Phase Separation Patterns Research Articles

Physical simulation of separating two immiscible liquids in the “Pobeda” smelting unit with localized melt sparging by means of side and basal tuyeres

The paper aims to find physicochemical patterns in the separation of liquid smelting products with the melt blasted by side and basal tuyeres installed in the area of a “Pobeda” smelting unit intended for charging and melting copper-containing charge. The study adopted the physical simulation method with the use of transparent media (vegetable oil and colored water) and a glass cuvette. The dynamic similarity between the sample and model was ensured by the constancy of the Archimedes number Ar. The initial ratio between the levels of less and more dense fluids was chosen according to the Weber number We. The Archimedes numbers per one side and one basal tuyere amounted to 5;3 and 12;6 (Variants 1 and 2, respectively). The completeness of phase separation was determined visually through filming the liquid-liquid interface emergence and the settlement front advance, as well as quantitatively via the sampling method with subsequent separation of water and oil through centrifugation. According to the condition Ar = idem, the blasting parameters were determined for the cold model with the installation of six basal and three side tuyeres, which were assumed to be located in the sparging zone of the melt. The phase separation patterns are shown to depend on the duration and intensity of the blast. Under Variant 1, blasting is characterized by the formation of a constant phase immiscibility profile at the end of the experiment, which occurs in a limited area of the settlement zone that is far from the sparging zone. At higher Archimedes numbers (Variant 2), the melt pool acquires a homogeneous structure in a shorter time, and no immiscibility boundaries are observed along the entire length of the melt. Thus, a cold modeling technique was developed to study the patterns of phase separation in the presence of a separate sparging zone in the melt pool. This provides a means to obtain objective parameters for the location of tuyeres and blasting conditions, thus ensuring a reduction in the mechanical losses of copper with slag at a given smelting capacity in the “Pobeda” unit.

Prediction of microstructural evolution of multicomponent polymers by Physics-Informed neural networks

As emerging concepts, leveraging physical information with machine learning to construct hybrid models enables a scientific data-driven paradigm for the investigation of complex kinetic issues in the field of polymer science. Herein, the model of physics-informed neural networks (PINNs), integrating advantages of neural networks with physics-based knowledge, is extended to predict the spatiotemporal patterns of phase-separated microstructures of multicomponent polymers. It is demonstrated that the PINN-based data-driven model can achieve the forward, backward and bidirectional predictions of spatiotemporally phase-separated patterns of homopolymer blends. All predicted patterns reveal a high accuracy and robustness of PINN-based data-driven model by leveraging a small amount of training data. Particularly, the PINN-based method can be harnessed to infer the latent physical law about the growth kinetics of phase-separated microstructures. In addition, PINN-based data-driven model can also be generalized to forecast the spatiotemporal patterns of microphase-separated nanostructures of block copolymers and infer their growth kinetics. Our study opens the possibility of learning non-equilibrium phenomena of complex polymer systems from only a few snapshots of microstructural evolution.

Morphological control of bicontinuous phase-separated patterns by preparing mixed monolayers using non-amphiphilic s-triazine derivatives with three fluorinated chains

In this study, the morphogenesis of the bicontinuous phase separation in mixed monolayers of a non-amphiphilic fluorocarbon derivative without a hydrophilic group and long-chain fatty acids is discussed. These fluorocarbon derivatives contain an s-triazine ring and three fluorocarbon chains. The corresponding fluorocarbon derivatives exhibit high crystallinity in the monolayers, allowing them to maintain crystalline regularity even in the "sea" region of the mixed monolayer that exhibits phase separation. In controlling the bicontinuous pattern, the formation of complex phase-separated morphology in the mixed system of fluorine-based derivatives and comb polymers, along with the high concentration and low diffusion conditions in the mixed hydrocarbon/fluorocarbon system, were examined. It was observed that the condensed phase domains became angular shape at a low temperature (5 °C), and the surface approached a bicontinuous feature at a high temperature (40 °C). With the formation of hydrogenated condensed domains, the "sea" region of fluorocarbon chains lost its order. At this point, the shape of the nanodomains tended to become more circular.

