Phase Separation Process Research Articles

Influence of boron incorporated biphasic calcium phosphate on mechanical, thermal, and biological properties of poly(vinylidene fluoride) membrane scaffold

AbstractIn this paper, boron (B)‐doped biphasic calcium phosphate (BCP)/poly(vinylidene fluoride) (PVDF) membrane scaffolds were developed by the combination of non‐solvent induced phase separation and lyophilization processes. In addition, the effects of the synthesized B‐incorporated BCP powders on the properties of the fabricated scaffolds were investigated. The physicochemical and morphological properties of the scaffolds were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy. The physical properties were evaluated by surface wettability and swelling measurements, whereas the mechanical properties were investigated by tensile strength measurements. The thermal behavior was determined by differential scanning calorimetry, the β‐crystallization ratio was calculated by FTIR, and the β‐phase structure was characterized by X‐ray diffraction. The bioactivity was evaluated in the simulated body fluid, and the cytotoxicity of the scaffolds was also investigated by performing in vitro cell culture experiments. The results showed that the incorporation of B into the PVDF matrix improved the hydrophilicity while reducing the degree of swelling of the scaffolds. Tensile strength was slightly reduced by the powder content, but yet the strength of all scaffolds was mechanically compatible with native bone. Increasing the B content up to 0.5 and 1 wt.% was improved the thermal properties, the β‐crystalline phase fraction, and thus the piezoelectricity. Furthermore, B‐doped BCP/PVDF‐based scaffolds significantly promoted bioactivity, cell viability, and proliferation without cytotoxicity, compared to the PVDF scaffold, depending on the B content. In conclusion, our results indicate that the PVDF‐based composites in the form of membrane scaffolds that support bone growth have the potential to be highly sought‐after candidates in the field of biomedical applications.

Protein Condensate Atlas from predictive models of heteromolecular condensate composition

Biomolecular condensates help cells organise their content in space and time. Cells harbour a variety of condensate types with diverse composition and many are likely yet to be discovered. Here, we develop a methodology to predict the composition of biomolecular condensates. We first analyse available proteomics data of cellular condensates and find that the biophysical features that determine protein localisation into condensates differ from known drivers of homotypic phase separation processes, with charge mediated protein-RNA and hydrophobicity mediated protein-protein interactions playing a key role in the former process. We then develop a machine learning model that links protein sequence to its propensity to localise into heteromolecular condensates. We apply the model across the proteome and find many of the top-ranked targets outside the original training data to localise into condensates as confirmed by orthogonal immunohistochemical staining imaging. Finally, we segment the condensation-prone proteome into condensate types based on an overlap with biomolecular interaction profiles to generate a Protein Condensate Atlas. Several condensate clusters within the Atlas closely match the composition of experimentally characterised condensates or regions within them, suggesting that the Atlas can be valuable for identifying additional components within known condensate systems and discovering previously uncharacterised condensates.

Liquid-Liquid Phase Separation Mediated Formation of Chiral 2D Crystalline Nanosheets of a Co-Assembled System.

The role of macromolecule-macromolecule and macromolecule-H2O interactions and the resulting perturbation of the H-bonded network of H2O in the liquid-liquid phase separation (LLPS) process of biopolymers are well-known. However, the potential of the hydrated state of supramolecular structures (non-covalent analogs of macromolecules) of synthetic molecules is not widely recognized for playing a similar role in the LLPS process. Herein, LLPS occurred during the co-assembly of hydrated supramolecular vesicles (bolaamphiphile, BA1) with a net positive charge (zeta potential, ζ = +60 ± 2mV) and a dianionic chiral molecule (disodium l-[+]-tartrate) is reported. As inferred from cryo-transmission electron microscopy (TEM), the LLPS-formed droplets serve as the nucleation precursors, dictating the structure and properties of the co-assembly. The co-assembled structure formed by LLPS effectively integrates the counter anion's asymmetry, resulting in the formation of ultrathin free-standing, chiral 2D crystalline sheets. The significance of the hydrated state of supramolecular structures in influencing LLPS is unraveled through studies extended to a less hydrated supramolecular structure of a comparable system (BA2). The role of LLPS in modulating the hydrophobic interaction in water paves the way for the creation of advanced functional materials in an aqueous environment.

