Hierarchically Superstructured Anisotropic Carbon Particles by Multiscale Assembly Driven by Spinodal Decomposition.

Hierarchical superstructures have novel shape-dependent properties, but well-defined anisotropic carbon superstructures with controllable size, shape, and building block dimensionality have rarely been accomplished thus far. Here, a hierarchical assembly technique is presented that uses spinodal decomposition (SD) to synthesize anisotropic oblate particles of mesoporous carbon superstructure (o-MCS) with nanorod arrays by integrating block-copolymer (BCP) self-assembly and polymer-polymer interface behaviors in binary blends. The interaction of major and minor phases in binary polymer blends leads to the formation of an anisotropic oblate particle, and the BCP-rich phase enables ordered packing and unidirectional alignment of carbon nanorods. Consequently, this approach enables precise control over particles' size, shape, and over the dimensionality of their components. Exploiting this functional superstructure, o-MCS are used as an anode material in potassium-ion batteries, and achieve a notable specific capacity of 156 mA h g-1 at a current density of 2 A g-1, and long-term stability for 3000 cycles. This work presents a significant advancement in the field of hierarchical superstructures, providing a promising strategy for the design and synthesis of anisotropic carbon materials with controlled properties, offering promising applications in energy storage and beyond.

Supersoft Polymer Melts in Binary Blends of Bottlebrush cis-1,4-Polyfarnesene and cis-1,4-Polyisoprene.

Binary blends of polyterpenes are employed comprising cis-1,4-polyfarnesene (PF) with a bottlebrush architecture, and linear cis-1,4-polyisoprene (PI) as model systems toward supersoft polymer melts. The bottlebrush PF results in a low plateau modulus ( G N 0 ≈ 3.5 × 10 4 ${G}_{N}^{0}\approx 3.5\ensuremath{\times{}}{10}^{4}$ Pa) that can further be reduced with the addition of PI. Depending on the fraction of short PI chains in the athermal and nearly isofrictional blends, plateau moduli in the range from 1 to 10 kPa can be achieved. Tube dilation is very efficient in the present binary blends as compared to more common blends comprising long/short or linear/star chains of identical polymer structure.

Dynamic Thermosetting Resins with Synergistic Enhanced Strength and Toughness through Combination with Rigid and Soft Microdomains.

Preparation of materials that possess highly strong and tough properties simultaneously is a great challenge. Thermosetting resins as a type of widely used polymeric materials without synergistic strength and toughness limit their applications in some special fields. In this report, an effective strategy to prepare thermosetting resins with synergistic strength and toughness, is presented. In this method, the soft and rigid microspheres with dynamic hemiaminal bonds are fabricated first, followed by hot-pressing to crosslink at the interfaces. Specifically, the rigid or soft microspheres are prepared via precipitation polymerization. After hot-pressing, the resulting rigid-soft blending materials exhibit superior strength and toughness, simultaneously. As compared with the precursor rigid or soft materials, the toughness of the rigid-soft blending films (RSBFs) is improved to 240% and 2100%, respectively, while the strength is comparable to the rigid precursor. As compared with the traditional crushing, blending, and hot-pressing of rigid or soft materials to get the nonuniform materials, the strength and toughness of the RSBFs are improved to 168% and 255%, respectively. This approach holds significant promise for the fabrication of polymer thermosets with a unique combination of strength and toughness.

Effect of the Addition of Inorganic Fillers on the Properties of Degradable Polymeric Blends for Bone Tissue Engineering.