Hierarchical Emulsion Structure and Functionality Regulated by Coexisting Bicontinuous Microemulsion and Liquid Crystal Domains.

Since microemulsions are usually low viscosity fluids, enhanced rheological properties while maintaining their structure-derived functionality have long been desired from an industrial application point of view. However, for instance, it is practically difficult to thicken bicontinuous microemulsions (BCMEs) without perturbing their alternating domain structure or to emulsify oils using BCME having ultralow interfacial tension as an external phase. In this study, a methodology called a BCLC emulsification technique has been constructed to obtain oil-in-water emulsions stabilized by coexisting BCME and liquid crystal (LC) phases. The produced emulsions based on polyglyceryl-10 diisostearate, polyglyceryl-6 dicaprate, cetyl ethylhexanoate, and water are structurally scrutinized by means of small- and wide-angle X-ray scattering (SWAXS), freeze fracture transmission electron microscopy (FF-TEM), and scanning electron assisted dielectric microscopy (SE-ADM). The data provide experimental evidence that this methodology enables one to control the bending elasticity of the interfacial membranes and consequent long-range order of the BCME domains. Moreover, closely correlated with the interfacial membrane properties, submicrometer-sized fine oil droplets are supported by the LC networks and agglomerated into spongy or network-like phase-separation patterns. The resulting nonfluidic, jelly emulsions are particularly useful in cosmetics because of combined BCME-derived high cleansing performance and excellent usability owing to the enhanced viscosity. The thickening mechanisms are essentially different from those of common lamellar-gel-stabilized oil-in-water emulsions, which utilize crystalline lamellar gel networks as oil droplet stabilizers.

A continuum model for morphology formation from interacting ternary mixtures: Simulation study of the formation and growth of patterns

Our interest lies in exploring the ability of a coupled nonlocal system of two quasilinear parabolic partial differential equations to produce phase separation patterns. The obtained patterns are referred here as morphologies. Our target system is derived in the literature as the rigorous hydrodynamic limit of a suitably scaled interacting particle system of Blume–Capel-type driven by Kawasaki dynamics. The system describes in a rather implicit way the interaction within a ternary mixture that is the macroscopic counterpart of a mix of two populations of interacting solutes in the presence of a solvent. Our discussion is based on the qualitative behavior of numerical simulations of finite volume approximations of smooth solutions to our system and their quantitative postprocessing in terms of two indicators (correlation and structure factor calculations). Our results show many similar qualitative features (e.g. general shape and approximate coarsening rates) which have been observed in previous works on the stochastic Blume–Capel model with three interacting species. The properties of the obtained morphologies (shape, connectivity, and so on) can play a key role in, e.g., the design of the active layer for efficient organic solar cells.

Simulation of various biofilm fractal morphologies by agent-based model

Biofilms are clusters of bacteria wrapped in extracellular matrix and polymers. The study of biofilm morphological transformation has been around for a long time and has attracted widespread attention. In this paper, we present a model for biofilm growth based on the interaction force, in which bacteria are treated as tiny particles and locations of particles are updated by calculating the repulsive forces among particles. We adapt a continuity equation to indicate nutrient concentration variation in the substrate. Based on the above, we study the morphological transformation of biofilms. We find that nutrient concentration and nutrient diffusion rate dominate different biofilm morphological transition processes, in which biofilms would grow into fractal morphology under the conditions of low nutrient concentration and nutrient diffusivity. At the same time, we expand our model by introducing a second particle to mimic extracellular polymeric substances (EPS) in biofilms. We find that the interaction between different particles can lead to phase separation patterns between cells and EPSs, and the adhesion effect of EPS can attenuate this phenomenon. In contrast to single particle system models, branches are inhibited due to EPS filling in dual particle system models, and this invalidation is boosted by the enhancement of the depletion effect.

