in order to clarify the main driving forces and their interplay behind these transitions and possibility of their accurate description within standard density functional theory calculations. The Curie temperature is obtained in Monte Carlo simulations using magnetic exchange interactions obtained by applying the magnetic force theorem within multiple scattering theory for different magnetic and atomic configurational states, including account for the thermal atomic displacements and exchange-correlation potential. The calculations show a very strong sensitivity of the results upon exchange-correlation potential, atomic order, and thermal atomic displacements. The calculated Curie temperature of a completely random alloy with the account of thermal lattice displacement is at least about 200 K below the known experimental data (780–800 K) depending on the above mentioned factors. The atomic order-disorder transition temperature is determined from effective chemical interactions, which apart from the chemical contribution (on the ideal fcc lattice) include contributions from lattice thermal vibrations and local lattice relaxations. The effective chemical interactions are strongly affected by the magnetic state, so the order-disorder transition temperature changes between 1000 and 140 K in the fully ordered ferromagnetic and paramagnetic states, respectively. For the reduced magnetization 0.7 (close to the experimental order-disorder transition temperature at 600 K), the order-disorder transition temperature varies between 550 and 700 K depending mostly on the exchange-correlation potential. The latter effect is the uncertainty in the choice of the exchange-correlation approximation in density functional theory calculations. Published by the American Physical Society 2024

Improved thermal properties and CMAS corrosion resistance of high-entropy RE zirconates by tuning fluorite-pyrochlore structure

The order-disorder transition (ODT) of RE zirconate (RE2Zr2O7) has received much attention due to its potential applications in the design of thermal barrier coatings (TBCs). A series of high entropy RE zirconates (RE = La, Sm, Gd, Er and Lu) were designed and synthesized in order to regulate the fluorite-pyrochlore phases, and to investigate the effect of phase composition on the microstructures and performances. The results showed that the sintering temperature, as well as equivalent ion radius, played an important role in regulating the phase transformation of fluorite-pyrochlore. The coexistence of pyrochlore-fluorite phases not only can result in the decrease in grain size but also increased the lattice strain of each phase, thereby enhancing the phonon scattering and contributing to the reduction in the thermal conductivity. The CMAS corrosion resistance was mainly related to phase compositions, and the thicknesses of reaction layer decreased gradually with the increasing fluorite phase content. The results will provide theoretical guidance for the microstructural design of high entropy RE zirconates as next generation TBC materials in future.

Optical, electrical, and crystal structure study of BaZr0.01Ti0.99O3 ceramics modified with Gd3+ and Y3+ rare-earth ions

Ceramics with compositions Ba0.95Gd0.034Ti0.99Zr0.01O3 (BGdZT) and Ba0.95Y0.034Ti0.99Zr0.01O3 (BYZT) were prepared using the solid-state reaction method. The single tetragonal phase (space group P4mm) of BGdZT and BYZT ceramics is verified by analyzing X-ray spectra using the Rietveld method. The analysis of the tolerance factor (t) reveals an order-disorder phase transition in the tetragonal structure, resulting from the displacement of Ti4+/Zr4+ along the c-axis. A significant correlation is observed between the tolerance factor (t) and the phase transition temperature (Tc), as well as between the band gap of optical measurements and the degree of displacement of Ti4+/Zr4+ along the c-axis. The analysis of high-temperature electrical properties indicates that the conduction mechanism in both studied materials is a correlated barrier hopping (CBH) model, and electrical conductivity improves with increasing densification. The non-Debye behavior is confirmed by the curves of the M′′ vs.ƒ(Hz). The combination of M′′/M′′max and Z′′/Z′′max traces confirms the type of short-range charge carrier mobility.

Room-Temperature Anisotropic Actuation Driven by a Synergistic Order-Disorder and Displacive Phase Transition in a Ferroelectric Crystal.

Actuating materials convert different forms of energy into mechanical responses. To satisfy various application scenarios, they are desired to have rich categories, novel functionalities, clear structure-property relationships, fast responses, and, in particular, giant and reversible shape changes. Herein, we report a phase transition-driven ferroelectric crystal, (rac-3-HOPD)PbI3 (3-HOPD = 3-hydroxypiperidine cation), showing intriguingly large and anisotropic room-temperature actuating behaviors. The crystal consists of rigid one-dimensional [PbI3] anionic chains running along the a-axis and discrete disk-like cations loosely wrapping around the chains, leaving room for anisotropic shape changes in both the b- and c-axes. The shape change is switched by a ferroelectric phase transition occurring at around room temperature (294 K), driven by the exceptionally synergistic order-disorder and displacive phase transition. The rotation of the cations exerts internal pressure on the stacking structure to trigger an exceptionally large displacement of the inorganic chains, corresponding to a crystal lattice transformation with length changes of +24.6% and -17.5% along the b- and c-axis, respectively. Single crystal-based prototype devices of circuit switches and elevators have been fabricated by exploiting the unconventional negative temperature-dependent actuating behaviors. This work provides a new model for the development of multifunctional mechanically responsive materials.

