Phase Separation In Polymer Blends Research Articles

Phase-separated polymer blends for controlled drug delivery by tuning morphology

Controlling drug release rate and providing physical and chemical stability to the active pharmaceutical ingredient are key properties of oral solid dosage forms. Here, we demonstrate a formulation strategy using phase-separated polymer blends where the morphology provides a route for tuning the drug release profile. By utilising phase separation of a hydrophobic and a hydrophilic polymer, the hydrophilic component will act as a channelling agent, creating a porous network upon dissolution that will dictate the release characteristics. With ptychographic X-ray tomography and scanning transmission X-ray microscopy we reveal how the morphology depends on both polymer fraction and presence of drug, and how the drug is distributed over the polymer domains. Combining X-ray imaging results with dissolution studies reveal how the morphologies are correlated with the drug release and showcase how tuning the morphology of a polymer matrix in oral formulations can be utilised as a method for controlled drug release.

Large-Scale Fabrication of Freestanding Polymer Ultrathin Porous Membranes for Transparent Transwell Coculture Systems.

Advancements in cell coculture systems with porous membranes have facilitated the simulation of human-like in vitro microenvironments for diverse biomedical applications. However, conventional Transwell membranes face limitations in low porosity (ca. 6%) and optical opacity due to their large thickness (ca. 10 μm). In this study, we demonstrated a one-step, large-scale fabrication of freestanding polymer ultrathin porous (PUP) membranes with thicknesses of hundreds of nanometers. PUP membranes were produced by using a gap-controlled bar-coating process combined with polymer blend phase separation. They are 20 times thinner than Transwell membranes, possessing 3-fold higher porosity and exhibiting high transparency. These membranes demonstrate outstanding molecular permeability and significantly reduce the cell-cell distance, thereby facilitating efficient signal exchange pathways between cells. This research enables the establishment of a cutting-edge in vitro cell coculture system, enhancing optical transparency, and streamlining the large-scale manufacturing of porous membranes.

Complex Effects of the External Electric Fields on the Phase Separation of Polymer Blends

Complex Effects of the External Electric Fields on the Phase Separation of Polymer Blends

High-Performance Nitric Oxide Gas Sensors Based on an Ultrathin Nanoporous Poly(3-hexylthiophene) Film.

Conjugated polymer (CP)-based organic field-effect transistors (OFETs) have been considered a potential sensor platform for detecting gas molecules because they can amplify sensing signals by controlling the gate voltage. However, these sensors exhibit significantly poorer oxidizing gas sensing performance than their inorganic counterparts. This paper presents a high-performance nitric oxide (NO) OFET sensor consisting of a poly(3-hexylthiophene) (P3HT) film with an ultrathin nanoporous structure. The ultrathin nonporous structure of the P3HT film was created via deposition through the shear-coating-assisted phase separation of polymer blends and selective solvent etching. The ultrathin nonporous structure of the P3HT film enhanced NO gas diffusion, adsorption, and desorption, resulting in the ultrathin nanoporous P3HT-film-based OFET gas sensor exhibiting significantly better sensing performance than pristine P3HT-film-based OFET sensors. Additionally, upon exposure to 10 ppm NO at room temperature, the nanoporous P3HT-film-based OFET gas sensor exhibited significantly better sensing performance (i.e., responsivity ≈ 42%, sensitivity ≈ 4.7% ppm-1, limit of detection ≈ 0.5 ppm, and response/recovery times ≈ 6.6/8.0 min) than the pristine P3HT-film-based OFET sensors.

Erratum to “Phase Separation of Polymer Blends Induced by an External Static Electric Field”

Erratum to “Phase Separation of Polymer Blends Induced by an External Static Electric Field”

Microdroplet-Facilitated Assembly of Thermally Activated Delayed Fluorescence-Encoded Microparticles with Non-interfering Color Signals.

Encoded microparticles (EMPs) have shown demonstrative value for multiplexed high-throughput bioassays such as drug discovery and diagnostics. Herein, we propose for the first time the incorporation of thermally activated delayed fluorescence (TADF) dyes with low-cost, heavy metal-free, and long-lived luminescence properties into polymer matrices via a microfluidic droplet-facilitated assembly technique. Benefiting from the uniform droplet template sizes and polymer-encapsulated structures, the resulting composite EMPs are highly monodispersed, efficiently shield TADF dyes from singlet oxygen, well preserve TADF emission, and greatly increase the delayed fluorescence lifetime. Furthermore, by combining with phase separation of polymer blends in the drying droplets, TADF dyes with distinct luminescent colors can be spatially separated within each EMP. It eliminates optical signal interference and generates multiple fluorescence colors in a compact system. Additionally, in vitro studies reveal that the resulting EMPs show good biocompatibility and allow cells to adhere and grow on the surface, thereby making them promising optically EMPs for biolabeling.

