Bioenabled Platform to Access Polyamides with Built-In Target Properties.

The diversification of platform chemicals is key to today's petroleum industry. Likewise, the flourishing of tomorrow's biorefineries will rely on molecules with next-generation properties from biomass. Herein, we explore this opportunity with a novel approach to monomers with custom property enhancements. Cyclic diacids with alkyl and aromatic decorations were synthesized from muconic acid by Diels-Alder cycloaddition, and copolymerized with hexamethylenediamine and adipic acid to yield polyamides with built-in hydrophobicity and flame retardancy. Testing shows a 70% reduction in water uptake and doubling of char production while largely retaining other key properties of the parent Nylon-6,6. The present approach can be generalized to access a wide range of performance-advantaged polyamides.

Gel Point Suppression in RAFT Polymerization of Pure Acrylic Cross-Linker Derived from Soybean Oil.

Here we report the reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylated epoxidized soybean oil (AESO), a cross-linker molecule, to high conversion (>50%) and molecular weight (>100 kDa) without macrogelation. Surprisingly, gelation is suppressed in this system far beyond the expectations predicated both on Flory-Stockmeyer theory and multiple other studies of RAFT polymerization featuring cross-linking moieties. By varying AESO and initiator concentrations, we show how intra- versus intermolecular cross-linking compete, yielding a trade-off between the degree of intramolecular linkages and conversion at gel point. We measured polymer chain characteristics, including molecular weight, chain dimensions, polydispersity, and intrinsic viscosity, using multidetector gel permeation chromatography and NMR to track polymerization kinetics. We show that not only the time and conversion at macrogelation, but also the chain architecture, is largely affected by these reaction conditions. At maximal AESO concentration, the gel point approaches that predicted by the Flory-Stockmeyer theory, and increases in an exponential fashion as the AESO concentration decreases. In the most dilute solutions, macrogelation cannot be detected throughout the entire reaction. Instead, cyclization/intramolecular cross-linking reactions dominate, leading to microgelation. This work is important, especially in that it demonstrates that thermoplastic rubbers could be produced based on multifunctional renewable feedstocks.

Combining Metabolic Engineering and Electrocatalysis: Application to the Production of Polyamides from Sugar.

Biorefineries aim to convert biomass into a spectrum of products ranging from biofuels to specialty chemicals. To achieve economically sustainable conversion, it is crucial to streamline the catalytic and downstream processing steps. In this work, a route that combines bio- and electrocatalysis to convert glucose into bio-based unsaturated nylon-6,6 is reported. An engineered strain of Saccharomyces cerevisiae was used as the initial biocatalyst for the conversion of glucose into muconic acid, with the highest reported muconic acid titer of 559.5 mg L(-1) in yeast. Without any separation, muconic acid was further electrocatalytically hydrogenated to 3-hexenedioic acid in 94 % yield despite the presence of biogenic impurities. Bio-based unsaturated nylon-6,6 (unsaturated polyamide-6,6) was finally obtained by polymerization of 3-hexenedioic acid with hexamethylenediamine.

The battle for the "green" polymer. Different approaches for biopolymer synthesis: bioadvantaged vs. bioreplacement.

Biopolymers have been used throughout history; however, in the last two centuries they have seen a decrease in their utilization as the proliferation of inexpensive and mass-produced materials from petrochemical feedstocks quickly became better-suited to meeting society's needs. In recent years, high petroleum prices and the concern of society to adopt greener and cleaner products has led to an increased interest in biorenewable polymers and the use of sustainable technologies to produce them. Industrial and academic researchers alike have targeted several routes for producing these renewable materials. In this perspective, we compare and contrast two distinct approaches to the economical realization of these materials. One mentality that has emerged we term "bioreplacement", in which the fields of synthetic biology and catalysis collaborate to coax petrochemical monomers from sugars and lignocellulosic feedstocks that can subsequently be used in precisely the same ways to produce precisely the same polymers as we know today. For example, the metabolic engineering of bacteria is currently being explored as a viable route to common monomers such as butadiene, isoprene, styrene, acrylic acid, and sebacic acid, amongst others. Another motif that has recently gained traction may be referred to as the "bioadvantage" strategy, where the multifunctional "monomers" given to us by nature are combined in novel ways using novel chemistries to yield new polymers with new properties; for these materials to compete with their petroleum-based counterparts, they must add some advantage, for example less cost. For instance, acrylated epoxidized soybean oil readily undergoes polymerization to thermosets and recently, thermoplastic rubbers. Additionally, many plants produce pre-polymeric or polymeric materials that require little or no post modification to extract and make use of these compounds.

