Kinetics Of Phase Separation Research Articles

Effect of redox conditions of glass melting on the structure and the properties of titanium-containing gahnite glass-ceramics

In order to develop glass-ceramics containing ions of variable valence in lower oxidation states, it is important to know how changing the redox conditions of glass melting affects structure and properties of glass-ceramics. The zinc aluminosilicate glass nucleated by TiO2 was melted with and without addition of As2O3 and heat-treated from 720° to 1350°C to obtain gahnite-based glass-ceramics. DSC, XRD analysis, Raman spectroscopy and TEM studies revealed that variation of glass melting redox conditions affects kinetics of liquid phase separation and rutile crystallization, composition and structure of gahnite and rutile, crystallization of the residual glass, and does not affect kinetics of gahnite crystallization, gahnite and rutile fractions and structure of glass-ceramics. In glass-ceramics prepared from glasses melted without As2O3, absorption in the visible and near-IR spectral ranges is due to octahedrally coordinated Ti3+ ions in gahnite nanocrystals. The study is important for development of rare-earth-free phosphors.

Interfacial behavior and extraction kinetics of phages in a salting-out extraction system of ammonium citrate and ethyl acetate

To fight the increasing emergence and spread of antimicrobial resistance, phages have regained much more interest as the potential substitute in recent years. Separation and purification of phages were developed by salting-out extraction (SOE) with advantages of simpleness, high efficiency, high yield and the easiness to scale-up over the traditional means. In this study, SOE system composed of ammonium citrate and ethyl acetate was used to investigate the partition behavior of phages, phase separation, and extraction kinetics. With the increase of phase volume ratio, the phage phiAB9 was progressively transferred from the bottom phase to the middle phase. Accordingly, the solubility and aggregation of the middle phase increased, and the color got darker. Furthermore, the phase inversion point was kept at phase volume ratio between 1.0 and 1.1, at which the phase separation time was the shortest. The extraction kinetics revealed that the partition behavior could be finished in 10 min without centrifugation. Finally, the SOE system was also viable alternatives for the isolation and purification of phage λ, phiKP1 and phiSM1. The mechanism of SOE process is very important for its application and scale up in phage separation.

Photopolymerization-induced phase separation kinetics explored by intermittent irradiation

In this work, we explore the kinetics of the photopolymerization-induced phase separation (photo-PIPS) process and the interplay of mechanisms controlling the development of the microstructure in a photosensitive resin comprised of pentaerythritol tetraacrylate (PETA) and 2-ethylhexyl methacrylate (2-EHMA) monomers with polypropylene glycol (PPG, Mn = 4000 g/mol) linear polymer additive and diphenyl(2,4,6-trimethylbenzoyl) phosphine oxide (TPO) photoinitiator. We control the kinetics of photopolymerization by interrupting the irradiation at various stages of the process and varying the light intensity. Evolution of the microstructure is monitored by transmittance testing and scanning electron microscopy (SEM) inspection of fractured surfaces that are exposed to methanol for the purpose of removing the phase-separated PPG content. The evolution of the network is monitored by real-time Fourier-transform infrared (FTIR) spectroscopy during irradiation and intermittent probing after the cessation of irradiation. Three mechanisms controlling the evolution of the microstructure are identified: phase separation, photoinitiator consumption, and microstructural refinement. Phase separation begins immediately after the onset of network development and leads to a rapid reduction of transmittance due to the formation of PPG-rich subdomains. Microstructural refinement takes place at later stages leading to a reduction of these subdomains, a gradual increase of the PPG concentration within subdomains and an associated increase of transmittance. TPO consumption takes place during irradiation and accounts, to a smaller extent, for the recovery of the transmittance. Interrupting the irradiation allows generation of materials with various degrees of conversion and sizes of phase-separated subdomains, which provides a new way to control material properties.

Effect of amphiphilic polymers on phase separating binary mixtures: A DPD simulation study.