Bone tissue exhibits self-healing properties; however, not all defects can be repaired without surgical intervention. Bone tissue engineering offers artificial scaffolds, which can act as a temporary matrix for bone regeneration. The aim of this study was to manufacture scaffolds made of poly(lactic acid), poly(ε-caprolactone), poly(propylene fumarate), and poly(ethylene glycol) modified with bioglass, beta tricalcium phosphate (TCP), and/or wollastonite (W) particles. The scaffolds were fabricated using a gel-casting method and observed with optical and scanning electron microscopes. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), wettability, and degradation tests were conducted. The highest content of TCP without W in the composition caused the highest hydrophilicity (water contact angle of 61.9 ± 6.3°), the fastest degradation rate (7% mass loss within 28 days), moderate ability to precipitate CaP after incubation in PBS, and no cytotoxicity for L929 cells. The highest content of W without TCP caused the highest hydrophobicity (water contact angle of 83.4 ± 1.7°), the lowest thermal stability, slower degradation (3% mass loss within 28 days), and did not evoke CaP precipitation. Moreover, some signs of cytotoxicity on day 1 were observed. The samples with both TCP and W showed moderate properties and the best cytocompatibility on day 4. Interestingly, they were covered with typical cauliflower-like hydroxyapatite deposits after incubation in phosphate-buffered saline (PBS), which might be a sign of their excellent bioactivity.

A Vitrimer Acts as a Compatibilizer for Polyethylene and Polypropylene Blends.

Polymer compatibilization plays a critical role in achieving polymer blends with favorable mechanical properties and enabling efficient recycling of mixed plastic wastes. Nonetheless, traditional compatibilization methods often require tailored designs based on the specific chemical compositions of the blends. In this study, we propose a new approach for compatibilizing polymer blends using a dynamically crosslinked polymer network, known as vitrimers. By adding a relatively small amount (1-5 w/w%) of a vitrimer made of siloxane-crosslinked high-density polyethylene (HDPE), we successfully compatibilized unmodified HDPE and isotactic polypropylene (iPP). The vitrimer-compatibilized blend exhibited enhanced elongation at break (120 %) and smaller iPP domain sizes (0.4 µm) compared to the control blend (22 % elongation at break, 0.9 µm iPP droplet size). Moreover, the vitrimer-compatibilized blend showed significantly improved microphase stability during annealing at 180 °C. This straightforward method shows promise for applications across various polymer blend systems.

Tough and Thermostable Polybutylene Terephthalate (PBT)/Vitrimer Blend with Enhanced Interfacial Compatibility.

Polymer blending is an efficient way to obtain extraordinary polymeric materials. However, once permanently cross-linked thermosets are involved in blending, there are challenges in designing and optimizing the structures and interfacial compatibility of blends. Vitrimer with dynamic covalent polymer networks provides an innovative opportunity for blending thermoplastics and thermosets. Herein, a reactive blending strategy is proposed to develop thermoplastic-thermoset blend with enhanced compatibility on the basis of dynamic covalent chemistry. Specifically, polybutylene terephthalate (PBT) and polymerized epoxy vitrimer can be directly melt blended to obtain tough and thermostable blends with desirable microstructures and interfacial interaction. Bond exchange facilitates the grafting of PBT and epoxy vitrimer chains, thus enhancing the interfacial compatibility and thermal stability of blends. The obtained blend balances the strength and stretchability of PBT and epoxy vitrimer, resulting in enhanced toughness. This work offers a new way of designing and fabricating new polymeric materials by blending thermoplastics and thermosets. It also suggests a facile direction towards upcycling thermoplastics and thermosets.

All-Organic Hyper-Crosslinked Polymer/Polyimide Composite Films with Ultralow High-Frequency Dielectric Constant.

The ever increasing demand for high-speed communication at high frequency promotes the rapid development of low-dielectric polymer films. Aromatic polyimide (PI) has been widely used as the main dielectrics in the flexible circuit board due to its excellent dielectric, mechanical, and thermal properties. Nevertheless, the dielectric constant of PI films at a high frequency range (several GHz) is relatively high and cannot satisfy the requirement of high-frequency communication. On this basis, a hyper-crosslinked polymer (HCP) and fabricated all-organic HCP/PI composite films through a physical blending method is synthesized. The porous structure of HCP is helpful to reduce the dielectric constant of PI matrix. The effects of HCP loadings on the dielectric, mechanical, and thermal properties of HCP/PI composite films are systematically investigated. The dielectric constants of the composite films can be reduced to 1.6-1.8 in the frequency range of 8.2-9.6 GHz when the HCP content reached 10 wt.%. The proposed method in this work is simple and effective to reduce the dielectric constant of PI and can be easily extended to other organic component-filled PI systems.