Magnetic-field-controlled growth of magnetoelastic phase domains in FeRh

Magnetic phase transition materials are relevant building blocks for developing green technologies such as magnetocaloric devices for solid-state refrigeration. Their integration into applications requires a good understanding and controllability of their properties at the micro- and nanoscale. Here, we present an optical microscopy study of the phase domains in FeRh across its antiferromagnetic–ferromagnetic phase transition. By tracking the phase-dependent optical reflectivity, we establish that phase domains have typical sizes of a few microns for relatively thick epitaxial films (200 nm), thus enabling visualization of domain nucleation, growth, and percolation processes in great detail. Phase domain growth preferentially occurs along the principal crystallographic axes of FeRh, which is a consequence of the elastic adaptation to both the substrate-induced stress and laterally heterogeneous strain distributions arising from the different unit cell volumes of the two coexisting phases. Furthermore, we demonstrate a magnetic-field-controlled directional growth of phase domains during both heating and cooling, which is predominantly linked to the local effect of magnetic dipolar fields created by the alignment of magnetic moments in the emerging (disappearing) FM phase fraction during heating (cooling). These findings highlight the importance of the magnetoelastic character of phase domains for enabling the local control of micro- and nanoscale phase separation patterns using magnetic fields or elastic stresses.

Evaluation of phase separation behavior of amine + organic solvent + H2O phase change absorbents

CO2 phase change absorbents, CPCAs, have attracted growing interest due to their potential of energy saving for CO2 capture. Unclear phase separation pattern is challenging for the efficient development of CPCAs. The effect of organic solvents properties on the phase separation process was investigated in this work. The difference of ion–dipole interaction between ion-organic solvent and ion-water was used to illustrate the phase separation behavior. Relative dielectric constant and ET(30) to water were proposed as indicators to provide guidance on the selection of organic solvents in CPCA. The organic solvents with less dielectric constant and ET(30) relative to water, were tend to phase split, and higher ion distribution coefficient obtained. The developed MEA CPCAs showed larger CO2 cyclic capacity than 30wt.%MEA, among which 1,4-dioxane CPCA was 49.0% higher than benchmark MEA solution.

Controlling the various phase-separated patterns in mixed monolayers of non-amphiphilic fluorinated derivatives and hydrogenated comb copolymers

Mixed monolayers were prepared on the water surface of non-amphiphilic fluorinated derivatives, as well as hydrocarbon-based comb copolymers, whose intermolecular interactions could be tuned using a copolymerization method. The phase-separated morphologies of the monolayers could also be controlled. Diamino-s-triazine rings, which were critical in morphology formation, were introduced into the hydrophilic groups of the comb copolymers for the phase-separated patterning. The phase-separation pattern was precisely controlled using various parameters, such as the chain length of the fluorinated derivatives, composition of the comb copolymers, mixing ratio, subphase temperature, and surface pressure. The obtained sea-island phase-separated patterns were classified into domain-like, circular, non-circular linear, donut-like, and centrally protruding circular domain morphologies. At 35 °C, a new nucleation phenomenon was observed inside the donut-shaped pattern that had developed through coagulation. During the phase separation of the current system, crystalline regularity was achieved in the fluorinated sea region around the domain, which was generally a continuous phase.

Multiple ultrasounds assisted phase separation and monotectic solidification of liquid ternary Al81.5Cu14.7Bi3.8 immiscible alloy

Multiple power ultrasounds were employed to investigate the phase transition process of ternary Al81.5Cu14.7Bi3.8 immiscible alloy by various exerting modes. As the ultrasonic sources increased, the liquid phase separation pattern transformed from (Bi)-rich layered macrosegregation into the uniform distribution of secondary (Bi) droplets. Meanwhile, the primary (Al) phase evolved from coarse dendrites into plenty of small spherical grains and also tended to be uniformly dispersed. The subsequently formed ternary (Al) + (Al2Cu) + (Bi) monotectic structure, featured by the alternative (Al) and (Al2Cu) lamellar structure with fine (Bi) grains distributed, was coarsened first and then refined. Numerical simulations showed that the transient cavitation and the acoustic streaming strength were significantly enhanced by increasing ultrasonic beams, with the fourfold ultrasounds producing the most prominent effects on the phase separation process. The intensive and enlarged cavitation areas greatly accelerated the nucleation of both the secondary liquid phase and primary solid phase, which refined the growing (Bi) droplets and (Al) dendrites. The strength and morphology of acoustic streaming were the key factors in offsetting Stokes motion and carrying the growing grains to various regions, resulting in a uniform microstructure. Furthermore, increasing ultrasonic sources improved the friction and wear properties of the solidified alloy, which indicated that the Al81.5Cu14.7Bi3.8 immiscible alloy may become an excellent wear-resistant material owing to the uniform monotectic structure fabricated by the fourfold ultrasounds.