We present the phase separation dynamics of a binary (AB), simple fluid (SF), and amphiphilic polymer (AP) mixture using dissipative particle dynamics simulation at d = 3. We study the effect of different AP topologies, including block copolymers, ring block copolymers (RCP), and miktoarm star polymers, on the evolution morphologies, dynamic scaling functions, and length scale of the AB mixture. Our results demonstrate that the presence of APs leads to significantly different evolution morphologies in SF. However, the deviation from dynamical scaling is prominent, mainly for RCP. Typically, the characteristic length scale for SF follows the power law R(t) ∼ tϕ, where ϕ is the growth exponent. In the presence of high AP, we observe diffusive growth (ϕ → 1/3) at early times, followed by saturation in length scale (ϕ → 0) at late times. The extent of saturation varies with constraints imposed on the APs, such as topology, composition ratio, chain length, and stiffness. At lower composition ratios, the system exhibits inertial hydrodynamic growth (ϕ → 2/3) at asymptotic times without clearly exhibiting the viscous hydrodynamic regime (ϕ → 1) at earlier times in our simulations. Our results firmly establish the existence of hydrodynamic growth regimes in low surfactant-influenced phase separation kinetics of binary fluids and settle the related ambiguity in d = 3 systems.

Surface phase-field surfactant fluid model and its practical closest point type finite difference computation

To investigate the fluid surfactant material on three-dimensional objects, we herein develop a simple and practical model based on phase-field method and design its efficient algorithm. The binary fluids and surfactant are represented by two order parameters. The fluid evolution is governed by the incompressible Navier–Stokes equations. To achieve high-performance computation, a linear semi-implicit scheme with stabilizers is proposed for the phase-field type equations in time. The projection method with pressure correction is used to decouple the velocity and the pressure. Based on the closest-point type embedded narrow domain method and a simple pseudo-Neumann boundary treatment, the calculation on curved surface is extended into a narrow band region including the surface. The surface spatial operators are approximately replaced by the standard spatial operators. In the three-dimensional narrow band, the finite difference method is used to discretize the equations on staggered grids. The mass compensation and vector projection techniques are designed to obtain physically meaningful solutions. In each time iteration, the proposed algorithm is efficient to implement. Numerical results indicate that the proposed method is capable to simulate surfactant-laden phase separation, fluid instabilities, and coarsening dynamics with variable mobility on various surfaces.

Regulating Phase Separation Kinetics for High-Efficiency and Mechanically Robust All-Polymer Solar Cells.

All-polymer solar cells (all-PSCs) possess excellent operation stability and mechanical robustness than other types of organic solar cells, thereby attracting considerable attention for wearable flexible electron devices. However, the power conversion efficiencies (PCEs) of all-PSCs are still lagging behind those of small-molecule-acceptor-based systems owing to the limitation of photoactive materials and unsatisfactory blend morphology. In this work, a novel terpolymer, denoted as PBDB-TFCl (poly4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b″]dithiophene-1,3-bis(2-ethylhexyl)-5,7-di(thiophen-2-yl)-4H,8H-benzo[1,2-c:4,5-c″]dithiophene-4,8-dione-4,8-bis(4-chloro-5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene), is used as an electron donor coupled with a ternary strategy to optimize the performance of all-PSCs. The addition of PBDB-TCl unit deepens the highest occupied molecular orbital energy level, reducing voltage losses. Moreover, the introduction of the guest donor (D18-Cl) effectively regulates the phase-transition kinetics of PBDB-TFCl:D18-Cl:PY-IT during the film formation, leading to ideal size of aggregations and enhanced crystallinity. PBDB-TFCl:D18-Cl:PY-IT devices exhibit a PCE of 18.6% (certified as 18.3%), judged as the highest value so far obtained with all-PSCs. Besides, based on the ternary active layer, the manufactured 36 cm2 flexible modules exhibit a PCE of 15.1%. Meanwhile, the ternary PSCs exhibit superior photostability and mechanical stability. In summary, the proposed strategy, based on molecular design and the ternary strategy, allows optimization of the all-polymer blend morphology and improvement of the photovoltaic performance for stable large-scale flexible PSCs.