Structure-Property Relationships of Shape Memory, Semicrystalline Polymers Fabricated by In Situ Polymerization and Crosslinking of Octadecyl Acrylate/Polybutadiene Blends.

The current work presents the study of a semicrystalline, shape memory polymer synthesized by simultaneous free radical polymerization and crosslinking in a blend of polybutadiene (PB) and octadecyl acrylate. Blending elastomers and phase change materials provide a modular method for new smart materials, such as shape memory polymers. In this system, grafted, side-chain crystalline poly(octadecyl acrylate) (PODA) fixes a programmed shape in the shape memory cycle, while crosslinked polybutadiene drives shape recovery. This work focuses on improving material parameters important for shape memory (crystallinity, gel fraction, melting temperature) by tuning the processing and formulation parameters (amount of crosslinker and PB weight fraction). The result is a shape memory PB-PODA copolymer that can be fabricated by melt processing and programmed without cooling below ambient temperature. It is found that good shape memory (i.e., high shape fixity and recovery) is obtained at a low PB weight fraction where a percolating PODA crystal network is formed at room temperature. The optimized sample shows excellent shape memory properties (fixity > 99%, recovery = 96%). It is shown that it is possible to mold this material into complex 3D shapes or topography with potential use in anticounterfeiting and antitampering applications.

Induced Smectic E Phase in a Binary Blend of Side-Chain Liquid Crystalline Polymers.

Two liquid crystalline polymers containing an azobenzene or cyanobiphenyl mesogenic side chain that adopt smectic A phases are mechanically mixed at 1:1 mesogen molar ratio at an isotropic phase temperature and then cooled. The resultant binary polymer mixture behaves like a single component as revealed by polarized microscopy observation and differential scanning calorimetry, indicating that the binary mixture forms a fully compatible polymer blend. Moreover, the simple polymer blend unexpectedly leads to a higher-ordered smectic E phase where a herringbone structure is formed with restricted mesogen axis rotation. These results suggest a specific intermolecular interaction between the two mesogens, thereby inducing unusual compatibilized polymer blends and the most ordered liquid crystal (LC) phase.

Unraveling the Co-Crystallization-Charge Transport Relation in Conjugated Polymer Blends via Meniscus-Assisted Solution-Shearing.

The ability to craft the co-crystallization in conjugated polymer blends represents an important endeavor for the enhancement of charge transport. However, simple and efficient approaches to co-crystallization have yet to be realized. Herein, for the first time, a robust meniscus-assisted solution-shearing (MASS) strategy is reported to achieve co-crystallization in the poly(2,5-bis(3-hexylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C6) and poly(2,5-bis(3-decylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C10) blended films, and correlate this co-crystalline structure to the charge transport properties. The as-cast PBTTT-C6/PBTTT-C10 blends exhibit co-crystalline or phase-separated structures influenced by their molecular weights. Interestingly, confined-shearing of the initial phase-separated blended solution to MASS produces the formation of their co-crystallization. The co-crystallization kinetics accompanied by the chain packing change and optical properties are scrutinized. Finally, the resulting organic field-effect transistors (OFETs) signify the cocrystal-facilitated charge transport in the blends. Conceptually, this efficient MASS strategy in rendering the co-crystallization in conjugated polymer blends can be readily extended to other conjugated polymer blends of interest for a variety of device applications.

Exploring the Blends' Miscibility of a Novel Chitosan Derivative with Enhanced Antioxidant Properties; Prospects for 3D Printing Biomedical Applications.