Detecting different amorphous – Amorphous phase separation patterns in co-amorphous mixtures with high resolution imaging FTIR spectroscopy

Many active pharmaceutical ingredients (API) in development suffer from low aqueous solubilities. Instead of the crystal form, the amorphous state can be used to improve the API’s apparent solubility. However, the amorphous state has a higher Gibb’s free energy and is inherently unstable and tends to transform back to the more stable crystal form. In co-amorphous mixtures, phase separation needs to occur before there can be crystallization. The aim of this study was to devise a method to study amorphous-amorphous phase separation with high resolution imaging Fourier transform infrared (FTIR) spectroscopy with seven 1:1 M ratio API-API binary mixtures being examined. The binary mixtures were amorphized by melt-quenching and stored above their glass transition temperature (Tg) to monitor their phase separation. Thermodynamic properties (crystallization tendency, melting point (Tm) and Tg) of these mixtures were measured with differential scanning calorimetry (DSC) to verify the amorphization method and to assess the optimal storage temperature. The phase separation was examined with FTIR imaging in the transmission mode. Furthermore, measurements with two pure APIs were performed to ensure that the alterations occurring in the spectra were caused by phase separation not storage stress. In addition, the reproducibility of the imaging FTIR spectrometer was verified. The spectra were analyzed with principal component analysis (PCA) and a characteristic peak comparison method. Scatter-plots were produced from the amount of phase separated pixels in the measurement area as a way of visualizing the progress of phase separation. The results indicated that imaging with FTIR spectroscopy can produce reproducible results and the progress of phase separation can be detected as either a sigmoidal or as a start-to-finish linear pattern depending on the substances.

Mechanically robust and highly conductive semi-interpenetrating network anion exchange membranes for fuel cell applications

A series of highly transparent semi-interpenetrating polymer network anion exchange membranes (SIPN AEMs) composed of a flexible and cation cross-linked polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (cQSEBS) component, and a rigid, highly-charged quaternized poly(2,6-dimethyl phenylene oxide) (QPPO) component are prepared. Flexible and rigid polymer backbones endow SIPN AEMs with excellent flexibility and mechanical strength. High charge content and well defined hydrophilic/hydrophobic phase separation patterns ensure SIPN AEMs with improved ionic conductivity. Alkali-resistant SEBS, enhanced dimensional stability and ordered microphase separation morphology contribute to the good chemical stability of SIPN-AEMs. Among these AEMs, SIPN-cQSEBS/QPPO-10 with an IEC of 1.93 mmol g−1 achieves a better trade-off between tensile strength (19.36 MPa at 25 °C in wet state), flexibility (58.43% at 25 °C in wet state) and OH− conductivity (103.1 mS cm−1 at 80 °C). Besides, SIPN-cQSEBS/QPPO-10 shows low swelling degree (15.4% at 80 °C) and high chemical stability (95.9%, 88.7%, 82.7% and 88.5% retention in weight, OH− conductivity, tensile strength and elongation at break, respectively, after immersing in 1 M NaOH at 80 °C for 30 days). Importantly, a fuel cell peak power density of 1.174 W cm−2 is obtained at 80 °C by using SIPN-cQSEBS/QPPO-10 as the separator.

Quantitative analysis of phase formation and growth in ternary mixtures upon evaporation of one component.

We perform a quantitative analysis of Monte Carlo simulation results of phase separation in ternary blends upon evaporation of one component. Specifically, we calculate the average domain size and plot it as a function of simulation time to compute the exponent of the obtained power law. We compare and discuss results obtained by two different methods, for three different models: two-dimensional (2D) binary-state model (Ising model), 2D ternary-state model with and without evaporation. For the ternary-state models, we study additionally the dependence of the domain growth on concentration, temperature and initial composition. We reproduce the expected 1/3 exponent for the Ising model, while for the ternary-state model without evaporation and for the one with evaporation we obtain lower values of the exponent. It turns out that phase separation patterns that can form in this type of systems are complex. The obtained quantitative results give valuable insights towards devising computable theoretical estimations of size effects on morphologies as they occur in the context of organic solar cells.