Synthesis of polyaniline-coated composite anion exchange membranes based on polyacrylonitrile for the separation of tartaric acid via electrodialysis.

The increasing need to tackle major societal challenges such as environmental sustainability and resource scarcity has heightened global interest in green and efficient separation technologies. The separation of organic acids, particularly tartaric acid, holds significant industrial importance in the food and pharmaceutical sectors. Purifying tartaric acid is crucial due to its roles as a chiral catalyst, antioxidant, and stabilizer, which are vital for ensuring product quality and efficiency. In this study, we synthesized heterogeneous anion exchange membranes by casting a solution of polyacrylonitrile (PAN) homogeneously dispersed with micronized anion exchange resin [polystyrene-divinylbenzene-trimethyl ammonium chloride (PS-DVB-TAC)]. These membranes were further coated with polyaniline (PANI) through in situ polymerization at different time intervals such as 2, 12, and 24 h. Cation exchange membranes were also prepared by solution casting of PAN dispersed with micronized cation exchange resin, sulfonated poly-styrene-co-divinylbenzene, and SPS-DVB. These synthesized anion exchange membranes with and without a PANI coating were examined for their separation performance of tartaric acid, along with the cation exchange membranes in a four-compartment electrodialyser at a constant voltage. The newly fabricated membranes were characterized by different techniques, including attenuated total reflectance-Fourier transform infrared spectroscopy for functional group analysis, scanning electron microscopy for their surface morphology, and the four-probe method for electrical conductivity. In addition, ion exchange capacity and water uptake have been measured. The electrodialysis experiments showed that 14.82 wt% of tartrate ions moved into the product compartment through the uncoated anion exchange membrane within 30 min at a voltage of 30 V. Under the same conditions, membranes coated with PANI at 2, 12, and 24 h raised the separation efficiency to 21.19%, 34.13%, and 37.21%, respectively. Findings indicate that membranes coated with PANI for extended periods demonstrate superior separation efficiency for tartaric acid. Consequently, this energy-efficient method shows significant potential for application in the food and pharmaceutical industries for separating tartaric acid and other organic and amino acids. This research can advance practical and sustainable separation technologies, addressing critical societal issues like resource efficiency and environmental sustainability.

Single-Use, Metabolite Absorbing, Resonant Transducer (SMART) Culture Vessels for Label-Free, Continuous Cell Culture Progression Monitoring.

Secreted metabolites are an important class of bio-process analytical technology (PAT) targets that can correlate to cell conditions. However, current strategies for measuring metabolites are limited to discrete measurements, resulting in limited understanding and ability for feedback control strategies. Herein, a continuous metabolite monitoring strategy is demonstrated using a single-use metabolite absorbing resonant transducer (SMART) to correlate with cell growth. Polyacrylate is shown to absorb secreted metabolites from living cells containing hydroxyl and alkenyl groups such as terpenoids, that act as a plasticizer. Upon softening, the polyacrylate irreversibly conformed into engineered voids above a resonant sensor, changing the local permittivity which is interrogated, contact-free, with a vector network analyzer. Compared to sensing using the intrinsic permittivity of cells, the SMART approach yields a 20-fold improvement in sensitivity. Tracking growth of many cell types such as Chinese hamster ovary, HEK293, K562, HeLa, and E. coli cells as well as perturbations in cell proliferation during drug screening assays are demonstrated. The sensor is benchmarked to show continuous measurement over six days, ability to track different growth conditions, selectivity to transducing active cell growth metabolites against other components found in the media, and feasibility to scale out for high throughput campaigns.