Continuous Emulsion Channels Achieved by Controlling the Aqueous–Oil Interface Solely with Rough Colloids

AbstractAs a new class of soft materials, continuous emulsion channels have been successfully stabilized solely by rough colloids, which exhibit unique capability in sterically controlling liquid–liquid interfaces. Once jammed at the interface, the roughness‐enhanced frictions can slow down the dynamics of phase separation, and the interlocking behaviors would constrain their relative motions and generate force structures that provide mechanical support for the created emulsions. Ethanol is used to ensure the particles’ absorption, whose migration can modify the interfacial tension, and increase the solubility of active ingredients (e.g., curcumin). Applying rough colloids in ethanol‐containing systems opens new pathways toward the generation of novel structures and materials, where the parallel but separate functionalities provided by various phases demonstrate wide‐ranging applications, especially in delivery systems with variably soluble components.

In-situ observation of phase separation dynamics for immiscible aqueous solution within ultrasonic field

A high-speed imaging technique was used to observe the phase separation process of water (H2O)-20 %succinonitrile (SCN) immiscible solution within ultrasound field. Combining with numerical simulation, the effects of ultrasonic cavitation and acoustic streaming on the fragmentation and migration of secondary droplets were revealed. It was found that the previously spherical or near-spherical secondary H2O-rich droplets formed under static condition were dynamically transformed into several novel forms, such as tadpole-like, string-beads, gourd-like, and threadlike patterns. The calculated results showed that the cavitation could fragment micron-scale H2O-rich droplets because of the produced higher shock wave pressure than the droplets’ Laplace pressure, and the subsequent droplet morphology evolution mainly depended on the liquid ejection volume determined by the distance between the droplets and the collapsing bubbles. Meanwhile, acoustic streaming, which generated shear force exceeding the surface tension of H2O-rich phase, stretched, split and finally fractured millimeter-sized or even larger secondary droplets into several smaller spherical sub-droplets. In comparison, the observed secondary droplet distribution characteristics in H2O-20 %SCN solution were similar to the Bi-rich particles in the ultrasonic solidification microstructures of Al-30 %Bi immiscible alloy, confirming that this work provided a deep understanding of the liquid phase separation mechanism within ultrasonic field.

Simply solvable model capturing the approach to statistical self-similarity for the diffusive coarsening of bubbles, droplets, and grains.

Aqueous foams and a wide range of related systems are believed to coarsen by diffusion between neighboring domains into a statistically self-similar scaling state, after the decay of initial transients, such that dimensionless domain size and shape distributions become time independent and the average grows as a power law. Partial integrodifferential equationsfor the time evolution of the size distribution for such phase separating systems can be formulated for arbitrary initial conditions, but these are cumbersome for analyzing data on nonscaling state preparations. Here we show that essential features of the approach to the scaling state are captured by an exactly-solvable ordinary differential equationfor the evolution of the average bubble size. The key ingredient is to characterize the bubble size distribution approximately, using the average size of all bubbles and the average size of the critical bubbles, which instantaneously neither grow nor shrink. The difference between these two averages serves as a proxy for the width of the size distribution. Solution of our model shows that behavior is controlled by a signed length δ that is proportional to the width of the initial distribution relative to that in the scaling state. In particular, δ is negative if the initial preparation is too monodisperse, and is positive if it is too polydisperse. To test our approach, we compare with data for quasi-two dimensional dry foams created with three different initial amounts of polydispersity. This allows us to readily identify the critical radius from the average area of six-sided bubbles, whose growth rate is zero by the von Neumann law. The growth of the average and critical radii agree quite well with exact solution, though the most monodisperse sample crosses over to the scaling state faster than expected. A simpler approximate solution of our model performs equally well. Our approach is applicable to 3d foams, which we demonstrate by re-analyzing prior data, as well as to froths of dilute droplets and to phase separation kinetics for more general systems such as emulsions, binary mixtures, and alloys.

