Graft Chains Research Articles

Increase of bridge length by ingenious grafting of ester chains, imparting epoxy resins superb thermal, smoke suppression, gas-phase flame retardancy, and mechanical properties

While bifunctional synergistic flame retardants have demonstrated efficacy in enhancing the fire safety of epoxy resins (EPs), the grafting of specific functional monomers into flame retardant molecules, elucidating their mechanisms of action through comparative analysis, and concurrently achieving a delicate balance among flame retardancy, heat resistance, and mechanical toughness remains a significant challenge. Herein, this research present an innovative strategy to derive a novel sulfur-based bifunctional flame retardant, DSTA, based on the structure of the original flame retardant, DST, by grafting the ester chains to increase the bridge length of the molecular structure. As expected, the addition of flexible ester chains enabled DSTA to have a very high initial decomposition temperature and the heat-resistance index. DSTA can be used in low dosage compared to DST, enabling EP to achieve UL-94 V-0 rating. Combustion behavior showed that DSTA had the best ability to heat and smoke suppression for EP, and had faster response speed and higher fire growth index. Notably, pyrolysis volatiles tested on DSTA revealed that the ester chains can pyrolysis to release large amounts of CO2, which occurs in the early stages of pyrolysis and works together with other N-containing inert gases and P-containing radicals in the gas-phase to efficiently extinguish flames. Meanwhile, DSTA improves all mechanical properties of EP, which was attributed to the presence of ester chains. In summary, this work presents a new strategy for examining the impact of specific functional groups on the flame retardant mechanisms of EP.

Quaternary Ammonium Salt Derivatives of Hyperbranched Polylysine with Enhanced Antibacterial Activity against Multidrug-Resistant Gram-Negative Bacteria.

Multidrug-resistant (MDR) Gram-negative bacteria infections have gradually become a more serious health problem recently, and antibacterial drugs are urgently needed to tackle MDR Gram-negative bacteria. Herein, we synthesized a series of quaternary ammonium salt derivatives of hyperbranched polylysine (HPL-Cm-n) with different alkyl chain lengths (m = 4, 8, 12, 16) and grafting ratios (n = 5.8-21.0) of alkyl quaternary ammonium salts (Cm). HPL-Cm-ns exhibited excellent antibacterial activities against drug-sensitive E. coli and P. aeruginosa, and specifically, HPL-C12-ns were also highly active against MDR E. coli and P. aeruginosa. The cytotoxicity and hemolytic activity of HPL-Cm-ns increased with the increase in the alkyl chain length and the grafting ratio of Cm. The killing study proved that HPL-C12-9.5 had fast killing kinetics and was bactericidal toward both drug-sensitive and MDR E. coli. The mechanistic studies showed that, similar to hyperbranched polylysine (HPL), HPL-C12-9.5 killed bacteria by disrupting the cell membranes and causing leakage of the cytoplasmic contents. HPL-C12-ns might have potential as an antibacterial agent to combat MDR Gram-negative bacteria.

Superparamagnetic iron oxide nanoparticles functionalized with on-demand redox-responsive contractible coordination polymer brush as molecular actuator driven by π-dimerization

Nanomachines require molecular actuators to be coupled to a condensed phase. In this work, a redox responsive 1D contractible coordination polymer (ZnL) used as non-interlocked actuator is grafted onto superparamagnetic iron oxide nanoparticles (SPIONs) in a brush-like configuration. Oxidized rod-like ZnL oligomers have ability to reversibly self-fold upon reduction via π-dimerization of their bis-viologen units. Unlike in usual responsive brushes, ZnL chains behave individually, generating spatially controlled mechanical motion at nanoparticle surface associated to significant variations of particle diameters. ZnL oligomers were “grafted to” SPIONs in a single step. Reduction of colloidal dispersions was perform by visible light illumination with the help of a photoreductant. π-dimerization was assessed by UV–vis–NIR and reversible contraction of ZnL brush was characterized by DLS. Effects of ZnL chains length and grafting density on mechanism and performance of contractibility were studied. ZnL brush can alternately be contracted and extended with excellent reversibility. Combined UV–vis–NIR, DLS and TGA analyses demonstrate that π-dimerization is only intramolecular and that chains behave as independent actuators. Maximal contraction of 22 nm is obtained for largest particles (DH = 86 nm). Full to partial contraction of the brush depends on grafting density with a threshold at ≈ 47 chains per particle.