The liquid-liquid phase separation signature predicts the prognosis and immunotherapy response in hepatocellular carcinoma.

Hepatocellular carcinoma (HCC) is a common and fatal malignancy characterized by poor patient prognosis and treatment outcome. The process of liquid-liquid phase separation in tumour cells alters the dysfunction of biomolecular condensation in tumour cells, which affects tumour progression and treatment. We downloaded the data of HCC samples from TCGA database and GEO database, and used a machine learning method to build a new liquid-liquid phase separation index (LLPSI) by liquid-liquid phase separation related genes. The LLPSI-related column line Figure was constructed to provide a quantitative tool for clinical practice. HCC patients were divided into high and low LLPSI groups based on LLPSI, and clinical features, tumour immune microenvironment, chemotherapeutic response, and immunotherapeutic response were systematically analysed. LLPSI, which consists of five liquid-liquid phase separation-associated genes (MAPT, WDR62, PLK1, CDCA8 and TOP2A), is a reliable predictor of survival in patients with HCC and has been validated in multiple external datasets. We found that the high LLPSI group showed higher levels of immune cell infiltration and better response to immunotherapy compared to the low LLPSI group, and LLPSI can also be used for prognostic prediction in various cancers other than HCC. Invitro experiments verified that knockdown of MAPT could inhibit the proliferation and migration of HCC. The LLPSI identified in this study can accurately assess the prognosis of patients with HCC and identify patient populations that will benefit from immunotherapy, providing valuable insights into the clinical management of HCC.

Enhanced UV Penetration and Cross-Linking of Isoporous Block Copolymer and Commercial Ultrafiltration Membranes using Isorefractive Solvent.

Amphiphilic block copolymers are promising candidates for the fabrication of ultrafiltration membranes with an isoporous integral asymmetric structure. The membranes are typically fabricated by the combination of block copolymer self-assembly and the non-solvent-induced phase separation (SNIPS) process resulting in isoporous integral asymmetric membranes. Certainly, all these membranes lack thermal and chemical stability limiting the usage of such materials. Within this study, the fabrication of completely cross-linked isoporous integral asymmetric block copolymer membranes is demonstrated by UV cross-linking resulting in chemical and thermal stable ultrafiltration membranes. The UV cross-linking process of PVBCB-b-P4VP (poly(4-vinylbenzocyclobutene)-b-poly(4vinylpyridine)) block copolymer membranes in dependency of irradiation time, intensity, distance between membrane and UV source and the wavelength is investigated. Furthermore, it is shown that the penetration depths can be increased by soaking the membranes in wave-guiding solutions before UV cross-linking is carried out. Moreover, a completely new and easy cross-linking strategy is developed based on isorefractive solvents resulting in thermal and chemically stable membranes that are cross-linked through the whole membrane thickness. Finally, the new cross-linking strategy in isorefractive solutions is transferred to commercial PVDF and PAN-co-PVC polymer membranes paving the way for more stable and sustainable ultrafiltration membranes.