Synthesis of MAPbBr3 -Polymer Composite Films by Photolysis of DMF: Toward Transparent and Flexible Optical Physical Unclonable Functions (PUFs) with Hierarchical Multilevel Complexity.

Physical entities with inherent randomness have been investigated as anti-counterfeiting labels based on physical unclonable functions (PUFs). Herein, a transparent and flexible optical PUF label associated with multilevel complexity is demonstrated by taking advantage of the optical properties of hierarchical morphologies of the composite film composed of metal halide perovskite nanoparticles (MAPbBr3 NPs) and the intrinsic spinodal-decomposition-like phase separation of polymer blend (PMMA/PS blend). Due to the combinatorial effects of the photolysis synthesis of MAPbBr3 and the thermodynamic instability of the PMMA/PS blend, randomized patterns emerge at two-level scales. These patterns are intrinsically non-deterministic, and therefore, the PUF labels from the multilevel random patterns are challenging to replicate. This is mainly attributed to random spot patterns (higher-level patterns) confined within intricate bicontinuous patterns (lower-level patterns).

Phase Separation of Polymer Blends Induced by an External Static Electric Field

Phase Separation of Polymer Blends Induced by an External Static Electric Field

Cell-Sized Confinement Initiates Phase Separation of Polymer Blends and Promotes Fractionation upon Competitive Membrane Wetting

Cell-Sized Confinement Initiates Phase Separation of Polymer Blends and Promotes Fractionation upon Competitive Membrane Wetting

Visualizing Surface Phase Separation in PS-PMMA Polymer Blends at the Nanoscale.

Phase-separated polymer blend films are an important class of functional materials with numerous technological applications in solar cells, catalysis, and biotechnology. These technologies are underpinned by the precise control of phase separation at the nanometer length-scales, which is highly challenging to visualize using conventional analytical tools. Herein, we introduce tip-enhanced Raman spectroscopy (TERS), in combination with atomic force microscopy (AFM), confocal Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS), as a sensitive nanoanalytical method to determine lateral and vertical phase-separation in polystyrene (PS)-poly(methyl methacrylate) (PMMA) polymer blend films. Correlative topographical, molecular, and elemental information reveals a vertical phase separation of the polymers within the top ca. 20 nm of the blend surface in addition to the lateral phase separation in the bulk. Furthermore, complementary TERS and XPS measurements reveal the presence of PMMA within 9.2 nm of the surface and PS at the subsurface of the polymer blend. This fundamental work establishes TERS as a powerful analytical tool for surface characterization of this important class of polymers at nanometer length scales.

Visualization of Macrophase Separation and Transformation in Immiscible Polymer Blends

Visualization of Macrophase Separation and Transformation in Immiscible Polymer Blends

Concurrently enhanced mechanical properties and capacitive performance in all-organic dielectric polymer blend via phase separation

Phase separation of polymer blends has attracted much interest in designing high-performance materials with specific mechanical and dielectric properties. To this end, three types of poly(methacrylic ester)s, including poly(methyl methacrylate) (PMMA), poly(butyl methacrylate) (PBMA), and poly(isobutyl methacrylate) [P(iBMA)], have been incorporated in the poly(vinylidene fluoride-co-hexafluoropropylene) [P(VDF-HFP)] matrix, respectively. As exemplified in P(VDF-HFP)/P(iBMA) blended films, a conspicuous phase separation is experimentally observed and the blended film presents an enhanced Young's modulus and a one-fold increment in the elongation over the pristine P(VDF-HFP). The excellent plasticity is benefited from the interfacial regions between the two phases, which could effectively pin the cracks and retard the slippage under deformation. Simultaneously, an ultra-high Weibull breakdown strength (∼774 MV/m) is obtained in the blends, benefiting from the improved Young's modulus and excellent plasticity. The blends are endowed with an excellent energy storage density (∼21 J/cm3 at 830 MV/m), along with an impressive cycling stability. In contrary, P(VDF-HFP)/PMMA and P(VDF-HFP)/PBMA blended films sacrifice the plasticity due to the scarcity of phase separation; therefore, even though Young's moduli have been improved, there is no remarkable improvement for breakdown strengths and energy storage performances. The experimental results are augmented by molecular dynamics simulations. This contribution provides a facile approach to develop high-performance polymer dielectric materials through a phase separation design and emphasize the importance of plasticity for breakdown strength.