Blends of polydimethylsiloxane-based polyurethane and poly (propylene glycol)-based polyurethane with co-continuous structures: Morphology evolution, synergistic effects and application in strain sensors

Blending is an effective way to improve properties of rubbers and develop new materials, so more than 75 % of the rubber consumption in the world is rubber blend. However, blending of thermoplastic elastomers has not yet been emphasized, and few successful examples have been reported. The main challenge for blend systems is compatibility of two components. Herein, a series of (polydimethylsiloxane-based PU)-g-(poly (propylene glycol)-based PU) ((PDMS-PU)-g-(PPG-PU)) graft copolymers with different graft chain lengths and hard segment contents (HSC) were synthesized and utilized as compatibilizers of PDMS-PU/PPG-PU blends. The influence of the structure of compatibilizers on the morphology of blends was investigated, and the compatibilization mechanism was proposed. With the solubilization, the phase structure of blends transforms from “droplet-in-matrix” morphologies to co-continuous ones, and the average size of PPG-PU dispersed phase decreases from 3.5 ± 0.45 μm to 230 ± 60 nm. This is the first time that thermoplastic PDMS-PU/PPG-PU blends with co-continuous structures have been successfully prepared. The properties of blends exhibit synergistic effects. For example, they show high tensile strength of PPG-PU in mechanical properties and unique properties of PDMS in dynamic mechanical properties, weather resistance, water resistance and biocompatibility. In addition, strain sensors were fabricated by introducing carbon nanotubes (CNTs) into the blends, which demonstrated remarkable sensing capability for diverse human body motions.

Effect of Grafting Density on the Crystallization Behavior of Molecular Bottlebrushes.

A unique case of sterically constrained crystallization arises in bottlebrush polymers bearing semicrystalline side chains. Bottlebrushes with grafted side chains can form crystalline structures governed by the complex interplay between side chain packing and backbone confinement. The confinement effect can be readily tuned by varying the side chain grafting density, thus affording control over the crystallization behavior of these systems. In this work, the grafting density effect on the crystallization behavior of molecular bottlebrushes comprising poly(ethylene oxide) (PEO) side chains grafted to a methacrylate backbone was systematically studied. Thermal analysis using differential scanning calorimetry showed that the bottlebrush polymers displayed suppressed crystallization temperatures, lower melting temperatures, and reduced crystallinities compared to linear homopolymer PEO. The crystalline morphology was investigated using polarized light, atomic force, and scanning electron microscopy. Isothermal crystallization experiments revealed a nonmonotonous dependence of the nucleation density on the side chain grafting density. The grafting density effect was also investigated using self-seeding experiments, revealing an increased clearing temperature and memory retention at higher grafting densities. This work highlights how grafting density influences the crystallization behavior of semicrystalline bottlebrushes, providing information for the processing and application of these unique polymers.

An endothelium membrane mimetic antithrombotic coating enables safer and longer extracorporeal membrane oxygenation application

Thrombosis and plasma leakage are two of the most frequent dysfunctions of polypropylene (PP) hollow fiber membrane (PPM) used in extracorporeal membrane oxygenation (ECMO) therapy. In this study, a superhydrophilic endothelial membrane mimetic coating (SEMMC) was constructed on polydopamine-polyethyleneimine pre-coated surfaces of the PPM oxygenator and its ECMO circuit to explore safer and more sustainable ECMO strategy. The SEMMC is fabricated by multi-point anchoring of a phosphorylcholine and carboxyl side chained copolymer (PMPCC) and grafting of heparin (Hep) to form PMPCC-Hep interface, which endows the membrane superior hemocompatibility and anticoagulation performances. Furthermore, the modified PPM reduces protein adsorption amount to less than 30 ng/cm2. More significantly, the PMPCC-Hep coated ECMO system extends the anti-leakage and non-clotting oxygenation period to more than 15 h in anticoagulant-free animal extracorporeal circulation, much better than the bare and conventional Hep coated ECMO systems with severe clots and plasma leakage in 4 h and 8 h, respectively. This SEMMC strategy of grafting bioactive heparin onto bioinert zwitterionic copolymer interface has great potential in developing safer and longer anticoagulant-free ECMO systems. Statement of significanceA superhydrophilic endothelial membrane mimetic coating was constructed on surfaces of polypropylene hollow fiber membrane (PPM) oxygenator and its ECMO circuit by multi-point anchoring of a phosphorylcholine and carboxyl side chain copolymer (PMPCC) and grafting of heparin (Hep). The strong antifouling nature of the PMPCC-Hep coating resists the adsorption of plasma bio-molecules, resulting in enhanced hemocompatibility and anti-leakage ability. The grafted heparin on the zwitterionic PMPCC interface exhibits superior anticoagulation property. More significantly, the PMPCC-Hep coating achieves an extracorporeal circulation in a pig model for at least 15 h without any systemic anticoagulant. This endothelial membrane mimetic anticoagulation strategy shows great potential for the development of safer and longer anticoagulant-free ECMO systems.