Spatial–temporal order–disorder transition in angiogenic NOTCH signaling controls cell fate specification

Angiogenesis is a morphogenic process resulting in the formation of new blood vessels from pre-existing ones, usually in hypoxic micro-environments. The initial steps of angiogenesis depend on robust differentiation of oligopotent endothelial cells into the Tip and Stalk phenotypic cell fates, controlled by NOTCH-dependent cell–cell communication. The dynamics of spatial patterning of this cell fate specification are only partially understood. Here, by combining a controlled experimental angiogenesis model with mathematical and computational analyses, we find that the regular spatial Tip–Stalk cell patterning can undergo an order–disorder transition at a relatively high input level of a pro-angiogenic factor VEGF. The resulting differentiation is robust but temporally unstable for most cells, with only a subset of presumptive Tip cells leading sprout extensions. We further find that sprouts form in a manner maximizing their mutual distance, consistent with a Turing-like model that may depend on local enrichment and depletion of fibronectin. Together, our data suggest that NOTCH signaling mediates a robust way of cell differentiation enabling but not instructing subsequent steps in angiogenic morphogenesis, which may require additional cues and self-organization mechanisms. This analysis can assist in further understanding of cell plasticity underlying angiogenesis and other complex morphogenic processes.

Spatial-temporal order-disorder transition in angiogenic NOTCH signaling controls cell fate specification.

Angiogenesis is a morphogenic process resulting in the formation of new blood vessels from pre-existing ones, usually in hypoxic micro-environments. The initial steps of angiogenesis depend on robust differentiation of oligopotent endothelial cells into the Tip and Stalk phenotypic cell fates, controlled by NOTCH-dependent cell-cell communication. The dynamics of spatial patterning of this cell fate specification are only partially understood. Here, by combining a controlled experimental angiogenesis model with mathematical and computational analyses, we find that the regular spatial Tip-Stalk cell patterning can undergo an order-disorder transition at a relatively high input level of a pro-angiogenic factor VEGF. The resulting differentiation is robust but temporally unstable for most cells, with only a subset of presumptive Tip cells leading sprout extensions. We further find that sprouts form in a manner maximizing their mutual distance, consistent with a Turing-like model that may depend on local enrichment and depletion of fibronectin. Together, our data suggest that NOTCH signaling mediates a robust way of cell differentiation enabling but not instructing subsequent steps in angiogenic morphogenesis, which may require additional cues and self-organization mechanisms. This analysis can assist in further understanding of cell plasticity underlying angiogenesis and other complex morphogenic processes.

A High Working Temperature Multiferroic Induced by Inverse Temperature Symmetry Breaking.

Molecular-based multiferroic materials that possess ferroelectric and ferroelastic orders simultaneously have attracted tremendous attention for their potential applications in multiple-state memory devices, molecular switches, and information storage systems. However, it is still a great challenge to effectively construct novel molecular-based multiferroic materials with multifunctionalities. Generally, the structure of these materials possess high symmetry at high temperatures, while processing an obvious order-disorder or displacement-type ferroelastic or ferroelectric phase transition triggered by symmetry breaking during the cooling processes. Therefore, these materials can only function below the Curie temperature (Tc), the low of which is a severe impediment to their practical application. Despite great efforts to elevate Tc, designing single-phase crystalline materials that exhibit multiferroic orders above room temperature remains a challenge. Here, an inverse temperature symmetry-breaking phenomenon was achieved in [FPM][Fe3(μ3-O)(μ-O2CH)8] (FPM stands for 3-(3-formylamino-propyl)-3,4,5,6-tetrahydropyrimidin-1-ium, which acts as the counterions and the rotor component in the network), enabling a ferroelastoelectric phase at a temperature higher than Tc (365 K). Upon heating from room temperature, two-step distinct symmetry breaking with the mm2Fm species leads to the coexistence of ferroelasticity and ferroelectricity in the temperature interval of 365-426 K. In the first step, the FPM cations undergo a conformational flip-induced inverse temperature symmetry breaking; in the second step, a typical ordered-disordered motion-induced symmetry breaking phase transition can be observed, and the abnormal inverse temperature symmetry breaking is unprecedented. Except for the multistep ferroelectric and ferroelastic switching, this complex also exhibits fascinating nonlinear optical switching properties. These discoveries not only signify an important step in designing novel molecular-based multiferroic materials with high working temperatures, but also inspire their multifunctional applications such as multistep switches.