Chitosan is a polysaccharide vastly examined in polymer science for its unique structure. In the present study, CS was derivatized with 2-methoxy-4vinylphenol (MVP) in four different ratios through a free radical reaction. The CS-MVP derivatives were characterized through FTIR, 1H-NMR, XRD, swelling, and solubility measurements. Owing to the enhanced antioxidant character of the MVP monomer, the antioxidant activity of the CS-MVP derivatives was assessed. In the optimum CS-MVP ratio, blends between CS and CS-MVP were prepared in ratios of 90:10, 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, 20:80, and 10:90 w/w, and their miscibility was examined by scanning electron microscopy (SEM) and viscosity measurements. In the optimum ratios, highly concentrated inks were prepared, and their viscosity measurements revealed the successful formation of highly viscous gels with shear thinning behavior. These inks could be appropriate candidates for biomedical and drug delivery applications.

The Effect of Polymer Blends on the In Vitro Release/Degradation and Pharmacokinetics of Moxidectin-Loaded PLGA Microspheres.

To investigate the effect of polymer blends on the in vitro release/degradation and pharmacokinetics of moxidectin-loaded PLGA microspheres (MOX-MS), four formulations (F1, F2, F3 and F4) were prepared using the O/W emulsion solvent evaporation method by blending high (75/25, 75 kDa) and low (50/50, 23 kDa) molecular weight PLGA with different ratios. The addition of low-molecular-weight PLGA did not change the release mechanism of microspheres, but sped up the drug release of microspheres and drastically shortened the lag phase. The in vitro degradation results show that the release of microspheres consisted of a combination of pore diffusion and erosion, and especially autocatalysis played an important role in this process. Furthermore, an accelerated release method was also developed to reduce the period for drug release testing within one month. The pharmacokinetic results demonstrated that MOX-MS could be released for at least 60 days with only a slight blood drug concentration fluctuation. In particular, F3 displayed the highest AUC and plasma concentration (AUC0-t = 596.53 ng/mL·d, Cave (day 30-day 60) = 8.84 ng/mL), making it the optimal formulation. Overall, these results indicate that using polymer blends could easily adjust hydrophobic drug release from microspheres and notably reduce the lag phase of microspheres.

Analysis of Dielectric Parameters of Fe2O3-Doped Polyvinylidene Fluoride/Poly(methyl methacrylate) Blend Composites.

In this paper, we report the effect of metal oxide (Fe2O3) loading in different weight ratios (0.5%, 1%, 2%, and 4%) on the structural and electrical parameters, viz., the complex dielectric constant, electric modulus spectra, and the AC conductivity, of polymeric composites of PVDF/PMMA (30/70 weight ratio) blend. The structural and geometric measurements have been analyzed with the help of peak location, peak intensity, and peak shape obtained from XRD as well as from FTIR spectra. The electrical properties have been investigated using an impedance analyzer in the frequency range 100 Hz to 1 MHz. The real parts of the complex permittivity and the dielectric loss tangent of these materials are found to be frequency independent in the range from 20 KHz to 1 MHz, but they increase with the increase in the concentration of nano-Fe2O3. The conductivity also increases with an increased loading of Fe2O3 in PVDF/PMMA polymer blends. The electric modulus spectra were used to analyze the relaxation processes associated with the Maxwell-Wagner-Sillars mechanism and chain segmental motion in the polymer mix.

Blending to Make Nonhealable Polymers Healable: Nanophase Separation Observed by CP/MAS 13 C NMR Analysis.

Can commodity polymers are made to be healable just by blending with self-healable polymers? Here we report the first study on the fundamental aspect of this practically challenging issue. Poly(ether thiourea) (PTUEG3 ; Tg =27 °C) reported in 2018 is extraordinary in that it is mechanically robust but can self-heal even at 12 °C. In contrast, poly(octamethylene thiourea) (PTUC8 ; Tg =50 °C), an analogue of PTUEG3 , cannot heal below 92 °C. We found that their polymer blend self-healed in a temperature range above 32 °C even when its PTUEG3 content was only 20 mol %. Unlike PTUEG3 alone, this polymer blend, upon exposure to high humidity, barely plasticized, keeping its excellent mechanical properties due to the non-hygroscopic nature of the PTUC8 component. CP/MAS 13 C NMR analysis revealed that the polymer blend was nanophase-separated, which possibly accounts for why such a small amount of PTUEG3 provided the polymer blend with humidity-tolerant self-healable properties.