Multiscale dynamics of charging and plating in graphite electrodes coupling operando microscopy and phase-field modelling

The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined with non-equilibrium thermodynamics implemented in a multi-dimensional (1D+1D to 3D) phase-field modeling framework to reveal the rate-dependent spatial dynamics of phase separation and plating in graphite electrodes. Here we visualize and provide mechanistic understanding of the multistage phase separation, plating, inter/intra-particle lithium exchange and plated lithium back-intercalation phenomena. A strong dependence of intra-particle lithiation heterogeneity on the particle size, shape, orientation, surface condition and C-rate at the particle level is observed, which leads to early onset of plating spatially resolved by a 3D image-based phase-field model. Moreover, we highlight the distinct relaxation processes at different state-of-charges (SOCs), wherein thermodynamically unstable graphite particles undergo a drastic intra-particle lithium redistribution and inter-particle lithium exchange at intermediate SOCs, whereas the electrode equilibrates much slower at low and high SOCs. These physics-based insights into the distinct SOC-dependent relaxation efficiency provide new perspective towards developing advanced fast charge protocols to suppress plating and shorten the constant voltage regime.

Phase separation and ripening in a viscoelastic gel

The process of phase separation in elastic solids and viscous fluids is of fundamental importance to the stability and function of soft materials. We explore the dynamics of phase separation and domain growth in a viscoelastic material such as a polymer gel. Using analytical theory and Monte Carlo simulations, we report a domain growth regime in which the domain size increases algebraically with a ripening exponent [Formula: see text] that depends on the viscoelastic properties of the material. For a prototypical Maxwell material, we obtain [Formula: see text], which is markedly different from the well-known Ostwald ripening process with [Formula: see text]. We generalize our theory to systems with arbitrary power-law relaxation behavior and discuss our findings in the context of the long-term stability of materials as well as recent experimental results on phase separation in cross-linked networks and cytoskeleton.

Nonsolvent-induced phase separation inside liquid droplets.

Nonsolvent-induced phase separation (NIPS) is a popular method for creating polymeric particles with internal microstructure, but many fundamental questions remain surrounding the kinetics of the complex coupled mass transfer and phase separation processes. In this work, we use simulations of a phase-field model to examine how (i) finite domain boundaries of a polymer droplet and (ii) solvent/nonsolvent miscibility affect the NIPS process. To isolate the effects of phase separation kinetics and solvent/nonsolvent mass transfer on the NIPS process, we study two different cases. First, we investigate droplet concentrations that originate inside the two-phase region, where phase separation kinetics alone governs the microstructure. Second, we investigate the effects of solvent/nonsolvent mass transfer by studying droplet concentrations that begin outside the two-phase region, where both phase separation kinetics and mass transfer play a role. In both cases, we find that qualitative NIPS behavior is a strong function of the relative location of the initial droplet composition with respect to the phase diagram. We also find that polymer/nonsolvent miscibility competes with solvent/nonsolvent miscibility in driving NIPS kinetic behavior. Finally, we examine polymer droplets undergoing solvent/nonsolvent exchange and find that the model predicts droplets that shrink with nearly Fickian diffusion kinetics. We conclude with a brief perspective on the state of simulations of NIPS processes and some recommendations for future work.

Crosslink-Induced Conformation Change of Intrinsically Disordered Proteins Have a Nontrivial Effect on Phase Separation Dynamics and Thermodynamics.

Biomolecule condensates formed via liquid-liquid phase separation (LLPS) play crucial roles within various cellular processes. Despite numerous theoretical and experimental discoveries, the general principle by which the protein conformation affects the propensity for LLPS remains poorly understood. Here, we systematically address this issue using a general coarse-grained model of intrinsically disordered proteins (IDPs) with different degrees of intrachain crosslinks. We find that an increased conformation collapse due to higher intrachain crosslink ratio f enhances the thermodynamic stability of protein phase separation and found the critical temperature Tc has a good scaling law with the proteins' average radius of gyration Rg. Such correlation is robust regardless of interaction types and sequence patterns. Strikingly, the growth dynamics of the LLPS process, contrary to the thermodynamic observation, is generally more favored at proteins with extended conformation. Faster condensate growing speed is again observed for higher-f collapsed IDPs, resulting altogether in a nonmonotonic dynamics as a function of f. A phenomenological understanding of the phase behavior is provided by a mean-field model with an effective Flory interaction parameter χ, which is found to have a good scaling law with conformation expansion. Our study shed lights on the general mechanism for understanding and modulation of phase separation with different conformation profiles and may provide new evidence in reconciling the contradictions in thermodynamic- and dynamic-controlled experimental LLPS observations.