Fe-Ni based alloys as rare-earth free gap permanent magnets

L10-ordered FeNi phase has potential as a rare-earth free permanent magnet due to its large magnetization and high Curie temperature. However, low long-range crystal ordering and weak magnetocrystalline anisotropy (Ku) impede its practical use in a technologically relevant permanent magnet. Employing density functional and Monte Carlo simulations, we demonstrate the substantial improvements on structural and thermal stability, disorder-order phase transition, and intrinsic permanent magnetic properties of Fe−Ni structures. We propose that this is achievable through the complementary elemental substitutions by metal elements (M) and interstitial doping with 2p elements. Fe1-xMxNi with simple metal (M = Ga and Al) and metalloid (M = Ge and Si) elemental substitutions at x = 0.5 are broadly known as Heusler (L21) structures with no permanent magnet characteristics. On the contrary, we find that for x = 0−0.5, L10-type structure is energetically favored over the Heusler-type structures. The predicted structures exhibit Ku values up to approximately 2.1 MJ/m3, which is roughly three times that of FeNi phase (0.68 MJ/m3), where the absolute value of Ku depends on the degree of L10 crystal ordering. Interstitial doping with B elevates Ku further up to a maximum value of 3.9 MJ/m3 (at 0 K), leading to room-temperature intrinsic permanent magnetic properties, including maximum energy density product (BH)max, anisotropy field μ0Ha, and hardness parameter κ, comparable to the widely investigated MnBi and MnAl permanent magnets. These results may serve as a guideline in designing Fe−Ni based rare-earth free gap permanent magnetic materials that were previously overlooked.

π Phase Interlayer Shift and Stacking Fault in the Kagome Superconductor CsV_{3}Sb_{5}.

The stacking degree of freedom is a crucial factor in tuning material properties and has been extensively investigated in layered materials. The kagome superconductor CsV_{3}Sb_{5} was recently discovered to exhibit a three-dimensional CDW phase below T_{CDW}∼94 K. Despite the thorough investigation of in-plane modulation, the out-of-plane modulation has remained ambiguous. Here, our polarization- and temperature-dependent Raman measurements reveal the breaking of C_{6} rotational symmetry and the presence of three distinct domains oriented at approximately 120° to each other. The observations demonstrate that the CDW phase can be naturally explained as a 2c staggered order phase with adjacent layers exhibiting a relative π phase shift. Further, we discover a first-order structural phase transition at approximately 65K and suggest that it is a stacking order-disorder phase transition due to stacking fault, supported by the thermal hysteresis behavior of a Cs-related phonon mode. Our findings highlight the significance of the stacking degree of freedom in CsV_{3}Sb_{5} and offer structural insights to comprehend the entanglement between superconductivity and CDW.

Order-disorder transition during shear thickening in bidisperse dense suspensions

Shear thickening of multimodal suspensions has proven difficult to understand because the rheology depends largely on the microscopic details of stress-induced frictional contacts at different particle size distributions (PSDs). Our discrete particle simulations below a critical volume fraction ϕc over a broad range of shear rates and PSDs elucidate the basic mechanism of order–disorder transition. Around the theoretical optimal PSD (relative content of small particles ζ1= 0.26), particles order into a layered structure in the Newtonian regime. At the onset of shear thickening, this layered structure transforms to a disordered one, accompanied by an abrupt viscosity jump. Minor increase in large-large particle contacts after the order–disorder transition causes apparent increase in radial force along the compressional axis. Bidisperse suspensions with less regular but stable layered structure at ζ1= 0.50 show good fluidity in the shear thickening regime. This work shows that in inertial flows where particle collisions dominate, order–disorder transition could play an essential role in shear thickening for bidisperse suspensions.

Collective motion of chiral particles in complex noise environments.

Collective motion of chiral particles in complex noise environments is investigated based on the Vicsek model. In the model, we added chirality, along with complex noise, affecting particles clustering motion. Particles can only avoid noise interference in a specific channel, and this consideration is more realistic due to the complexity of the environment. Via simulations, we find that the channel proportion, p, critically influences chiral particle synchronization. Specifically, we observe a disorder-order transition at critical [Formula: see text], only when [Formula: see text], the system can achieve global synchronization. Combined with our definition of spatial distribution parameter and observation of the model, the reason is that particles begin to escape from the noise region under the influence of complex noise. In addition, the value of [Formula: see text] increases linearly with velocity, while it decreases monotonically with the increase in chirality and interaction radius. Interestingly, an appropriate noise amplitude minimizes [Formula: see text]. Our findings may inspire novel strategies to manipulate self-propelled particles of distinct chirality to achieve desired spatial migration and global synchronization.