Study of the efficiency of sodium silicate water softening processes

The current state of natural water resourses requires preliminary softening for almost all drinking waters and waters for energy purposes. Therefore, the search for effective softening technologies and reagents is especially relevant today. Researches in this field are constantly increasing every year due the intensive quality deterioration of the natural waters. The processes of calcium and magnesium ions removing from water are on central place in such researches. It is traditionally considered that magnesium ions are more difficult to remove from water than calcium ions because magnesium ions form less quantity of insoluble compounds. The total efficiency of water softening processes depends on the residual content of both cations. Therefore, researchers also pay a lot of attention to magnesium ions removing. Sodium hydroxide and sodium phosphate are considered as a perspective reagents in such processes. However, the use of first reagent is associated with a significant increase of pH index, and the use of second reagent requires a big quantity of the reagent and needs the alkaline medium for sufficient efficiency. Therefore, in this work, we investigated the effectiveness of sodium silicate in the processes of magnesium and calcium ions removing from the aqueous medium. A characteristic feature of the solid phase formation in reaction between magnesium cations and silicate anions is the significant reaction dependence on the pH index. In neutral environment, the formation of a solid phase in model solutions was not visually fixed. However, some decrease of water hardness after filtering through "blue tape" filter paper is still observed. And it is decrease with increasing of pH index. The most effective softening process can be obtained at pH levels > 10. It was not possible to obtain any positive results during study of settling and filtering processes of the formed solid phase. At the same time, the ratio between the components and the initial water hardness does not affect the clarification process practically. However, sodium silicate can be quite effective in stoichiometric or higher ratios. But a significant disadvantage of such method is a pH index increasing when the components are mixed. It requires futher adjusting the pH level in the treated water. And this is aditional stage of water treatment. It was not possible to obtain positive results when aluminum hydroxide was used as a settling and filtering intensifier. With the ratio K = [SiO32-, mg-eq]/[Mg2+, mg-eq] = 1 and different doses of aluminum ions, there is no significant intensification of sedimentation processes in the range of aluminum ions doses from 10 to 70 mg/dm3. And with aluminum doses less than 30 mg/dm3, there is even inhibition of the settling process. Like in the case of sodium silicate silicate treatment of magnesium containing solutions, the precipitation of calcium silicate strongly depends on the pH level. High efficiency of process is observed only in a highly alkaline environment. Under other conditions, the softening efficiency is significantly reduced. With an excess or lack of a precipitant, more compact particles are formed. The settling process for such particles occur more faster. At the same time, for a stoichiometric or near ratio between the components, particles of the branched structure are formed. Such particles settle twice slowly and occupy a larger imaginary volume. With a stoichiometric ratio of components, the speed is significantly slowed down, and when K = [SiO32-, mg-eq]/[Ca2+, mg-eq] ≥ 1,0 all filter pores are blocked during the first 10 min and liquid phase transportation stops. Reducing the initial water hardness to 20 mg-eq/dm3 does not significantly change the situation. Clarification of the suspension occurs partially. A significant amount of suspended particles remains in the mother solution. The flocculating ability of silicon compounds does not appeared under these conditions. When the content of calcium ions is reduced to 10,2 mg-eq/dm3, treatment with an equivalent amount of sodium silicate does not lead to a solid phase formation. Although after filtering through the "blue tape" filter the water hardness decreases. At the same time, the filtration properties of the solid phase formed during the softening process are the same as the filtration properties of carbonates, phosphates and hydroxides, so the reagent cannot be recommended for use in low- and medium-productivity systems, where the filtration is a main phase separation process.

Chemically reactive and aging macromolecular mixtures. I. Phase diagrams, spinodals, and gelation

Multicomponent macromolecular mixtures often form higher-order structures, which may display non-ideal mixing and aging behaviors. In this work, we first propose a minimal model of a quaternary system that takes into account the formation of a complex via a chemical reaction involving two macromolecular species; the complex may then phase separate from the buffer and undergo a further transition into a gel-like state. We subsequently investigate how physical parameters such as molecular size, stoichiometric coefficients, equilibrium constants, and interaction parameters affect the phase behavior of the mixture and its propensity to undergo aging via gelation. In addition, we analyze the thermodynamic stability of the system and identify the spinodal regions and their overlap with gelation boundaries. The approach developed in this work can be readily generalized to study systems with an arbitrary number of components. More broadly, it provides a physically based starting point for the investigation of the kinetics of the coupled complex formation, phase separation, and gelation processes in spatially extended systems.

Enhanced separation of oil-in-water emulsion by cyclic penetration of emulsion droplets through an oil layer