Three-dimensional bimodal pore-rich G/MXene sponge amalgamated with vanadium diselenide nanosheets as a high-performance electrode for electrochemical water-oxidation/reduction reactions.

Exploring new strategies to design non-precious and efficient electrocatalysts can provide a solution for sluggish electrocatalytic kinetics and sustainable hydrogen energy. Transition metal selenides are potential contenders for bifunctional electrocatalysis owing to their unique layered structure, low band gap, and high intrinsic activities. However, insufficient access to active sites, lethargic water dissociation, and structural degradation of active materials during electrochemical reactions limit their activities, especially in alkaline media. In this article, we report a useful strategy to assemble vanadium diselenide (VSe2) into a 3D MXene/rGO-based sponge-like architecture (VSe2@G/MXe) using hydrothermal and freeze-drying approaches. The 3D hierarchical meso/macro-pore rich sponge-like morphology not only prevents aggregation of VSe2 nanosheets but also offers a kinetics-favorable framework and high robustness to the electrocatalyst. Synergistic coupling of VSe2 and a MXene/rGO matrix yields a heterostructure with a large specific surface area, high conductivity, and multi-dimensional anisotropic pore channels for uninterrupted mass transport and gas diffusion. Consequently, VSe2@G/MXe presented superior electrochemical activity for both the HER and OER compared to its counterparts (VSe2 and VSe2@G), in alkaline media. The overpotentials required to reach a cathodic and anodic current density of 10 mA cm-2 were 153 mV (Tafel slope = 84 mV dec-1) and 241 mV (Tafel slope = 87 mV dec-1), respectively. The Rct values at the open circuit voltage were as low as 9.1 Ω and 1.41 Ω for the HER and OER activity, respectively. Importantly, VSe2@G/MXe withstands a steady current output for a long 24 h operating time. Hence, this work presents a rational design for 3D microstructures with optimum characteristics for efficient bifunctional alkaline water-splitting.

Ti3C2Tx MXene reinforcement: a nickel-vanadium selenide/MXene based multi-component composite as a battery-type electrode for supercapacitor applications.

Designing innovative microstructures and implementing efficient multicomponent strategies are still challenging to achieve high-performance and chemo-mechanically stable electrode materials. Herein, a hierarchical three-dimensional (3D) graphene oxide (GO) assisted Ti3C2Tx MXene aerogel foam (MXene-GAF) impregnated with battery-type bimetallic nickel vanadium selenide (NiVSe) has been prepared through a hydrothermal method followed by freeze-drying (denoted as NiVSe-MXene-GAF). 3D-oriented cellular pore networks benefit the energy storage process through the effective lodging of NiVSe particles, improving the access of the electrolyte to the active sites, and alleviating volume changes during redox reactions. The 3D MXene-GAF conductive matrix and heterostructured interface of MXene-rGO and NiVSe facilitated the rapid transport of electrical charges and ions during the charge-discharge process. As a result of the synergism of these effects, NiVSe-MXene-GAF exhibited remarkable electrochemical performance with a specific capacity of 305.8 mA h g-1 at 1 A g-1 and 99.2% initial coulombic efficiency. The NiVSe-MXene-GAF electrode delivered a specific capacity of 235.1 mA h g-1 even at a high current density of 12 A g-1 with a 76.8% rate performance. The impedance measurements indicated a low bulk solution resistance (Rs = 0.71 Ω) for NiVSe-MXene-GAF. Furthermore, the structural robustness of NiVSe-MXene-GAF guaranteed long-term stability with a 91.7% capacity retention for successive 7000 cycles. Thus, developing NiVSe-MXene-GAF provides a progressive strategy for fabricating high-performance 3D heterostructured electrode materials for energy storage applications.

Facile synthesis of NiSe2-ZnO nanocomposites for enhanced photocatalysis and wastewater remediation.