An Aggregation-Suppressed Polymer Blending Strategy Enables High-Performance Organic and Quantum Dot Hybrid Solar Cells.

Solution-processing hybrid solar cells with organics and colloidal quantum dots (CQDs) have drawn substantial attention in the past decade. Nevertheless, hybrid solar cells based on the recently developed directly synthesized CQD inks are still unexplored. Herein, a facile polymer blending strategy is put forward to enable directly synthesized CQD/polymer hybrid solar cells with a champion efficiency of 13%, taking advantage of the conjugated polymer blends with finely optimized aggregation behaviors. The spectroscopic and electrical investigations on carrier transport and recombination indicate that polymer blends can endow fast carrier transport and less recombination over the single counterparts. Moreover, the blending strategy offers a "dilution effect" for top-notch photovoltaic polymers with excessively strong aggregation tendency, resulting in moderate feature domain size and surface roughness, which afford fast hole transport and therefore high photovoltaic performance. The effectiveness of this strategy is successfully validated using two pairs of photovoltaic polymers. Accordingly, the relationships between polymer morphology, carrier transport, and photovoltaic performance are established to advance the progress of CQD/polymer hybrid solar cells. Such progress stresses that the utilization of aggregation-suppressed polymer blends is a facile approach toward the fabrication of high-efficiency organic-inorganic hybrid solar cells.

Improving Charge Injection at Gold/Conjugated Polymer Contacts by Polymer Insulator-Assisted Annealing for Transistors.

The poor chemical miscibility between metal and organic materials usually leads to both structural and energetic mismatches at gold/organic interfaces, and thereby, high contact resistance of organic electronic devices. This study shows that the contact resistance of organic field-effect transistors is significantly reduced by one order of magnitude, by reforming the contact interface between gold electrodes and conjugated polymers upon a polymer insulator-assisted thermal annealing. Upon an optimized solution process, the conjugated polymer is homogenously distributed within the amorphous polymer insulator matrix with relatively low glass transition temperature, and thus, even a moderate annealing temperature can induce sufficient motion of conjugated polymer chains to simultaneously adjust the polymer orientation and improve the packing of gold atoms. Consequently, gold/conjugated polymer contact is reorganized after annealing, which improves both charge transport from bulk gold to interface and charge injection from gold into conjugated polymers. This method, with appropriate insulator matrix, is effective for improving the injection of both holes and electrons, and widely applicable for many unipolar and ambipolar conjugated polymers to optimize the device performance and simultaneously increase the optical transparency (over 80%). A frequency doubler and a phase modulator are demonstrated, respectively, using the ambipolar transistors with optimized charge injection properties.

Water-Soluble Reactive Polymer Blends for Stable Memory Layers in Low-Voltage Nonvolatile Organic Memory Transistors with High Mobility and Data-Retention Characteristics.

Here low-voltage nonvolatile organic memory transistors, featuring high charge-carrier mobility and outstanding data-retention characteristics, by employing water-soluble reactive polymer blends as a gate-insulating memory layer are demonstrated. Blend films of poly(vinyl alcohol) (PVA) and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPSA) (PVA:PAMPSA) are prepared from their aqueous solutions with various molar ratios of PAMPSA (0-18 mol%) and thermally annealed at 70 and 110 °C. Organic field-effect transistors (OFETs) are fabricated by depositing poly(3-hexylthiophene) (P3HT) channel layers on the thermally treated PVA:PAMPSA films. Results show that the hole mobility of OFETs is remarkably increased (≈294 times at 70 °C and ≈42 times at 110 °C) by adding only 2 mol% PAMPSA to the PVA films and further improved at 10 mol% PAMPSA (>11.7 cm2  V-1 s-1 at 70 °C and >3.8 cm2  V-1  s-1 at 110 °C). The hysteresis characteristics are rather strengthened for the PVA:PAMPSA layers by annealing at 110 °C due to the formation of cross-linking sites, even though the OFETs with the pristine PVA layers do almost lose hysteresis characteristics at 110 °C. The optimized OFETs with the PVA:PAMPSA layers (10 mol%, 110 °C) deliver excellent data retention characteristics during >10 000 memory cycles at a voltage range of -5 to +5 V.