The separation of emulsion components is a typical heterogeneous phase separation process. This process can be promoted by coalescence of the dispersed phase droplets. However, the coalescence would be inhibited due to the interface between the continuous and dispersed phases. The separation efficiency can be increased by increasing the probability of collisions between the droplets, and this can be realized by increasing the area of contact among the dispersed phase droplets. In this study, a new enhanced separation method involving the circulation of emulsion droplets containing an emulsified oil phase through an oil layer is proposed. The migration of the emulsified oil phase from the millimeter-sized droplets to the oil layer was studied. This migration enabled efficient separation of the oil and water phases, and this process was assessed by using a dyeing agent in the oil phase and by monitoring the variation in the turbidity. The influence of main factors such as the circulating droplet size, thickness of the oil layer, and effect of the circulation rate on the separation was determined. The turbidity of the emulsion reduced from 394.33 NTU to 10.98 NTU, with a separation efficiency of 97.22 % under the optimum operation conditions. The linear fitting relationship for the main factors that affect separation with the duration or number of circulation cycles was obtained. The results indicate that the novel strategy of using an additional oil layer and circulating emulsion droplets through it is promising for oil–water separation, especially via gravity separation.

Micron-Sized Thiol-Functional Polysilsesquioxane Microspheres with Open and Interconnected Macropores: Effects of the System Composition on the Porous Structure and Particle Size of the Microspheres.

Control of the porous structure and particle size is essential for improving the properties of polysilsesquioxane (PSQ) microspheres. Herein, using the strategy combining inverse suspension polymerization, two-step sol-gel- and polymerization-induced phase separation processes, micron-sized thiol-containing macroporous PSQ (TMPSQ) microspheres with controllable morphologies, adjustable particle diameters (4.9-17.3 μm), and pore sizes (40-3774 nm) were prepared. The morphology and size of the TMPSQ microspheres were characterized by SEM. The mercury intrusion method was employed to analyze the porous structure of the microspheres. The effects of the composition of the sol-gel disperse phase, the mass ratio of the sol-gel disperse phase to the oil continuous phase (WRW/O), and the Span 80 mass content in the oil continuous phase on the morphology, particle diameter and pore size of the TMPSQ microspheres were investigated. Results indicated that the composition of the sol-gel disperse phase determines the morphology and porous structure of the microspheres, and WRW/O and Span 80 content have remarkable impacts on the morphology and particle size of the microspheres. This study is beneficial to the design and fabrication of functional PSQ microspheres with desired properties and promising application prospects.

Effect of SiO2-doped nanoparticle/electrostatic spinning system on the electro-optical properties of polymer dispersed liquid crystals for smart windows

ABSTRACT Polymer Dispersed Liquid Crystal (PDLC) films are attracting increasing attention as versatile and innovative material for use in electrical switching and flexible devices. This paper investigates the effect of a Poly(methyl methacrylate (PMMA) nanospun membrane system doped with SiO2 nanoparticles on the electro-optical properties and transmittance/voltage slopes of thiol- and acrylate-based PDLC films. Experimental samples were prepared for testing by adding mixtures of liquid crystals and crosslinkers in different proportions to liquid crystal cassettes doped with PMMA/SiO2 nanospun membranes. The size of the polymer mesh was found to influence all parameters of PDLC. The phase separation process, which determines the morphology and electro-optical properties of PDLC films, is directly affected by the doping of different components of PMMA/SiO2. The doping of the PMMA/SiO2 system resulted in improved optoelectronic properties of PDLC films, significantly enhanced weathering resistance, and increased the degree of intelligent regulation of the transmittance of PDLC films. Thus, by developing PDLC-doped reticulated nanofibre films with faster response times and better electro-optical properties, the potential for technological applications of PDLC-based devices in optical windows, displays, energy storage and flexible devices can be significantly enhanced.

Additive manufacturing of porous ceramic structures by indirect powder bed fusion with laser beam using a novel polyamide/alumina-based feedstock

Porous alumina structures were developed by indirect Powder Bed Fusion with Laser Beam (PBF-LB), employing a novel feedstock (composite granules) based on alumina (Al2O3), bio-renewable polyamide 612 (PA612), and micron-sized graphite (MG) using a commercial PBF-LB machine that operates with a low-power visible light diode laser. Regular and slightly rounded composite granules were prepared via the thermally induced phase separation (TIPS) process in dimethyl sulfoxide (DMSO) using 0.05 vol% of PA612, 40/60 vol% of Al2O3/PA612 and 6.25 wt% of MG, and then characterized via density measurements, Hausner's ratio, SEM-EDS, particle size distribution, Raman spectroscopy, DSC, and TGA. Experimental conditions to be used in the PBF-LB process were determined in order to obtain high-quality green porous structures with a controlled geometry. After the heating treatments, sintered components with good structural integrity, a high open porosity associated with interconnected pores in the struts, and a ceramic matrix with microsized-equiaxial grains were obtained. The evaluation of the mechanical properties was performed by diametral compression testing. In order to improve these properties, a vacuum infiltration process involving a low-concentration alumina-ethanol suspension was used on pre-sintered discs. As a consequence of the infiltration process, the discs showed improved mechanical properties after sintering without the porosity having been significantly affected.