In this study, NiSe2 nanocubes, ZnO rods, and their composites were prepared by simple chemical methods to investigate their photocatalytic response and antibacterial activity. The optimal concentration of NiSe2 nanocubes was explored for enhanced photocatalytic performance by varying its percentage in the NiSe2-ZnO composites. The findings suggested that the optical response of ZnO was significantly improved and shifted towards visible region by incorporating NiSe2 as a co-catalyst. The photocatalytic properties of NiSe2, ZnO, and NiSe2-ZnO composites were assessed under visible light by using methylene blue (MB) as a model pollutant. The results showed that the optimized composite containing 75% NiSe2 with ZnO exhibited outstanding photocatalytic efficiency of 97%. The degradation of MB dye by NiSe2, ZnO, and their composites followed the pseudo-first-order reaction kinetics (Langmuir-Hinshelwood model). Furthermore, the prepared NiSe2-ZnO composite displayed exceptional reusability and stability over a number of cycles, demonstrating its practical applicability. This research presents unique findings, showcasing the comparative antibacterial performance of NiSe2, ZnO, and NiSe2-ZnO nanocomposites against Bacillus cereus (B. cereus). Of all the prepared photocatalysts, the 75% NiSe2-ZnO nanocomposite revealed the best performance, exhibiting an inhibition zone of 28 mm.

Fabrication of a highly efficient CuO/ZnCo2O4/CNTs ternary composite for photocatalytic degradation of hazardous pollutants.

In the current study, CuO, ZnCo2O4, CuO/ZnCo2O4, and CuO/ZnCo2O4/CNTs photocatalysts were prepared to remove crystal violet (CV) and colorless pollutants (diclofenac sodium and phenol) from wastewater. Herein, sol-gel and co-precipitation methods were used to synthesize CuO and ZnCo2O4, respectively. The sonication method was used to synthesize CuO/ZnCo2O4 and a CNTs-based composite (CuO/ZnCo2O4/CNTs). From the UV-Vis spectra of CuO, ZnCo2O4, CuO/ZnCo2O4, and CuO/ZnCo2O4/CNTs, the optical band gap value was calculated to be 2.11, 2.18, 1.71 and 1.63 eV respectively. The photocatalytic results revealed that CuO/ZnCo2O4/CNTs exhibited higher degradation of 87.7% against CV dye, 82% against diclofenac sodium, and 72% against phenol as compared to other prepared photocatalysts. The OH˙ radical is identified as the active species in the photocatalytic process over CuO/ZnCo2O4/CNTs. The impact of several parameters, such as pH, concentration, and catalyst dosage, has also been investigated. The better activity of the CNTs-based composite was due to the synergic effect of both CuO/ZnCo2O4 nanocomposite and carbon nanotubes. Therefore, the synthesized CuO/ZnCo2O4/CNTs photocatalyst has the potential to degrade organic wastewater effluents effectively.

Harnessing the synergistic potential of TiO2-CuSe composites for enhanced photocatalytic and antibacterial activities.

With growing environmental concerns, the removal of toxic industrial dyes from wastewater has become a critical global issue. In this study, TiO2-CuSe composites were synthesized using a cost-effective and simple chemical method to determine the optimal concentration of CuSe for the efficient degradation of methylene blue (MB) under visible light. The TiO2 samples exhibited a mix of rutile and anatase phases, while CuSe formed in a hexagonal phase. Both TiO2 and CuSe were observed to have agglomerated particles with indistinct boundaries. The optical bandgap shifted towards the visible region from 3.25 eV (pure TiO2) to 2.91 eV with increasing the amount of CuSe in the composites. The photocatalytic activity of TiO2, CuSe, and TiO2-CuSe composites was evaluated by monitoring MB degradation, with the composites outperforming the individual components under visible light. Notably, the TiO2-20% CuSe composite (AK-4) demonstrated superior efficiency, removing 98% of MB in just 70 minutes. The photocatalysts also exhibited enhanced antibacterial properties, effectively reducing E. coli colonies from 1.71 × 1012 CFU mL-1 (pure TiO2) to 1 × 1010 CFU mL-1 for the AK-4 composite. This study suggests that visible light-activated TiO2-CuSe composites could be effective for both water purification and bacterial infection control.