Alternating Graft Copolymer Carrying PLA Graft Chains at Every Other Unit: Sequence Impacts on Crystallization Behaviors.

Alternating graft copolymers were precisely synthesized via selective cyclopolymerization of pendant-transformable divinyl monomer (1), post-polymerization modification via aminolysis with alkylamine, and ring-opening polymerization of l-lactide (LLA) from the hydroxy pendant group in alternating sequence. The poly(LLA) (PLLA) graft chain on the alternating copolymer gave a higher crystallization degree on the isothermal treatment than that on the random counterpart likely because of the periodic sequence. The comonomer pendant group from alkylamine in the aminolysis reaction in the alternating sequence affected the crystallization behaviors, and the oligoethylene glycol (OEG) group promoted the crystallization thanks to the larger free volume effect. As for the stereocomplex formation of the racemic mixture of enantiomeric PLLA and poly(d-lactide) (PDLA) chains, the alternating graft copolymer gave a higher degree of stereocomplex crystallization in the mixture with the enantiomer homopolymer than the random analogue.

The Effect of Carbon Nanotubes and Carbon Microfibers on the Piezoresistive and Mechanical Properties of Mortar

Sustainability, safety and service life expansion in the construction sector have gained a lot of scientific and technological interest during the last few decades. In this direction, the synthesis and characterization of smart cementitious composites with tailored properties combining mechanical integrity and self-sensing capabilities have been in the spotlight for quite some time now. The key property for the determination of self-sensing behavior is the electrical resistivity and, more specifically, the determination of reversible changes in the electrical resistivity with applied stress, which is known as piezoresistivity. In this study, the mechanical and piezoresistive properties of mortars reinforced with carbon nanotubes (CNTs) and carbon micro-fibers (CMFs) are determined. Silica fume and a polymer with polyalkylene glycol graft chains were used as dispersant agents for the incorporation of the CNTs and CMFs into the cement paste. The mechanical properties of the mortar composites were investigated with respect to their flexural and compressive strength. A four-probe method was used for the estimation of their piezoresistive response. The test outcomes revealed that the combination of the dispersant agents along with a low content of CNTs and CMFs by weight of cement (bwoc) results in the production of a stronger mortar with enhanced mechanical performance and durability. More specifically, there was an increase in flexural and compressive strength of up to 38% and 88%, respectively. Moreover, mortar composites loaded with 0.4% CMF bwoc and 0.05% CNTs bwoc revealed a smooth and reversible change in electrical resistivity vs. compression loading—with unloading comprising a strong indication of self-sensing behavior. This work aims to accelerate progress in the field of material development with structural sensing and electrical actuation via providing a deeper insight into the correlation among cementitious composite preparation, admixture dispersion quality, cementitious composite microstructure and mechanical and self-sensing properties.

Polystyrene Brush Evolution by Grafting to Reaction on Deglazed and Not-Deglazed Silicon Substrates.

Two model substrates for the grafting to reaction are considered: not-deglazed silicon, whose surface is coated by a thin oxide layer with reactive silanol groups on its surface; and deglazed silicon, where the oxide layer is removed by treatment with hydrofluoric acid. The reactive polymers are hydroxy-terminated polystyrenes with molecular weights ranging from 3.9 to 13.9kgmol⁻1. The grafting to reaction is carried out at different temperatures and for different periods of time on the two different substrates. The thickness and the thermal stability of the resulting brushes are evaluated. Furthermore, the grafting of a highly dispersed system is simulated by blending two polymers with different molecular weights. Although the brush thickness growth is found to be faster on deglazed silicon, the preferential grafting of short chains occurs with equal chain selection propensity on both substrates.