Bioinspired Superhydrophobic All-In-One Coating for Adaptive Thermoregulation.

The development of scalable and passive coatings that can adapt to seasonal temperature changes while maintaining superhydrophobic self-cleaning functions is crucial for their practical applications. However, the incorporation of passive cooling and heating functions with conflicting optical properties in a superhydrophobic coating is still challenging. Herein, an all-in-one coating inspired by the hierarchical structure of a lotus leaf that combines surface wettability, optical structure, and temperature self-adaptation is obtained through a simple one-step phase separation process. This coating exhibits an asymmetrical gradient structure with surface-embedded hydrophobic SiO2 particles and subsurface thermochromic microcapsules within vertically distributed hierarchical porous structures. Moreover, the coating imparts superhydrophobicity, high infrared emission, and thermo-switchable sunlight reflectivity, enabling autonomous transitions between radiative cooling and solar warming. The all-in-one coating prevents contamination and over-cooling caused by traditional radiative cooling materials, opening up new prospects for the large-scale manufacturing of intelligent thermoregulatory coatings.

Phase separation provides a mechanism to drive phenotype switching.

Phenotypic switching plays a crucial role in cell fate determination across various organisms. Recent experimental findings highlight the significance of protein compartmentalization via liquid-liquid phase separation in influencing such decisions. However, the precise mechanism through which phase separation regulates phenotypic switching remains elusive. To investigate this, we established a mathematical model that couples a phase separation process and a gene expression process with feedback. We used the chemical master equation theory and mean-field approximation to study the effects of phase separation on the gene expression products. We found that phase separation can cause bistability and bimodality. Furthermore, phase separation can control the bistable properties of the system, such as bifurcation points and bistable ranges. On the other hand, in stochastic dynamics, the droplet phase exhibits double peaks within a more extensive phase separation threshold range than the dilute phase, indicating the pivotal role of the droplet phase in cell fate decisions. These findings propose an alternative mechanism that influences cell fate decisions through the phase separation process. As phase separation is increasingly discovered in gene regulatory networks, related modeling research can help build biomolecular systems with desired properties and offer insights into explaining cell fate decisions.

Recyclable and leakage-suppressed microcellular liquid–metal composite foams for stretchable electromagnetic shielding

The metallic conductivity and high liquidity of liquid metal (LM) make LM-polymer composites exhibit high electrical conductivity, large stretchability, and excellent mechanical–electrical decoupling, which provide significant advantages in the fabrication of stretchable electromagnetic interference (EMI) shielding materials. However, problems such as undesired LM leakage, high density, and poor recyclability due to the frequent use of chemically cross-linked polymers limit the applications of LM-polymer composites. Herein, we report the fabrication of stretchable and recyclable microcellular thermoplastic polyurethane (TPU)/LM composite foams (TLFs) with controllable LM distribution through a water–vapor-induced phase separation (WVIPS) process. The sedimentation of LM droplets helps to improve the shielding effectiveness (SE) of TLF, while the microcellular structure enables TLF with more uniform LM dispersion to achieve high leakage resistance. Moreover, the stretch-activated TLF shows high electrical stability with only slight resistance changes during stretching and exhibits a strain-insensitive shielding behavior. As a stretchable joule heater, the sample has outstanding Joule-heating performance, with stable temperature dropping only slightly under large tensile strains. More importantly, the excellent solubility of TPU, combined with a solution-based WVIPS process, allows our TLFs to be easily recycled into new products with very similar structure and performance to those before recycling, indicating the ideal recyclability of such materials.