Evaporation Patterns of Dextran-Poly(Ethylene Glycol) Droplets with Changes in Wettability and Compatibility.

The dextran–PEG system is one of the most famous systems exhibiting phase separation. Various phase behaviors, including the evaporation process of the dextran–PEG system, have been studied in order to understand the physicochemical mechanism of intracellular phase separation and the effect of condensation on the origin of life. However, there have been few studies in dilute regime. In this study, we focused on such regimes and analyzed the pattern formation by evaporation. The specificity of this regime is the slow onset of phase separation due to low initial concentration, and the separated phases can have contrasting wettability to the substrate as evaporation progresses. When the polymer concentration is rather low (<5 wt%), the dextran–PEG droplets form a phase-separated pattern, consisting of PEG at the center and dextran ring of multiple strings pulling from the ring. This pattern formation is explained from the difference in wettability and compatibility between dextran and PEG upon condensation. At the initial dilute stage, the dextran-rich phase with higher wettability accumulates at the contact line of the droplet to form a ring pattern, and then forms multiple domains due to density fluctuation. The less wettable PEG phase recedes and pulls the dextran domains, causing them to deform into strings. Further condensation leads to phase separation, and the condensed PEG with improved wettability stops receding and prevents a formed circular pattern. These findings suggest that evaporation patterns of polymer blend droplets can be manipulated through changes in wettability and compatibility between polymers due to condensation, thus providing the basis to explore origins of life that are unique to the process of condensate formation from dilute systems.

Supercritical fluid foaming of nanoscale phase patterned structures: An approach to lightweight hierarchical porous foams with superior thermal insulation

• Nanoscale phase patterns are observed in cyclic olefin copolymer (COC) blends. • Hierarchically porous foams are created by supercritical CO 2 foaming of COC blends. • Lightweight and superior thermal insulated foams are developed. Hierarchically porous (HP) design provides an effective alternative to develop lightweight thermal insulation (T-I) materials, which play an important role in efficient energy management. Unlike elaborate synthetic methods, achieving HP features via supercritical fluid (SCF) techniques is still at an early stage. In this study, a facile and effective approach is reported to develop tailored HP foams via SCF foaming of binary blends with nanoscale phase separation patterns. The resultant cyclic olefin copolymer (COC) blend foams are extremely lightweight (50 kg m −3 ) and have excellent thermal conductivity of 25.8 mW m -1 K −1 , which is on par with the thermal conductivity of air. Through the SCF foaming process, tunable HP structures can be created from COC blends with nanoscale phase patterns (phase size from ∼ 150 to 240 nm). Different from traditional T-I polystyrene foams, chemical resistant COC blend foams are good candidates for durable coatings, and a dual-mode thermal device was successfully assembled with active photothermal conversion functionality and passive T-I performance, which exhibited a temperature difference of 32 °C between the two surfaces under illumination (2.4 × 10 5 lx). This opens up a new perspective for the development of lightweight, chemically resistant and highly thermally insulating foams for thermal management applications.

Detecting Different Amorphous – Amorphous Phase Separation Patterns in Co-Amorphous Mixtures with High Resolution Imaging FTIR Spectroscopy

Detecting Different Amorphous – Amorphous Phase Separation Patterns in Co-Amorphous Mixtures with High Resolution Imaging FTIR Spectroscopy

Interaction of huntingtin with PRMTs and its subsequent arginine methylation affects HTT solubility, phase transition behavior and neuronal toxicity.

