Phase Separation Process Research Articles

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.

The role of physicochemical processes in the formation of the 3D genome and compartmentalization of the cell nucleus.

The review analyzes the role of physicochemical processes in the formation of the function-dependent architecture of the cell nucleus, built on the platform of a folded genome. The main attention is paid to various forms of the phase separation process, primarily the processes of liquid-liquid phase separation and polymer-polymer phase separation. The role of these processes in the formation of chromatin compartments and maintenance of three-dimensional genome architecture is discussed in detail. The relationship between genome activity and the creation of functional compartments in the cell nucleus is also analyzed.

Formation of Polyimide Membranes via Non-Solvent Induced Phase Separation: Insight from Molecular Dynamics Simulations.

Molecular dynamics simulations were applied to investigate the formation of P84 polyimide membranes through the non-solvent induced phase separation (NIPS) process, considering two scenarios: one using a conventional organic solvent like n-methyl-2-pyrrolidone (NMP) and the other a greener alternative, γ-butyrolactone (GBL), with water serving as the non-solvent. Different compositions of polymer solutions were established along the binodal boundaries of the respective systems, derived from experimental cloud point data on the ternary phase diagram. The resulting polymer membranes were analyzed and compared in terms of their morphology. The wettability of their surfaces was notably affected by the polymer content in the initial casting solution and demonstrated a correlation with the Brunauer-Emmet-Teller (BET) specific surface area of the associated polymer nanostructures. The GBL solvent systems produced porous polymers qualitatively similar to those obtained with NMP, albeit with slightly narrower pore size distributions.

Towards Single-Polymer-Based Fully Printed Textile-Based Flexible Ag2O-Zn Battery for Wearable Electronics

Printed textile-based flexible batteries are gaining attention in several applications, but they are becoming more relevant to the health care industry in terms of realizing wearable and skin-conformable electronic devices. A flexible battery must ideally be deformable along multiple directions. In this work, with an aim to develop a fully printed omnidirectional deformable battery, we report the fabrication process of a novel single-polymer-based flexible non-rechargeable planar Ag2O-Zn battery on a textile substrate using the stencil printing method. Except for the electrolyte, all the components of the battery, including the current collectors, the anode, the cathode, and the separator membrane, are fabricated using a single polymer, namely styrene–ethylene–butylene–styrene (SEBS). To fabricate the SEBS separator, we introduce the solvent evaporation-induced phase separation (SEIPS) process. In the SEIPS method, toluene and dimethyl sulfoxide (DMSO) are selected as the solvent–nonsolvent pair. The SEBS: toluene: DMSO system with a wt% ratio of 6:85:9 showed improved performance regarding the OCV tests. A polyacrylic acid (PAA)-based alkaline polymer gel is used as an electrolyte. The demonstrated process is simple, and, with suitable modifications, it should find its use in the development of digitally printed alkaline batteries.

Multifunctional Nanofibrous Hollow Microspheres for Enhanced Periodontal Bone Regeneration.

Destructive periodontitis destroys alveolar bone and eventually leads to tooth loss. While guided bone regeneration, which is based on creating a physical barrier to hinder the infiltration of epithelial and connective tissues into defect sites, has been widely used for alveolar bone regeneration, its outcomes remain variable. In this work, a multifunctional nanofibrous hollow microsphere (NFHMS) is developed for enhanced alveolar bone regeneration. The NFHMS is first prepared via combining a double emulsification and a thermally induced phase separation process. Next, E7, a short peptide with high specific affinity to bone marrow-derived stem cells (BMSCs), is conjugated onto the surface of NFHMS. After that, bone forming peptide (BFP), a short peptide derived from bone morphology protein 7 isloaded in calcium phosphate (CaP) nanoparticles, which are further encapsulated in the hollow space of the NFHMS-E7 to form NFHMS-E7-CaP/BFP. The NFHMS-E7-CaP/BFP selectively promoted the adhesion of BMSCs and expelled the adhesion of fibroblasts and epithelial cells. In addition, the BFP is sustainedly released from the NFHMS-E7-CaP/BFP to enhance the osteogenesis of BMSCs. A rat challenging fenestration defect model showed that the NFHMS-E7-CaP/BFP significantly enhanced alveolar bone tissue regeneration. This work provides a novel bioengineering approach for guided bone regeneration.

Liquid-liquid phase separation of microtubule-binding proteins in the regulation of spindle assembly.

Cell division is a highly regulated process essential for the accurate segregation of chromosomes. Central to this process is the assembly of a bipolar mitotic spindle, a highly dynamic microtubule (MT)-based structure responsible for chromosome movement. The nucleation and dynamics of MTs are intricately regulated by MT-binding proteins. Over the recent years, various MT-binding proteins have been reported to undergo liquid-liquid phase separation, forming either single- or multi-component condensates on MTs. Herein, we provide a comprehensive summary of the phase separation characteristics of these proteins. We underscore their critical roles in MT nucleation, spindle assembly and kinetochore-MT attachment during the cell division process. Furthermore, we discuss the current challenges and various remaining unsolved problems, highlights the ongoing research efforts aimed at a deeper understanding of the role of the phase separation process during spindle assembly and orientation. Our review aims to contribute to the collective knowledge in this area and stimulate further investigations that will enhance our comprehension of the intricate mechanisms governing cell division.