Eco-conscious upcycling of sugarcane bagasse into flexible polyurethane foam for mechanical & acoustic relevance.

This study explores the use of sugarcane bagasse (SCB), a byproduct of sugarcane processing, as a bio-filler in the production of flexible polyurethane foam (FPU), focusing on its benefits for both the environment and the economy. By varying the inclusion of SCB waste from 1 to 6 wt%, the research aims to enhance the FPU's mechanical and acoustic characteristics. Techniques such as Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM) were utilized to analyze the chemical structure and surface characteristics of both SCB and the FPU/SCB composites. Additionally, tests on gel fraction, density, and mechanical properties were conducted. The results indicate that adding 4 wt% SCB to FPU considerably improved the foam's properties. This modification resulted in a 148.63% increase in apparent density, a 228.47% rise in compressive strength, and a 116.24% boost in tensile strength. Furthermore, sound absorption across various frequency ranges was enhanced compared to the control foam. Additionally, the findings show that SCB effectively shifts sound absorption characteristics to lower frequencies. Specifically, at a low frequency of 500 Hz, the sound absorption coefficient increased to 0.4 with a foam thickness of 20 mm. This demonstrates that SCB can significantly improve FPU's performance, making it an attractive option for applications requiring noise mitigation, such as in the automotive and construction industries, thereby offering a sustainable solution to waste management and materials innovation.

An integrated experimental and theoretical approach to probe Cr(vi) uptake using decorated halloysite nanotubes for efficient water treatment.

Halloysite nanotubes (HNTs) were surface functionalized using four distinct chemical moieties (amidoxime, hydrazone, ethylenediamine (EDA), and diethylenetriamine (DETA)), producing modified HNTs (H1-H4) capable of binding with Cr(vi) ions. Advanced techniques like FTIR, XRD, SEM, and EDX provided evidence of the successful functionalization of these HNTs. Notably, the functionalization occurred on the surface of HNTs, rather than within the interlayer or lumen. These decorated HNTs were effective in capturing Cr(vi) ions at optimized sorption parameters, with adsorption rates ranging between 58-94%, as confirmed by atomic absorption spectroscopy (AAS). The mechanism of adsorption was further scrutinized through the Freundlich and Langmuir isotherms. Langmuir isotherms revealed the nearest fit to the data suggesting the monolayer adsorption of Cr(vi) ions onto the nanotubes, indicating a favorable adsorption process. It was hypothesized that Cr(vi) ions are primarily attracted to the amine groups on the modified nanotubes. Quantum chemical calculations further revealed that HNTs functionalized with hydrazone structures (H2) demonstrated a higher affinity (interaction energy -26.33 kcal mol-1) for the Cr(vi) ions. This can be explained by the formation of stronger hydrogen bonds with the NH moieties of the hydrazone moiety, than those established by the OH of oxime (H1) and longer amine chains (H3 and H4), respectively. Overall, the findings suggest that these decorated HNTs could serve as an effective and cost-efficient solution for treating water pollution.

Beyond the ordinary: exploring the synergistic effect of iodine and nickel doping in cobalt hydroxide for superior energy storage applications.

This study explores the iodine and nickel-doped cobalt hydroxide (I & Ni-co-doped-Co(OH)2) as a potential material for energy storage and conversion applications owing to its excellent electrochemical characteristics. According to our analysis, it was revealed that this material exhibits pseudocapacitive-like behavior, as evident from distinct redox peaks observed in cyclic voltammetry, which confirms its ability to store charges. The diffusion coefficient analysis reveals that this material possesses conductivity and rapid diffusion kinetics, making it particularly advantageous compared to materials synthesized in previous studies. Charge-discharge measurements were performed to analyze the charge storage capacity and stability of this material after 3000 consecutive cycles, showing its excellent stability with minimum loss of capacitance. Furthermore, its anodic and cathodic linear sweep voltammetry curves were measured to evaluate its oxygen evolution and hydrogen evolution reaction performance. The results showed that the material exhibited an excellent water splitting performance, which suggests its potential practical application for hydrogen production. This increased activity was attributed to the doping of α-Co(OH)2, which improved its structural stability, electrical conductivity, and charge transfer efficiency. Thus, I & Ni-co-doped-Co(OH)2 possesses enhanced properties that make it an excellent material for both energy storage and hydrogen generation applications.