Synthesis and self-assembly of high grafting density core-shell bottlebrush polymer with amphiphilic side chain

Self-assembly of bottlebrush polymers are widely studied in photonic bandgap materials, biomedical materials and nanomaterial with different structures. In this work, high grafting density bottlebrush polymer with amphiphilic QPDMA[FeCl4]-b-PS side chains grafting on every carbon atom of the backbone are prepared via grafting from approach. The para-isocyanobenzoate monomer modified with chain transfer agent (CTA) is designed and synthesized to prepared polymer backbones with CTA grafting on each atoms. The core-shell bottlebrush block copolymer is prepared by sequential reversible addition-fragmentation chain transfer polymerization of dimethylaminoethyl methacrylate and styrene. The inner core follows quaternization and ion exchange to form water soluble QPDMA[FeCl4] magnetic block. The resulting core-shell bottlebrush magnetic polymer (PCN-g-[QPDMA[FeCl4]-b-PS]) self-assembles into nanowires with magnetic QPDMA[FeCl4] as core and PS as corona in the shell selected solvent dichloromethane, the length of nanowires increases with self-assembly time. While it self-assembles into nanoparticle clusters in core selected aqueous solution. And, the thermal and magnetic properties are affected by the self-assembly morphology. Especially, the as prepared PCN-g-[QPDMA[FeCl4]-b-PS] and the nanoparticles cluster self-assembly are paramagnetic, but the nanowire self-assembly is superparamagnetic.

Stability and lipid oxidation of oil-in-water emulsion stabilized by Maillard conjugates of soybean phosphatidylethanolamine with different polysaccharides

Lipid oxidation and instability in oil-in-water (O/W) emulsion are the main challenges in emulsion-based foods. Polysaccharide-induced Maillard conjugation of soybean phosphatidylethanolamine (SP) holds great potential in improving physicochemical stability of emulsions. This work applied tamarind gum, pectin, inulin and maltodextrin to conjugate with SP to obtain the four Maillard conjugates (MCs), and investigated their difference in interface and anti-oxidant abilities in emulsions. Results showed that lower polymerization degree of polysaccharide moieties (tamarind gum＞pectin＞maltodextrin＞inulin) caused higher glycation degree in MC: inulin-SP-MC＞maltodextrin-SP-MC＞pectin-SP-MC ≈ tamarind gum-SP-MC, which corresponded their color changes. Compared with unconjugated mixtures, interface activity and anti-oxidant abilities of MCs were strengthened. Among the four MCs, tamarind gum-SP-MC (7.77 mN/m) and pectin-SP-MC (8.42 mN/m) could decrease interfacial tension more largely. It was due to the faster interface saturation benefited from broader steric network of tamarind gum and pectin moieties, and stable interfacial absorption facilitated by improved zeta potential and lipophilicity. Pectin-SP-MC also exhibited the highest anti-oxidant ability (DPPH scavenging ability of 97.81% and ferric-reducing antioxidant power of 2.742 A). It was attributed to the combined effects of grafting degree, interface activity and chain length of pectin moiety. As a result, emulsions stabilized by pectin-SP-MC had less water loss, smaller droplet sizes, and lower contents of oxidation products. Maillard reaction between SP and pectin was favorable to produce MCs with higher potential for the improvements of physical and oxidative stability of O/W emulsions.

Local grafting heterogeneities control water intrusion and extrusion in nanopores

Hydrophobic nanoporous materials can only be intruded by water forcibly, typically increasing pressure. For some materials, water extrudes when the pressure is lowered again. Controlling intrusion/extrusion hysteresis is central in technological applications, including energy materials, high performance liquid chromatography, and liquid porosimetry, but its molecular determinants are still elusive. Here, we consider water intrusion/extrusion in mesoporous materials grafted with hydrophobic chains, showing that intrusion/extrusion is ruled by microscopic heterogeneities in the grafting. For example, intrusion/extrusion pressures can vary more than 60 MPa depending on the chain length and grafting density. Coarse-grained molecular dynamics simulations reveal that local changes in radius and contact angle produced by grafting heterogeneities can pin the water interface during intrusion or facilitate vapor bubble nucleation in extrusion. These microscopic insights can directly impact the design of energy materials and chromatography columns, as well as the interpretation of porosimetry results.

A Flexible Ammonia Gas Sensor Based on a Grafted Polyaniline Grown on a Polyethylene Terephthalate Film.

A novel NH3 gas sensor is introduced, employing polyaniline (PANI) with a unique structure called a graft film. The preparation method was simple: polydopamine (PD) was coated on a flexible polyethylene terephthalate (PET) film and PANI graft chains were grown on its surface. This distinctive three-layer sensor showed a response value of 12 for 50 ppm NH3 in a dry atmosphere at 50 °C. This value surpasses those of previously reported sensors using structurally controlled PANI films. Additionally, it is on par with sensors that combine PANI with metal oxide semiconductors or carbon materials, the high sensitivity of which have been reported. To confirm our film's potential as a flexible sensor, the effect of bending on the its characteristics was investigated. This revealed that although bending decreased the response value, it had no effect on the response time or recovery. This indicated that the sensor film itself was not broken by bending and had sufficient mechanical strength.