Alginates Combined with Natural Polymers as Valuable Drug Delivery Platforms.

Alginates (ALG) have been used in biomedical and pharmaceutical technologies for decades. ALG are natural polymers occurring in brown algae and feature multiple advantages, including biocompatibility, low toxicity and mucoadhesiveness. Moreover, ALG demonstrate biological activities per se, including anti-hyperlipidemic, antimicrobial, anti-reflux, immunomodulatory or anti-inflammatory activities. ALG are characterized by gelling ability, one of the most frequently utilized properties in the drug form design. ALG have numerous applications in pharmaceutical technology that include micro- and nanoparticles, tablets, mucoadhesive dosage forms, wound dressings and films. However, there are some shortcomings, which impede the development of modified-release dosage forms or formulations with adequate mechanical strength based on pure ALG. Other natural polymers combined with ALG create great potential as drug carriers, improving limitations of ALG matrices. Therefore, in this paper, ALG blends with pectins, chitosan, gelatin, and carrageenans were critically reviewed.

Maleic Anhydride-Grafted PLA Preparation and Characteristics of Compatibilized PLA/PBSeT Blend Films.

Poly(butylene sebacate-co-terephthalate) (PBSeT) is a biodegradable flexible polymer suitable for melt blending with other biodegradable polymers. Melt blending with a compatibilizer is a common strategy for increasing miscibility between polymers. In this study, PBSeT polyester was synthesized, and poly(lactic acid) (PLA) was blended with 25 wt% PBSeT by melt processing with 3-6 phr PLA-grafted maleic anhydride (PLA-g-MAH) compatibilizers. PLA-g-MAH enhanced the interfacial adhesion of the PLA/PBSeT blend, and their mechanical and morphological properties confirmed that the miscibility also increased. Adding more than 6 phr of PLA-g-MAH significantly improved the mechanical properties and accelerated the cold crystallization of the PLA/PBSeT blends. Furthermore, the thermal stabilities of the blends with PLA-g-MAH were slightly enhanced. PLA/PBSeT blends with and without PLA-g-MAH were not significantly different after 120 h, whereas all blends showed a more facilitated hydrolytic degradation rate than neat PLA. These findings indicate that PLA-g-MAH effectively improves PLA/PBSeT compatibility and can be applied in the packaging industry.

Influence of PCL and PHBV on PLLA Thermal and Mechanical Properties in Binary and Ternary Polymer Blends.

PLLA, PCL and PHBV are aliphatic polyesters which have been researched and used in a wide range of medical devices, and all three have advantages and disadvantages for specific applications. Blending of these materials is an attractive way to make a material which overcomes the limitations of the individual polymers. Both PCL and PHBV have been evaluated in polymer blends with PLLA in order to provide enhanced properties for specific applications. This paper explores the use of PCL and PHBV together with PLLA in ternary blends with assessment of the thermal, mechanical and processing properties of the resultant polymer blends, with the aim of producing new biomaterials for orthopaedic applications. DSC characterisation is used to demonstrate that the materials can be effectively blended. Blending PCL and PHBV in concentrations of 5-10% with PLLA produces materials with average modulus improved by up to 25%, average strength improved by up to 50% and average elongation at break improved by 4000%, depending on the concentrations of each polymer used. PHBV impacts most on the modulus and strength of the blends, whilst PCL has a greater impact on creep behaviour and viscosity. Blending PCL and PHBV with PLLA offers an effective approach to the development of new polyester-based biomaterials with combinations of mechanical properties which cannot be provided by any of the materials individually.