Diffusion mediated thermally induced phase separation for preparing poly(vinylidene fluoride) membranes with enhanced separation performances

Thermally induced phase separation (TIPS) process is an appealing method for preparing poly(vinylidene fluoride) (PVDF) membranes for separation. In this work, we developed a diffusion mediated thermally induced phase separation (d-TIPS) to prepare PVDF membranes with great molecules separation performances. We investigated the thermodynamics of ternary polymer solutions including PVDF, caprolactam (CPL), and Polyethylene glycol (PEG). We controlled liquid–liquid phase separation and the CPL diffusion by adjusting the addition of PEG and molecular weight to modulate the evolution of morphology from spherulitic to bicontinuous structure. The resulting membrane was characterized by morphology, surface chemistry, tensile strength, water contact angle, and perm-selectivity. The membrane was further stretched for enhanced strength, permeance, and rejection. This work provides a fundamental understanding of the diffusion mediated thermally induced phase separation and shows the great potential of PVDF membranes in macromolecules separation.

Rapid attainment of full wettability through surface PEGylation of hydrophobic polyvinylidene fluoride membranes via spray-coating for enhanced anti-biofouling performances

This manuscript explores the development of antifouling membranes fabricated by vapor-induced phase separation (VIPS) process and their spray-coating modification with an aqueous solution of a copolymer comprising butyl methacrylate and poly(ethylene glycol) methyl ether methacrylate, designated as poly(BMA-r-PEGMA). An initial optimization phase focused on improving the modification quality, with the aim of enhancing the wettability on both the top and bottom surfaces of the membranes, despite spraying on the top surface only. Our findings reveal that a sprayed solution concentration of 10 mg/mL, a pressure of 0.25 MPa, and a scan rate of 3000 mm/min achieved a decrease in water contact angle to 0 in less than 12 s for both membrane surfaces (the top surface directly exposed to the spray, and the bottom surface facing the instrument stage), suggesting that the spray-coating modifies the entire membrane’s bulk. The presence of the copolymer on both surfaces was also evidenced by FTIR and XPS tests. Further biofouling assessments demonstrated the performances of the optimized membrane (OM). In static attachment tests, the OM exhibited a high reduction in Escherichia coli adhesion, with less than 10 % adhering bacteria, compared to unmodified membranes. During the filtration of bacteria-containing wastewater, the OM boasted a flux recovery ratio approaching 60 % (against less than 40 % for a commercial hydrophilic membrane), a rejection rate of 99.3 %, and a water permeability of 2500 LMH/bar. Moreover, the OM was stable over a 4-week period, with a resistance to E. coli attachment remaining similar to prior immersion. These findings underscore the significant potential of spray-coating to develop stable and effective antifouling microfiltration membranes for the removal of microorganisms from wastewater.

A prion-like domain is required for phase separation and chloroplast RNA processing during cold acclimation in Arabidopsis.

Arabidopsis (Arabidopsis thaliana) plants can produce photosynthetic tissue with active chloroplasts at temperatures as low as 4°C, and this process depends on the presence of the nuclear-encoded, chloroplast-localized RNA-binding protein CP29A. In this study, we demonstrate that CP29A undergoes phase separation in vitro and in vivo in a temperature-dependent manner, which is mediated by a prion-like domain (PLD) located between the two RNA recognition motif domains of CP29A. The resulting droplets display liquid-like properties and are found near chloroplast nucleoids. The PLD is required to support chloroplast RNA splicing and translation in cold-treated tissue. Together, our findings suggest that plant chloroplast gene expression is compartmentalized by inducible condensation of CP29A at low temperatures, a mechanism that could play a crucial role in plant cold resistance.

Deep dewatering of sludge and resource recovery of hydroxyapatite: A recyclable approach via ionic liquid biphasic system and hydrogen bonds reformation

Deep dewatering of Waste Activated Sludge (WAS) through mechanical processes remains inefficient, primarily due to the formation of a stable hydrogen bonding network between the biopolymers and water, which consequently leads to significant water trapped by Extracellular Polymeric Substances (EPS). In this study, a novel and recyclable treatment for WAS based on Ionic Liquids (ILs) was established, named IL-biphasic aqueous system (IL-ABS) treatment. Specifically, the IL-ABS formed in WAS facilitated rapid and efficient in-situ deep dewatering while concurrently recovering hydroxyapatite. The water content decreased from an initial 98.27 % to 65.35 % with IL-ABS, formed by 1-Butyl-3-methylimidazolium bromide (BmimBr) and K3PO4 synthesized from waste H3PO4. Moreover, the recycled BmimBr maintaining the water content of the dewatered sludge consistently between 65.61 % and 67.25 % across five cycles, exhibited remarkable reproducibility. Through three-dimensional excitation-emission matrix, lactate dehydrogenase analyses and confocal laser scanning microscopy, the high concentration of BmimBr in the upper phase effectively disrupted the cells and EPS, which exposed protein and polysaccharide on the EPS surface. Subsequently, the K3PO4 in the lower phase led to an enhanced salting-out effect in WAS. Furthermore, FT-IR analysis revealed that K3PO4 disrupted the original hydrogen bonds between EPS and water. Then, BmimBr formed numerous hydrogen bonds with the sludge flocs, leading to deep dewatering and agglomeration of the sludge flocs during the unique phase separation process of IL-ABS. Notably, sludge-derived hydroxyapatite product exhibited remarkable adsorption capacity for prevalent heavy metal contaminants such as Pb2+, Cd2+ and Cu2+, with efficiencies comparable to those of commercial hydroxyapatite, thereby achieving the resource utilization of waste H3PO4. Moreover, economic calculations demonstrated the suitability of this novel treatment. This innovative treatment exhibits potential for practical applications in the non-mechanical deep dewatering of WAS.