Interplay of photopolymerization and phase separation kinetics and the resulting structure-property relationship of photocurable resins

In this work we develop thermoset materials with heterogeneous microstructures on sub-micron scales by photopolymerization-induced phase separation (photo-PIPS). To this end, we designed a photo-curable resin based on pentaerythritol tetraacrylate (PETA), an acrylate monomer, combined with 2-ethylhexyl methacrylate (2-EHMA), a methacrylate diluent. Polypropylene glycol (PPG) was used as a phase separation agent. Phase separation was monitored by reactive light transmittance using a custom-built light transmission apparatus and through dynamic mechanical analysis (DMA). The photopolymerization kinetics and the microstructure morphology were characterized using real-time Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), respectively. We observe double phase separation: PETA and 2-EHMA separate due to different reactivities, while PPG phase separates as the network develops due to immiscibility. A synergy is observed between the two processes: PPG phase separation leads to an enhanced separation of 2-EHMA. Phase separation leads to reduced transmittance due to scattering, which is primarily associated with the separation of 2-EHMA. Phase separation also causes the reduction of stiffness due to the formation of PPG subdomains. The kinetics is enhanced by increasing the PPG molecular weight and increasing the irradiation intensity.

Determining Phase Separation Dynamics with an Automated Image Processing Algorithm

Key words high-throughput experimentation - separation - liquid–liquid extraction - algorithms - emulsion

Kinetics of Water-Induced Amorphous Phase Separation in Amorphous Solid Dispersions via Raman Mapping.

The poor bioavailability of an active pharmaceutical ingredient (API) can be enhanced by dissolving it in a polymeric matrix. This formulation strategy is commonly known as amorphous solid dispersion (ASD). API crystallization and/or amorphous phase separation can be detrimental to the bioavailability. Our previous work (Pharmaceutics 2022, 14(9), 1904) provided analysis of the thermodynamics underpinning the collapse of ritonavir (RIT) release from RIT/poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA) ASDs due to water-induced amorphous phase separation. This work aimed for the first time to quantify the kinetics of water-induced amorphous phase separation in ASDs and the compositions of the two evolving amorphous phases. Investigations were performed via confocal Raman spectroscopy, and spectra were evaluated using so-called Indirect Hard Modeling. The kinetics of amorphous phase separation were quantified for 20 wt% and 25 wt% drug load (DL) RIT/PVPVA ASDs at 25 °C and 94% relative humidity (RH). The in situ measured compositions of the evolving phases showed excellent agreement with the ternary phase diagram of the RIT/PVPVA/water system predicted by PC-SAFT in our previous study (Pharmaceutics 2022, 14(9), 1904).

Phase separation kinetics of block copolymer melts confined under moving parallel walls: A DPD study