Fully Atom-Efficient Solvent-Mediated Biopolymer Manufacturing: A Base Case Illustrated with Macromolecular Surfactants Tailored to Stable Polymer-Water Interfaces.

This work introduces a novel 1-pot, 0-waste, 0-VOC methodology for synthesizing polymeric surfactants using acrylated epoxidized soybean oil and acrylated glycerol as primary monomers. These macromolecular surfactants are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization, allowing for tunable hydrophilic-lipophilic balance (HLB) and ionic properties. We characterize the copolymers' chemical composition and surface-active properties, and evaluate their effectiveness in forming and stabilizing emulsions of semiepoxidized soybean oil and poly(acrylated epoxidized high oleic soybean oil). Comprehensive analyses, including gel permeation chromatography, nuclear magnetic resonance spectroscopy, dynamic light scattering, particle size distribution, zeta potential, and critical micelle concentration, provide detailed insights into the copolymers and the emulsions they form. The results demonstrate that the RAFT-polymerized surfactants offer long-lasting stability and effectively disperse both common oil-in-water emulsions and highly viscous and hydrophobic polymer latexes. These surfactants outperform traditional small molecule surfactants by reducing particle size and preventing phase separation, even over extended storage periods. Stable polymer-water interfaces are achieved through HLB control, tailored by monomer composition, and the final product requires no additional purification since polymerization occurs in liquid surfactants. While small molecules contribute to rapid micelle formation, the polymeric components enhance long-term stability through steric repulsion and slower dynamics. This method enables even the emulsification of polymers with submicron particle size, which ordinarily requires emulsion polymerization. Integrating biobased polymeric surfactants with advanced polymer processing techniques opens new possibilities for transforming highly hydrophobic polymers into latexes, facilitating downstream applications. This innovation enhances the environmental sustainability of surfactant production and broadens the potential for polymer emulsification technologies. Additionally, the integrated solution-processing approach demonstrated here can be applied to other emerging polymers, where judiciously selected nonvolatile solvents facilitate the polymerization and play a role in the final application.

Iron/vanadium co-doped tungsten oxide nanostructures anchored on graphitic carbon nitride sheets (FeV-WO3@g-C3N4) as a cost-effective novel electrode material for advanced supercapacitor applications.

In this work, we studied the effect of iron (Fe) and vanadium (V) co-doping (Fe/V), and graphitic carbon nitride (g-C3N4) on the performance of tungsten oxide (WO3) based electrodes for supercapacitor applications. The lone pair of electrons on nitrogen can improve the surface polarity of the g-C3N4 electrode material, which may results in multiple binding sites on the surface of electrode for interaction with electrolyte ions. As electrolyte ions interact with g-C3N4, they quickly become entangled with FeV-WO3 nanostructures, and the contact between the electrolyte and the working electrode is strengthened. Herein, FeV-WO3@g-C3N4 is fabricated by a wet chemical approach along with pure WO3 and FeV-WO3. All of the prepared samples i.e., WO3, FeV-WO3, and FeV-WO3@g-C3N4 were characterized by XRD, FTIR, EDS, FESEM, XPS, Raman, and BET techniques. Electrochemical performance is evaluated by cyclic voltammetry (CV), galvanic charge/discharge (GCD), and electrochemical impedance spectroscopy (EIS). It is concluded from electrochemical studies that FeV-WO3@g-C3N4 exhibits the highest electrochemical performance with specific capacitance of 1033.68 F g-1 at scan rate 5 mV s-1 in the potential window range from -0.8 to 0.25 V, that is greater than that for WO3 (422.76 F g-1) and FeV-WO3 (669.76 F g-1). FeV-WO3@g-C3N4 has the highest discharge time (867 s) that shows it has greater storage capacity, and its coulombic efficiency is 96.7%, which is greater than that for WO3 (80.1%) and FeV-WO3 (92.1%), respectively. Furthermore, excellent stability up to 2000 cycles is observed in FeV-WO3@g-C3N4. It is revealed from EIS measurements that equivalent series resistance and charge transfer values calculated for FeV-WO3@g-C3N4 are 1.82 Ω and 0.65 Ω, respectively.