Facile Strategy for Modulating the Nanoporous Structure of Ultrathin π-Conjugated Polymer Films for High-Performance Gas Sensors.

Conventional conjugated polymer (CP) films based on organic field-effect transistors (OFETs) tend to limit the performance of gas sensors owing to restricted analyte diffusion and limited interactions with the charge carriers that accumulate in the first few monolayers of the CP film in contact with the dielectric layer. Herein, a facile strategy is presented for modulating the morphology and charge-transport properties of nanoporous CP films using shearing-assisted phase separation of polymer blends for fabricating OFET-based chemical sensors. This approach enables the formation of nanoporous films with pore size and thickness in the ranges of 90-550 and 7-27 nm, respectively, which can be controlled simply by varying the shear rate. The resulting OFET sensors exhibit excellent sensing performance when exposed to NH3 gas, demonstrating a high responsivity (≈70.7%) at 10 ppm and good selectivity toward NH3 over various organic solvent vapors. After a comprehensive analysis of the morphology and electrical properties of the CP films, it is concluded that morphological features, such as film thickness and surface area, affect the sensing performance of nanoporous-film-based OFET sensors more significantly compared to the charge-transport characteristics of the films.

Mechanical and Morphological Properties of Bio-Phenolic/Epoxy Polymer Blends.

Polymer blends is a well-established and suitable method to produced new polymeric materials as compared to synthesis of a new polymer. The combination of two different types of polymers will produce a new and unique material, which has the attribute of both polymers. The aim of this work is to analyze mechanical and morphological properties of bio-phenolic/epoxy polymer blends to find the best formulation for future study. Bio-phenolic/epoxy polymer blends were fabricated using the hand lay-up method at different loading of bio-phenolic (5 wt%, 10 wt%, 15 wt%, 20 wt%, and 25 wt%) in the epoxy matrix whereas neat bio-phenolic and epoxy samples were also fabricated for comparison. Results indicated that mechanical properties were improved for bio-phenolic/epoxy polymer blends compared to neat epoxy and phenolic. In addition, there is no sign of phase separation in polymer blends. The highest tensile, flexural, and impact strength was shown by P-20(biophenolic-20 wt% and Epoxy-80 wt%) whereas P-25 (biophenolic-25 wt% and Epoxy-75 wt%) has the highest tensile and flexural modulus. Based on the finding, it is concluded that P-20 shows better overall mechanical properties among the polymer blends. Based on this finding, the bio-phenolic/epoxy blend with 20 wt% will be used for further study on flax-reinforced bio-phenolic/epoxy polymer blends.

Solvo-selective imprinting of a thin polymer blend film for creating multi-length scale patterns

Controlling and spatial ordering of the phase separation in ultra-thin polymer-blend films is a viable approach to create complex surface structures with unique properties. This study reports a facile solvo-selective patterning technique in a phase-separated polymer blend thin film comprising of immiscible polymers polystyrene (PS) and poly(methyl methacrylate) (PMMA). The pattern replication was achieved using capillary force lithography by imprinting the blend films with cross-linked polydimethylsiloxane stamp with grating patterns. The replication was done in the presence of 1-chloropentane or acetic acid vapours, which are selective solvents for PS and PMMA, respectively. This engendered capillary flow of only one phase while the domains of the second phase remain rigid. Depending on the initial as-cast morphology of the film which is a function of the relative proportion of PS and PMMA, a variety of structures were obtained by combining the phase-separated domains with the structure imposed by the stamp. This method can be considered as a simple, one-step technique for creating hierarchical patterns that are likely to find applications in modulating properties of soft surfaces.