We use dissipative particle dynamics (DPD) simulations to study the effect of shear on domain morphology and kinetics of microphase separating critical diblock copolymer (BCP) bulk melts. The melt is confined within two parallel amorphous solid walls at the top and bottom of the simulation box. The shear is induced by allowing the walls to move in a direction with a specific velocity. We explore the following cases: (i) walls are fixed, (ii) only the top wall moves, (iii) both walls move in the same direction, and (iv) both walls move in opposite directions. After the temperature quench from an uniformly mixed state, we monitor the effect of shear on evolution morphology, scaling behavior, characteristic length scale and growth laws of the evolving system. The characteristic length scale follows typical power-law behavior at early times and saturates at late times when both walls are fixed. The length scale changes significantly with shear rates caused by wall velocities. The usual lamellar morphology, which is not achieved for case 1 within the considered simulation time steps, is noticed much earlier for the nonzero wall velocity cases. Specifically, it is seen much before in case 4 than in the other cases. We find that the shear viscosity decreases (shear-thinning) with shear rate for all the cases at a given coarsening time. Overall, we report the influence rule of shear rates on microphase separation kinetics of BCP melts. This study can provide a scheme to anticipate and design anisotropic microstructures under the application of externally controlled wall shear that may further guide in producing the various composite materials with superior mechanical and physical properties.

Hydrodynamic effects in kinetics of phase separation in binary fluids: Critical versus off-critical compositions.

Via hydrodynamics-preserving molecular dynamics simulations we study growth phenomena in a phase-separating symmetric binary mixture model. We quench high-temperature homogeneous configurations to state points inside the miscibility gap, for various mixture compositions. For compositions at the symmetric or critical value we capture the rapid linear viscous hydrodynamic growth due to advective transport of material through tubelike interconnected domains. For state points very close to any of the branches of the coexistence curve, the growth in the system, following nucleation of disconnected droplets of the minority species, occurs via a coalescence mechanism. Using state-of-the-art techniques, we have identified that these droplets, between collisions, exhibit diffusive motion. The value of the exponent for the power-law growth, related to this diffusive coalescence mechanism, has been estimated. While the exponent nicely agrees with that for the growth via the well-known Lifshitz-Slyozov particle diffusion mechanism, the amplitude is stronger. For the intermediate compositions we observe initial rapid growth that matches the expectations for viscous or inertial hydrodynamic pictures. However, at later times these types of growth cross over to the exponent that is decided by the diffusive coalescence mechanism.

Preparation of Porous Epoxy Resin Materials by Reaction-Induced Phase Separation Regulated Using Fumed Silica

Significant attention has been paid to improving the microstructure of polymer blends by stabilizing their phase interface with inorganic nanoparticles. During the preparation of porous epoxy resin materials by reaction-induced phase separation, the microstructure of the porous epoxy resin materials is controlled by fumed silica. The phase separation and chemical kinetics have been monitored by optical microscopy, differential scanning calorimetry, and rheometry, and the microstructure has been characterized by scanning electron microscopy and mercury porosimetry. Upon comparison of the phase separation process of the epoxy blend before and after the addition of fumed silica, it is evident that the fumed silica are preferentially dispersed in the pore-forming agent phase; at the phase interface, the coarsening rate of the phase structure is decreased, the reaction rate is decreased, and the gelation is delayed. With an increase in the mass fraction of the fumed silica, the pore size of the porous epoxy resin materials decreases gradually, and the structure is fined. This result provides an approach for the fine control of the microstructure of porous epoxy resin materials. In addition, the fumed silica in the porous epoxy resin material can be removed by acid etching without affecting the structure of the porous material. Furthermore, the effect of the fumed silica on the structure of the closed-hole epoxy resin system has been investigated.

Phase separation kinetics of binary mixture in the influence of bond disorder: sensitivity to quench temperature

ABSTRACT Morphologies in phase-separating systems can significantly influence final material properties. We present extensive Monte Carlo simulation results on segregation kinetics of critical binary mixture (-Ising system) with a fraction of bond disorder introduced regularly. The effect of various quench temperatures is studied on growth kinetics and scaling properties of evolved morphologies. The morphology changes from their usual bicontinuous isotropic patterns at zero disorder to short strips and lamellar patterns (anisotropy) with the increasing disorder at shallow quench depth. The domain evolution at lower disorder remains at a transient growth regime for deep quench; however, the lamellar pattern is observed at high disorder for the same quench depth. The scaling behavior changes significantly with quench depths at the higher fraction of disorder. Though, a tiny deviation is observed at lower disorder fractions for shallow quench depths. The length scale freezes () to finite size at the higher disorder asymptotically.