Huntington's disease (HD) is an incurable neurodegenerative disorder caused by a CAG expansion in the huntingtin gene (HTT). Post-translational modifications of huntingtin protein (HTT), such as phosphorylation, acetylation and ubiquitination, have been implicated in HD pathogenesis. Arginine methylation/dimethylation is an important modification with an emerging role in neurodegeneration; however, arginine methylation of HTT remains largely unexplored. Here we report nearly two dozen novel arginine methylation/dimethylation sites on the endogenous HTT from human and mouse brain and human cells suggested by mass spectrometry with data-dependent acquisition. Targeted quantitative mass spectrometry identified differential arginine methylation at specific sites in HD patient-derived striatal precursor cell lines compared to normal controls. We found that HTT can interact with several type I protein arginine methyltransferases (PRMTs) via its N-terminal domain. Using a combination of in vitro methylation and cell-based experiments, we identified PRMT4 (CARM1) and PRMT6 as major enzymes methylating HTT at specific arginines. Alterations of these methylation sites had a profound effect on biochemical properties of HTT rendering it less soluble in cells and affected its liquid-liquid phase separation and phase transition patterns in vitro. We found that expanded HTT 1-586 fragment can form liquid-like assemblies, which converted into solid-like assemblies when the R200/205 methylation sites were altered. Methyl-null alterations increased HTT toxicity to neuronal cells, while overexpression of PRMT 4 and 6 was beneficial for neuronal survival. Thus, arginine methylation pathways that involve specific HTT-modifying PRMT enzymes and modulate HTT biochemical and toxic properties could provide targets for HD-modifying therapies.

A novel jamming phase diagram links tumor invasion to non-equilibrium phase separation

SummaryIt is well established that the early malignant tumor invades surrounding extracellular matrix (ECM) in a manner that depends upon material properties of constituent cells, surrounding ECM, and their interactions. Recent studies have established the capacity of the invading tumor spheroids to evolve into coexistent solid-like, fluid-like, and gas-like phases. Using breast cancer cell lines invading into engineered ECM, here we show that the spheroid interior develops spatial and temporal heterogeneities in material phase which, depending upon cell type and matrix density, ultimately result in a variety of phase separation patterns at the invasive front. Using a computational approach, we further show that these patterns are captured by a novel jamming phase diagram. We suggest that non-equilibrium phase separation based upon jamming and unjamming transitions may provide a unifying physical picture to describe cellular migratory dynamics within, and invasion from, a tumor.

Lattice Boltzmann simulation for phase separation with chemical reaction controlled by thermal diffusion.

This study investigates phase separation behavior and pattern formation in a binary fluid with chemical reaction controlled by thermal diffusion. By incorporating the Arrhenius equation into the lattice Boltzmann method (LBM), the coupling effects of the pre-exponential factor K, viscosity [Formula: see text], and thermal diffusion D on phase separation were successfully evaluated. The effect of the competition between thermal diffusion and concentration on the phase separation morphology and dynamics of binary mixtures under a chemically reacting controlled by slow cooling is assessed based on the extended LBM. The calculations indicated that increases in viscosity and thermal diffusion can obtain interconnected structures (ISs) and lamellar structures (LSs) for cases with small K. However, concentric phase-separated structures (CSs) were observed in cases with large K. The increase in the degree and efficiency of phase separation were significantly greater in cases with decreased viscosity and increased thermal diffusion.

Ice needles weave patterns of stones in freezing landscapes

Patterned ground, defined by the segregation of stones in soil according to size, is one of the most strikingly self-organized characteristics of polar and high-alpine landscapes. The presence of such patterns on Mars has been proposed as evidence for the past presence of surface liquid water. Despite their ubiquity, the dearth of quantitative field data on the patterns and their slow dynamics have hindered fundamental understanding of the pattern formation mechanisms. Here, we use laboratory experiments to show that stone transport is strongly dependent on local stone concentration and the height of ice needles, leading effectively to pattern formation driven by needle ice activity. Through numerical simulations, theory, and experiments, we show that the nonlinear amplification of long wavelength instabilities leads to self-similar dynamics that resemble phase separation patterns in binary alloys, characterized by scaling laws and spatial structure formation. Our results illustrate insights to be gained into patterns in landscapes by viewing the pattern formation through the lens of phase separation. Moreover, they may help interpret spatial structures that arise on diverse planetary landscapes, including ground patterns recently examined using the rover Curiosity on Mars.