Site-Directed Electrochemical Grafting for Amplified Detection of Antibody Pharmaceuticals.

Antibody pharmaceuticals have become the most popular immunotherapeutic drugs and are often administered with low serum drug dosages. Hence, the development of a highly sensitive method for the quantitative assay of antibody levels is of great importance to individualized therapy. On the basis of the dual signal amplification by the glycan-initiated site-directed electrochemical grafting of polymer chains (glyGPC), we report herein a novel strategy for the amplified electrochemical detection of antibody pharmaceuticals. The target of interest was affinity captured by a DNA aptamer ligand, and then the glycans of antibody pharmaceuticals were decorated with the alkyl halide initiators (AHIs) via boronate cross-linking, followed by the electrochemical grafting of the ferrocenyl polymer chains from the glycans of antibody pharmaceuticals through the electrochemically controlled atom transfer radical polymerization (eATRP). As the glycans can be decorated with multiple AHIs and the grafted polymer chains are composed of tens to hundreds of electroactive tags, the glyGPC-based strategy permits the dually amplified electrochemical detection of antibody pharmaceuticals. In the presence of trastuzumab (Herceptin) as the target, the glyGPC-based strategy achieved a detection limit of 71.5 pg/mL. Moreover, the developed method is highly selective, and the results of the quantitative assay of trastuzumab levels in human serum are satisfactory. Owing to its uncomplicated operation and cost-effectiveness, the glyGPC-based strategy shows great promise in the amplified electrochemical detection of antibody pharmaceuticals.

An Efficient and Accurate SCF Algorithm for Block Copolymer Films and Brushes Using Adaptive Discretizations.

Self-consistent field (SCF) theory serves as a robust tool for unraveling the intricate behavior exhibited by soft polymeric materials. However, the accuracy and efficiency of SCF calculations are crucially dependent on the numerical methods employed for system discretization and equation-solving. Here, we introduce a simple three dimensional SCF algorithm that uses real-space methods and adaptive discretization, offering improved accuracy and efficiency for simulating polymeric systems at surfaces. Our algorithm's efficacy is demonstrated through simulations of two distinct polymeric systems, namely, block copolymer (BCP) films and polymer brushes. By enhancing spatial resolution in regions influenced by external forces and employing finer contour discretization at grafting chain ends, we achieve significantly more accurate results at very little additional cost, enabling the study of 3D polymeric systems that were previously computationally challenging. To facilitate the widespread use of the algorithm, we have made our 1D-3D SCF code publicly available.

Hydrophobization of surfaces on cellulose nanofibers by enzymatic grafting of partially 2-deoxygenated amylose

Recently, attention has been paid to cellulose nanofibers, such as 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibers (TOCN), as new bio-based materials. In addition, hydrophobized surface on TOCNs can be expected to provide new applications. Based on our previous finding that partially 2-deoxygenated (P2D)-amylose, which was synthesized by GP-catalyzed enzymatic copolymerization of D-glucal with α-d-glucose 1-phosphate (Glc-1-P) as comonomers, was hydrophobic, in this study, hydrophobization of surfaces on TOCNs was investigated by the GP-catalyzed enzymatic grafting of P2D-amylose chains on TOCNs. After maltooligosaccharide primers were modified on TOCNs, the GP-catalyzed enzymatic copolymerization of D-glucal with Glc-1-P was performed for grafting of P2D-amylose chains. 1H NMR spectroscopic analysis confirmed the production of P2D-amylose-grafted TOCNs with different 2-deoxyglucose/Glc unit ratios. The powder X-ray diffraction profiles of the products indicated that the entire crystalline structures were strongly affected by the unit ratios and chain lengths of the grafted polysaccharides. The SEM images observed differences in nanofiber diameter in the reaction solutions and surface morphology after film formation, due to grafting of P2D-amylose chains from TOCNs. The water contact angle measurement of a cast film prepared from the product indicated its hydrophobicity.