Controllable Phase Separation Engineering of Iron-Cobalt Alloy Heterojunction for Efficient Water Oxidation.

The tailor-made transition metal alloy-based heterojunctions hold a promising prospect for the electrocatalytic oxygen evolution reaction (OER). Herein, a series of iron-cobalt bimetallic alloy heterojunctions are purposely designed and constructed via a newly developed controllable phase separation engineering strategy. The results show that the phase separation process and alloy component distribution rely on the metal molar ratio (Fe/Co), indicative of the metal content dependent behavior. Theoretical calculations demonstrate that the electronic structure and charge distribution of iron-cobalt bimetallic alloy can be modulated and optimized, thus leading to the formation of an electron-rich interface layer, which likely tunes the d-band center and reduces the adsorption energy barrier toward electrocatalytic intermediates. As a result, the Fe0.25Co0.75/Co heterojunction exhibits superior OER activity with a low overpotential of 185 mV at 10 mA cm-2. Moreover, it can reach industrial-level current densities and excellent durability in high-temperature and high-concentration electrolyte (30 wt % KOH), exhibiting enormous potential for industrial applications.

Fluorescent protein tags affect the condensation properties of a phase-separating viral protein.

Fluorescent protein (FP) tags are extensively used to visualize and characterize the properties of biomolecular condensates despite a lack of investigation into the effects of these tags on phase separation. Here, we characterized the dynamic properties of µNS, a viral protein hypothesized to undergo phase separation and the main component of mammalian orthoreovirus viral factories. Our interest in the sequence determinants and nucleation process of µNS phase separation led us to compare the size and density of condensates formed by FP::µNS to the untagged protein. We found an FP-dependent increase in droplet size and density, which suggests that FP tags can promote µNS condensation. To further assess the effect of FP tags on µNS droplet formation, we fused FP tags to µNS mutants to show that the tags could variably induce phase separation of otherwise noncondensing proteins. By comparing fluorescent constructs with untagged µNS, we identified mNeonGreen as the least artifactual FP tag that minimally perturbed µNS condensation. These results show that FP tags can promote phase separation and that some tags are more suitable for visualizing and characterizing biomolecular condensates with minimal experimental artifacts.

Robust Photocatalytic MICROSCAFS® with Interconnected Macropores for Sustainable Solar-Driven Water Purification.

Advanced oxidation processes, including photocatalysis, have been proven effective at organic dye degradation. Tailored porous materials with regulated pore size, shape, and morphology offer a sustainable solution to the water pollution problem by acting as support materials to grafted photocatalytic nanoparticles (NPs). This research investigated the influence of pore and particle sizes of photocatalytic MICROSCAFS® on the degradation of methyl orange (MO) in aqueous solution (10 mg/L). Photocatalytic MICROSCAFS® are made of binder-less supported P25 TiO2 NPs within MICROSCAFS®, which are silica-titania microspheres with a controlled size and interconnected macroporosity, synthesized by an adapted sol-gel method that involves a polymerization-induced phase separation process. Photocatalytic experiments were performed both in batch and flow reactors, with this latter one targeting a proof of concept for continuous transformation processes and real-life conditions. Photocatalytic degradation of 87% in 2 h (batch) was achieved, using a calibrated solar light simulator (1 sun) and a photocatalyst/pollutant mass ratio of 23. This study introduces a novel flow kinetic model which provides the modeling and simulation of the photocatalytic MICROSCAFS® performance. A scavenger study was performed, enabling an in-depth mechanistic understanding. Finally, the transformation products resulting from the MO photocatalytic degradation were elucidated by high-resolution mass spectrometry experiments and subjected to an in silico toxicity assessment.

