We report the occurrence of kinetic arrest of the first-order phase transition from R3c to Pbnm in supercooled La(x)MnO(3±δ) (x = 1 and 0.9, i.e. δ > 0.125). Structural studies have been done, employing low temperature transmission electron microscopy (LT-TEM) and low temperature x-ray diffraction (LT-XRD) techniques. No phase transformation was observed even in La(x)MnO(3±δ) aged for ~12 h at 98 K. The evidence of the occurrence of kinetic arrest was realized at low temperatures through in situ electron beam triggered nucleation and perpetual devitrification of the R3c phase into a Pbnm phase. It was clearly evidenced that the R3c structure of La(x)MnO(3±δ), below its ferromagnetic transition temperature, is metastable and prone to be transformed to a Pbnm orthorhombic structure following initiation by an electron beam trigger. The electron beam transformed Pbnm phase was found to transform back to the R3c phase through a first-order phase transition occurring close to the ferromagnetic to paramagnetic transition (T(c)) during heating. The glass-like kinetics of the arrested R3c phase has been investigated through resistance relaxation measurements, showing a decreasing logarithmic rate of decay of the arrested R3c phase towards the stable Pbnm phase with decreasing temperature, down to 5 K. On the basis of the correlations observed in the resistance-versus-temperature, magnetization-versus-temperature, magnetization-versus-field, resistance relaxation and LT-XRD measurements, the occurrence of kinetic arrest has been attributed to the suppression of Jahn-Teller distortion by double exchange across the insulator-metal transition.
We demonstrate a novel yet straightforward methodology of stabilizing aqueous two-phase systems (ATPS) using oppositely charged nanoparticles (OCNPs). We employ commercialgrade, Ludox, OCNPs to induce self-assembly. This self-assembly route promotes the stronger adsorption of nanoparticles at the water− water interface by triggering the formation of 2D and 3D aggregates of varying sizes and shapes. The interplay of this size and shape promotes stability due to increased Gibbs detachment energy and modulates the resulting cluster adsorption at the interface, thereby the structural state of emulsions. We demonstrate the influence of polymers' and particles' composition on the structural transformation from droplet−bijel− droplet using a phase diagram. For the first time, such a structural transition and the single pathway are reported within the domain of ATPS to produce stable bijels or colloidal capsules. It is asserted that the essential condition of three-phase contact angle (θ) = 90°t o favor the formation of bijels can be established by selecting a suitable experimental condition using a phase diagram without employing any complicated surface modification procedures reported in the literature. Further, the mechanistic route favoring the formation of bijels and emulsion droplets at different experimental regimes is presented based on the empirical study using turbidity and zeta potential measurements. These studies reveal that the formation of bijels will be most favored when the parameter M (ratio of weight fraction of positively charged nanoparticles to negatively charged nanoparticles) is chosen between 0.7 and 4. It is intriguing to note the fact that, while the droplets stabilized by OCNPs have shown good resilience under high centrifugal action, the bijels produced in this way continued to remain stable for a long time, offering a facile route to prepare the bijels with a hierarchical bicontinuous network structure.
Summary The conventional method for multiphase flash is the sequential usage of phase-stability and phase-split calculations. Multiphase flash requires the conventional method to obtain multiple false solutions in phase-split calculations and correct them in phase-stability analysis. Improvement of the robustness and efficiency of multiphase flash is important for compositional flow simulation with complex phase behavior. This paper presents a new algorithm that solves for stationary points of the tangent-plane-distance (TPD) function defined at an equilibrium-phase composition for isobaric-isothermal (PT) flash. A solution from the new algorithm consists of two groups of stationary points: tangent and nontangent stationary points of the TPD function. Hence, equilibrium phases, at which the Gibbs free energy is tangent to the TPD function, are found as a subset of the solution. Unlike the conventional method, the new algorithm does not require finding false solutions for robust multiphase flash. The advantage of the new algorithm in terms of robustness is more pronounced for more-complex phase behavior, for which multiple local minima of the Gibbs free energy are present. Case studies show that the new algorithm converges to a lower Gibbs free energy compared with the conventional method for the complex fluids tested. It is straightforward to implement the algorithm because of the simple formulation, which also allows for an arbitrary number of iterative compositions. It can be robustly initialized even when no K value correlation is available for the fluid of interest. Although the main focus of this paper is on robust solution of multiphase flash, the new algorithm can be used to initialize a second-order convergent method in the vicinity of a solution.
The rheological properties of cells and tissues are central to embryonic development and homeostasis in adult tissues and organs and are closely related to their physiological activities. This work presents our study of rheological experiments on cell monolayer under serum starvation compared to healthy cell monolayer with full serum. Serum starvation is one of the most widely used procedures in cell biology. However, the effect of deprivation of serum concentration on the material properties of cells is still unknown. Therefore, we performed macro-rheology experiments to investigate the effect of serum starvation on a fully confluent Madin–Darby Canine Kidney cell monolayer. The material properties, such as linear and non-linear viscoelastic moduli, of the monolayer, were measured using oscillatory shear experiments under serum-free [0% fetal bovine serum (FBS)] and full serum (10% FBS) conditions. Our results indicate that a serum-starved cell monolayer shows a different rheological behavior than a healthy cell monolayer. The loss and storage moduli decrease for the step-change in oscillatory strain amplitude experiments for a serum-starved cell monolayer and do not recover fully even after small deformation. In comparison, a healthy cell monolayer under full serum condition remains flexible and can fully recover even from a large deformation at higher strain. The effect of adhesion due to fibronectin was also studied in this work, and we found a significant difference in slip behavior for cell monolayer with and without serum.
This communication presents a simple yet straightforward method for preparing water-in-water-in-water particle-stabilized double emulsions, also known as Pickering double emulsions. The approach involves using oppositely charged nanoparticles (OCNPs) in two distinct fluid phases, promoting self-assembly and the formation of aggregates with varying sizes and compositions. By enhancing the interfacial area through the adsorption of aggregates at the interface, this method increases the Gibbs detachment energy of particles between the two aqueous phases, forming stable double emulsions. Furthermore, we investigated the impact of the molecular weight of polyethylene oxide and dextran in the respective fluid phases and the mass ratio (M) of the OCNPs on double emulsion formation. The results demonstrate that the molecular weight of the polymers used in the aqueous phase is a critical parameter influencing the structural formation of the emulsion and the generation of double emulsions. Consequently, double emulsions are formed when equal molecular weight polymer mixtures are employed at an appropriate M, with the dispersed phase placed in the highly viscous continuous phase. The proposed method offers a one-step synthesis process, enabling easy preparation, and exhibits excellent stability for at least 30 days. This study represents the first reported approach for the one-step synthesis of multiple emulsions in an aqueous two-phase system utilizing a Pickering emulsion template.
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