Enhanced adsorption of polystyrene nanoplastics by cetyltrimethylammonium bromide surface-modified magnetic rice straw biochar: Efficient performance and adsorption mechanisms

Nanoplastics, characterized by their small size, high diffusion, and stability, have attracted wide attention worldwide as a new potentially threatening pollutant. In this study, magnetic rice straw biochar modified with cetyltrimethylammonium bromide (CTAB) was prepared and utilized for the adsorption removal of polystyrene nanoparticles (PSNPs, <100 nm). The characteristics and adsorption performance of CTAB modified magnetic biochar (MBC-CTAB) were systematically investigated using characterization techniques and batch adsorption experiments. The grafting of alkyl chains onto the biochar surface through surfactant modification improved the surface activity and adsorption capacity of the magnetic biochar towards nanoplastics. Moreover, the application of an external magnetic field facilitated the rapid separation and recovery of MBC-CTAB. MBC-CTAB exhibited a removal efficiency of 99.56 % for 20 mg/L PSNPs, with a maximal adsorption capacity of 54.07 mg/g at 298 K. The presence of anions such as HPO42− and CO32− as well as dissolved organic compounds like humic acid creates significant competition between PSNPs, thereby inhibiting the adsorption capacity of MBC-CTAB towards PSNPs. The mechanism of MBC-CTAB for nanoplastics adsorption can be attributed to electrostatic interaction, hydrophobic interactions, pore filling, and surface complexation. This study demonstrates the feasibility of using surfactant-modified biochar for the adsorption of nanoplastics, providing a promising option for the development of new pollutant treatment technologies and the mitigation of the adverse impacts of nanoplastics on the environment and ecosystems.

Effects of Polyether Amine Canopy Structure on Heavy Metal Ions Adsorption of Magnetic Solvent-Free Nanofluids.

Three Fe3O4 magnetic solvent-free nanofluids with different amine-based coronal layer structures are synthesized and characterized by using magnetic Fe3O4 as the core, silane coupling agent as the corona, and polyether amines with different graft densities and chain lengths as the canopy. The concentration of heavy metal ions after adsorption is measured by atomic absorption spectrometry (AAS) to study the effect of Fe3O4 magnetic solvent-free nanofluids on the adsorption performance of the heavy metal ions lead (Pb(II)) and copper (Cu(II)) in water. The adsorption of Fe3O4 magnetic solvent-free nanofluid was explored by changing external condition factors such as adsorption contact time and pH. Additionally, the adsorption model is established. The magnetic solvent-free nanofluid is separated from water by applying an external magnetic field to the system, and desorption and cyclic adsorption tests are carried out. Based on the adsorption mechanism, the structure design of Fe3O4 magnetic solvent-free nanofluid was optimized to achieve optimal adsorption performance.

PVDF-HFP Based, Quasi-Solid Nanocomposite Electrolytes for Lithium Metal Batteries.

Composite polymer electrolytes are systems of choice for future solid-state lithium metal batteries (LMBs). Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) is among the most interesting matrices to develop new generation quasi-solid electrolytes (QSEs). Here it is reported on nanocomposites made of PVDF-HFP and pegylated SiO2 nanoparticles. Silica-based hybrid nanofillers are obtained by grafting chains of poly(ethylene glycol) methyl ether (PEG) with different molecular weight on the surface of silica nanoparticles. The functionalized nanofiller improves the mechanical, transport and electrochemical properties of the QSEs, which show good ionic conductivity values and high resistance against dendrite penetration, ensuring boosted long and safe device operation. The most promising result is obtained by dispersing 5wt% of SiO2 functionalized with short PEG chains (PEG750, Mw = 750gmol-1) in the PVDF-HFP matrix with an ease solvent-casting procedure. It shows ionic conductivity of 0.1mScm-1 at 25°C, more than 250h resistance to stripping/plating, and impressive results during cycling tests in LMB with LiFePO4 cathode.

Bidispersity Improves the Toughness and Impact Resistance of Star-Polymer Thin Films.

Branched polymer architectures are used to tune the mechanical properties of impact-resistant thin films through parameters, such as chain length and grafting density. While chain dispersity affects molecular properties, such as interpenetration and entanglements, structure-property relationships accounting for dispersity are challenging to obtain experimentally and are often neglected in computational models. We employ molecular dynamics simulations to model the high-rate tensile elongation and nanoballistic impact of thin films composed of bidisperse star polymers with varying arm lengths. We find that, at fixed molecular weight, high dispersity can significantly enhance the toughness and impact resistance of the films without decreasing their elastic modulus. Bidisperse stars with fewer longer arms are less entangled, but stretch and interpenetrate for longer times during crazing, leading to increased toughness. These findings highlight controlled dispersity as a design strategy to improve the mechanical properties of polymer composites across Pareto fronts.