Computational study on CO2 absorption mechanism and structure–activity relationship of biphasic solvent

The biphasic solvents are conducive to improving the efficiency of CO2 capture and reducing the energy consumption caused by regeneration. This study explored their reaction process at the molecular level based on density functional theory (DFT): selection of diamines such as active amines with distinct amino groups, 1,4-butanediamine (BDA) and N-(2-aminoethyl)ethanolamine (AEEA), and with typical phase separation promoters, 2-(diethylamino)ethanolamine (DEEA), and N,N,N′,N′,N′′-pentamethyldiethylenetriamine (PMDETA). This study systematically explores the potential reaction paths in CO2 capture to quantitatively assesse the structure–activity relationships among different amines in different stages of absorption, the influence of reaction sequence on reaction rates, and further elucidates the characteristics of product formation and its impact on the phase separation process. The results indicated that the zwitterion mechanism is widely applicable and remains the dominant explanation for the biphasic solvent CO2 capture mechanism. The intramolecular proton transfer reaction is the key to influencing the absorption rate of CO2, but in the case of interproton transfer, the rate-determining step needs to be judged in conjunction with the type of amino groups on it. And the amine groups on AEEA react with CO2 in different orders, forming distinct zwitterions that have similar activity in later intramolecular proton transfers. Under the zwitterion mechanism, primary amino groups exhibit stronger proton affinity than secondary ones. In solvents approaching saturation stage, DEEA reacts with AEEA and CO2 earlier than PMDETA. This study reveals the reaction mechanism of biphasic solvents and the key paths in different phases, providing insights for developing new solvents.

The origin of the straight propagation of the σ phase in a Ni-based single crystal superalloy at elevated temperature

Topologically close-packed (TCP) phases, although inherently hard, are commonly perceived as detrimental in various alloys. In Ni-based single crystal superalloys (Ni-SXs), the primary adverse impact of TCP phases on material mechanical properties stems from their direct propagation, disrupting the original γ/γ′ dual-phase structure and leading to cleavage along the TCP phases under applied stress. Understanding the specific reasons for the straight propagation of TCP phases through the complex phase structure is essential for mitigating or potentially reversing their detrimental effects on material performance, a challenge that remains elusive. This study addressed this challenge by employing ultra-high spatial and energy resolution transmission electron microscopy (TEM) characterization, coupled with in situ scanning transmission electron microscopy (STEM) heating experiments in a fourth-generation Ni-based single crystal superalloy. Our research unveiled a significant phase-separation process during the incubation stage preceding σ phase formation at elevated temperatures, driven by the diffusion of atoms. Notably, domains of the γ′ phase, characterized by a scale of tens of nanometers, emerged within preexisting γ phases, and vice versa. This phenomenon reconstructed the original γ/γ′ dual-phase structure, leading to a finely refined dual-phase structure. The refined structure effectively reduced the diffusion distance of alloy elements necessary for forming σ phases. Consequently, the σ phases nucleated randomly and propagated directly through the newly refined γ/γ′ dual-phase structure. Throughout the thickening process, the notable difference in the diffusivity of alloying elements eventually resulted in the growth of a highly defective σ phase structure.

Controlling the polymorphs of PVDF membranes: Effects of a salt additive on PVDF polarization during phase separation processes

Polyvinylidene fluoride (PVDF) membranes, acclaimed for their outstanding chemical resistance, thermal stability, and mechanical properties, play a crucial role in diverse industrial purification applications. While various methods have been employed for fabricating PVDF membranes such as thermally induced, evaporation-induced, vapor-induced, and nonsolvent-induced phase separation processes, controlling the polarity of PVDF chains using these techniques remains challenging. Recent studies have shown that the nonpolar α-phase PVDF is susceptible to organic acid fouling owing to hydrophobic interactions, whereas the β-phase PVDF has demonstrated polarity and offers antifouling properties. Herein, porous PVDF membranes predominantly composed of the β-phase were successfully fabricated by incorporating a small amount of LiCl salt into the PVDF dope solution. The addition of LiCl influences ion–dipole moments between ions and PVDF during phase separation, simultaneously affecting the PVDF chain arrangement and membrane morphology. Since the LiCl additive alters both the pore size and structure of PVDF membranes, both freestanding and non-woven supported membranes were prepared and characterized to assess the effects of polarity and pore size on fouling tendency. Characterizations of prepared PVDF membranes revealed considerable changes in the PVDF polymorph, membrane morphology, pore size, and antifouling properties upon introducing the salt additive. Our findings imply that β-phase–dominant PVDF membranes can be effectively utilized in water purification applications.