One-pot fabrication of polymer micro/nano-discs via phase separation and a roll-to-roll coating process

Disc-shaped particles are one of the unique and promising shapes that can improve adhesion to interfaces and can function as the key feature in various applications; e.g. injectable drug carriers. However, most of these methods include the shape deformation process from spheres to discs using various external stimuli or require multiple processing steps, which is complicated and has limitations in terms of continuous fabrication. We herein propose a novel method combining polymer blend phase separation and a roll-to-roll coating process to continuously fabricate polymer micro/nano-discs in a one-pot manner on a large-scale. The evaporation of solvent during a roll-to-roll coating process encourages the formation of homogenous island-like domains composed of the minor component dispersed in a matrix of the major component on a water-soluble polyvinyl alcohol (PVA) film. In fact, polyvinylpyrrolidone (PVP) was chosen as the major component since it dissolves in both water and chloroform. Another polymer, polystyrene (PS), as a minor component was dissolved in chloroform with PVP. A PVP and PVA matrix film can be easily washed out by water, and micro/nano-discs of the PS minor component can be obtained in a one-pot manner. This method is shown to be capable of continuously fabricating PS micro/nano-discs at a very high rate of ∼108 particles/min. The effects of fabrication conditions, such as the blend ratio and total polymer concentration on the dimensions of the PS discs were investigated, and a maximum aspect ratio (ratio between diameter and thickness) of 6.3 (diameter ∼830 nm, thickness ∼130 nm) was demonstrated. The method proposed in this study could provide a straightforward and time-saving way to continuously fabricate micro/nano-discs via polymer phase separation and a roll-to-roll coating process.

Interfacial aggregation of Janus rods in binary polymer blends and their effect on phase separation.

Janus particles interfacially self-assemble into different structures when incorporated into multiphase systems. Dissipative particle dynamics simulations are employed herein to investigate the interplay between aggregation mechanisms and phase separation in polymer blends. Shorter rods with a standing configuration become increasingly "caged" or trapped in larger aggregates as weight fraction increases, which is reflected in the way that their diffusion is coupled to their aggregation rates. Janus rods of higher aspect ratios that are tilted at the interface aggregate side-by-side and are able to hinder phase separation kinetics. This is due to a combination of individual Janus rod conformations at the interface, their intrinsic aggregation mechanisms, aggregate fractal dimension, and aggregation rates, and can also be traced back to the scaling of the diffusion coefficient of aggregates with their size. Findings presented provide insight into the mechanisms governing two dimensionally growing colloidal aggregates at fluid interfaces, more specifically, those associated with Janus particles, and shed light on the potential of these systems in paving the way for designing new functional materials.

Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

AbstractThis Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so‐called bottom‐up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copolymers are discussed, and the effects of microsphere size on phase separated structures and theoretical simulations of morphologies are also reviewed. The alignment of functional nanoparticles in phase separated polymer microspheres and applications of nanostructured and hybrid polymer microspheres are summarized.

Rigidochromic conjugated polymers carrying main-chain molecular rotors.

We design and prepare rigidochromic conjugated polymers that carry molecular rotors in the main chain. We show how a suitable design maintains the mechanosensitivity of the rotors upon incorporation into an extended π-conjugated system. Construction of donor-acceptor polymers enables their use as ratiometric probes for polymer micromechanics, which we evidence through micromechanical imaging of a phase-separated polymer blend.

Selective location and migration of poly(methyl methacrylate)- grafted clay nanosheets with low grafting density in poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The location and migration of poly (methyl methacrylate)-grafted clay (clay-g-PMMA) nanosheets with low grafting density in a phase-separated polymer blend of poly (methyl methacrylate)/poly (styrene-co-acrylonitrile) (PMMA/SAN) was investigated. The grafting density and molecular weight for grafted PMMA chains on the surface of clay nanosheets was about 0.04 chains/nm2 and 7.8 × 104, respectively, indicating that the grafted chains might exhibit the mushroom-like distribution. With phase separation of PMMA/SAN blend matrix, the well-dispersed clay-g-PMMA nanosheets in the blend matrix were first located in the SAN-rich phase and then gradually migrated to the interface between PMMA and SAN. The first abnormal location of modified clay in the blend matrix might be attributed to the favorable interaction between clay-g-PMMA and SAN induced by the miscibility of grafted PMMA/surrounding SAN chains and the unfavorable interaction between clay-g-PMMA and PMMA without any interpenetration of grafted and matrix chains. The enhanced miscibility between grafted PMMA and surrounding SAN just began to be destroyed after being annealed for a long time, resulting in the final migration of clay-g-PMMA to the interface of PMMA/SAN (thermodynamic equilibrium state).