Cavitation-Mediated Fracture Energy Dissipation in Polylactide at Rubbery Soybean Oil-Based Block Copolymer Interfaces Formed via Reactive Extrusion.

Here, we spearhead a new approach to biopolymer impact modification that demonstrates superior performance while maintaining greater than 99% compostability. Using soybean-based monomers, a virtually untapped resource in terms of commercial volume and overall cost, a series of hyperbranched block copolymers were synthesized and melt-processed with poly(l-lactide) (PLA) to yield impact resistant all-polymer composites. Although PLA impact modification has been treated extensively, to date, the only practical solutions have relied on non-compostable petroleum-based rubbers. This study illustrates the activity of energy dissipation mechanisms such as cavitation, classically relegated to well-entangled petroleum-based rubbers, in poorly entangled hyperbranched soybean-based rubbers. Furthermore, we present a complete study of the mechanical performance and morphology of these impact modified PLA composites. The significance of combining deformation theory with a scalable green alternative to petroleum-based rubbers opens up a potential avenue for cheap compostable engineering thermoplastics.

Passivation-driven speciation, dealloying and purification.

Thin passivating surface oxide layers on metal alloys form a dissipation horizon between dissimilar phases, hence harbour an inherent free energy and composition gradient. We exploit this gradient to drive order and selective surface separation (speciation), enabling redox-driven enrichment of the core by selective conversion of low standard reduction potential (E°) components into oxides. Coupling this oxide growth to volumetric changes during solidification allows us to create oxide crystallites trapped in a metal ('ship-in-a-bottle') or extrusion of metal fingerlings on the heavily oxidized particle. We confirm the underlying mechanism through high temperature X-ray diffraction and characterization of solidification-trapped particle states. We demonstrate that engineering the passivating surface oxide can lead to purification via selective dealloying with concomitant enrichment of the core, leading to disparate particle morphologies.

Polystyrene-block-Polydimethylsiloxane as a Potential Silica Substitute for Polysiloxane Reinforcement.

Here we report microphase-separated poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) as a reinforcing filler in PDMS thermosets that overcomes the long-standing problem of aging in the processing of silica-reinforced silicone. Surprisingly, PS-b-PDMS reinforced composites display comparable mechanical performance to silica-modified analogs, even though the modulus of PS is much smaller than that of silica and there is no evidence of percolation with respect to the rigid PS domains. We have found that a few unique characteristics contribute to the reinforcing performance of PS-b-PDMS. The strong self-assembly behavior promotes batch-to-batch repeatability by having well-dispersed fillers. The structure and size of the fillers depend on the loading and characteristics of both filler and matrix, along with the shear effect. The reinforcing effect of PS-b-PDMS is mostly brought by the entanglements between the corona layer of the filler and the matrix, rather than the hydrodynamic reinforcement of the PS phase.

Shear-induced network-to-network transition in a block copolymer melt.

A tricontinuous (10,3)c network phase is documented in a poly(cyclohexylethylene-b-ethylethylene-b-ethylene) triblock copolymer melt based on small-angle x-ray scattering. Application of shear transforms the self-assembled soft material into a single crystal (10,3)d network while preserving the short-range threefold connector geometry. Long-range topological restructuring reduces the space group symmetry, from Fddd to Pnna, maintaining orthorhombic lattice symmetry. Both phases are stable to long time annealing, indicative of nearly degenerate free energies and prohibitive kinetic barriers.