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At least 883 records · Page 49

Polaron Delocalization in Donor–Acceptor Polymers and its Impact on Organic Electrochemical Transistor Performance

Abstract Donor–acceptor (D‐A) polymers are promising materials for organic electrochemical transistors (OECTs), as they minimize detrimental faradaic side‐reactions during OECT operation, yet their steady‐state OECT performance still lags far behind their all‐donor counterparts. We report three D‐A polymers based on the diketopyrrolopyrrole unit that afford OECT performances similar to those of all‐donor polymers, hence representing a significant improvement to the previously developed D‐A copolymers. In addition to improved OECT performance, DFT simulations of the polymers and their respective hole polarons also reveal a positive correlation between hole polaron delocalization and steady‐state OECT performance, providing new insights into the design of OECT materials. Importantly, we demonstrate how polaron delocalization can be tuned directly at the molecular level by selection of the building blocks comprising the polymers’ conjugated backbone, thus paving the way for the development of even higher performing OECT polymers.

Moser, Maximilian↗

The Influence of Alkyl Spacers and Molecular Weight on the Charge Transport and Storage Properties of Oxy‐Bithiophene‐Based Conjugated Polymers

Abstract Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.

Yu, Hang [Department of Physics and Centre for Pro↗

Transient Covalent Polymers through Carbodiimide‐Driven Assembly

Biochemical systems make use of out-of-equilibrium polymers generated under kinetic control. Inspired by these systems, many abiotic supramolecular polymers driven by chemical fuel reactions have been reported. Conversely, polymers based on transient covalent bonds have received little attention, even though they have the potential to complement supramolecular systems by generating transient structures based on stronger bonds and by offering a straightforward tuning of reaction kinetics. In this study, we show that simple aqueous dicarboxylic acids give poly(anhydrides) when treated with the carbodiimide EDC. Transient covalent polymers with molecular weights exceeding 15,000 are generated which then decompose over the course of hours to weeks. Disassembly kinetics can be controlled using simple substituent effects in the monomer design. The impact of solvent polarity, carbodiimide concentration, temperature, pyridine concentration, and monomer concentration on polymer properties and lifetimes has been investigated. The results reveal substantial control over polymer assembly and disassembly kinetics, highlighting the potential for fine-tuned kinetic control in nonequilibrium polymerization systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing Antisolvent Use in the STRAP Process by Enabling a Temperature–Controlled Polymer Dissolution and Precipitation for the Recycling of Multilayer Plastic Films

The recently reported processing strategy called solvent-targeted recovery and precipitation (STRAP) enables deconstruction of multilayer plastic packaging films into their constituent resins by selective dissolution. It uses a series of solvent washes that are guided by thermodynamic calculations of polymer solubility. In this work, the use of antisolvents in the STRAP process was reduced and solvent mixtures were considered to enable the temperature-controlled dissolution and precipitation of the target polymers in multilayer films. This was considered as a means to further improve the STRAP process and its estimated costs. Two STRAP approaches were compared based on different polymer precipitation techniques: precipitation by the addition of an antisolvent (STRAP-A) and precipitation by decreasing the solvent temperature (STRAP-B). Both approaches were able to separate the constituent polymers in a post-industrial film composed primarily of polyethylene (PE), ethylene vinyl alcohol (EVOH), and polyethylene terephthalate (PET) with near 100 % material efficiency. Technoeconomic analysis indicates that the minimum selling price (MSP) of the recycled resins with STRAP-B is 21.0 % lower than that achieved with STRAP-A. This provides evidence that thermally driven polymer precipitation is an option to reduce the use of antisolvents, making the STRAP process more economically and environmentally attractive. A third process, STRAP-C, was demonstrated with another post-industrial multilayer film of a different composition. Here, the results demonstrate that this process can also recover polymers at similar costs to those of virgin resins, indicating that the STRAP technology is flexible and can remain economically competitive as the plastic feed complexity is increased.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aqueous Polymer Modification of Cellulose Nanofibrils by Grafting‐Through a Reactive Methacrylate Group

Abstract Modifying the surface of cellulose nanofibrils (CNFs) produced by mechanical refinement with a variety of polymer functional groups in an entirely water‐based system is challenging because only surface hydroxyl groups are accessible. To address this limitation, an entirely water‐based, polymer modification scheme is developed. CNFs are functionalized with a reactive methacrylate functional group followed by subsequent grafting‐through polymerization. This modification worked with a variety of water‐soluble and water‐insoluble (meth)acrylates and (meth)acrylamides, grafting up to 45 wt% polymer on to the CNFs. The reaction conditions introducing the methacrylate functional group are adjusted to vary the degree of functionality. Soxhlet extraction of modified samples demonstrates that the reactive methacrylate group is necessary to facilitate polymer grafting. The degree of functionalization of the polymers is studied via quantitative transmission IR spectroscopy and the morphology of the resulting cellulose nanofibrils is studied via a combination of optical, scanning electron, and atomic force microscopy. High levels of polymer modification do not significantly affect the micrometer‐scale fibril morphology.

Kelly, Peter V.↗

Dimethyl‐methylphenyl copolysiloxanes by dimethylsilanolate‐initiated ring opening polymerization. Evidence for linearity of the resulting polymer structures

ABSTRACT Recently, we reported that dimethylsilanolate‐initiated anionic ring opening polymerization of dimethylsiloxy‐ and diphenylsiloxy‐cyclic siloxanes results in polymer chain branching by dimethylsilanolate‐induced cleavage of only one Si‐C Ar side bond in diphenylsiloxy repeat units, leading to formation of “Ph‐T‐branches”, and not extending to the cleavage of the second phenyl group. We attributed this behavior to electronic structures of the participating dimethylsiloxy‐, diphenylsiloxy and Ph‐T‐branch silicons and predicted that copolymers prepared by this synthetic route from dimethylsiloxy‐ and methylphenylsiloxy‐cyclics should not undergo branching at all but should have perfect linear chain configuration. Here, we describe results of a study of two such dimethylsilanolate‐initiated ring opening polymerizations of dimethylsiloxy‐ and methyphenylsiloxy‐cyclic tetramers and characterization of the resulting polymers by SEC‐MALS‐VIS, Mark‐Houwink‐Sakurada relationship and 29 Si NMR. The results obtained clearly confirmed our prediction of expected linearity of these polymer chains and also indicated that the resulting polymers were completely amorphous even at as low methylphenylsiloxy‐content as 3.9 mol %. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1122–1129

Zlatanic, Alisa↗

A Donor Polymer Based on a Difluorinated Pentathiophene Unit Enabling Enhanced Performance for Nonfullerene Organic Solar Cells

Abstract For oligothiophene‐based donor polymers, changing the number of thiophene rings in each repeating unit is a simple and effective approach to tune their optical and electronic properties. While bithiophene‐, terthiophene‐, and quaterthiophene‐based polymers have been widely known and studied, pentathiophene‐based ones are rarely reported. Here, the pentathiophene‐based polymer PT5T, which yields extremely poor device performance with an efficiency of only 0.37%, is synthesized. However, after the introduction of two fluorine atoms to the center thiophene unit, the resulting polymer (PT5T‐2F) yields dramatic improvement in device performance with the fill factor and the power conversion efficiency improved to 70.8% and 9.69%, respectively. The morphological study shows that the difluorinated pentathiophene building block introduces enhanced molecular aggregation and crystallinity of PT5T‐2F, which facilitates the formation of bulk heterojunction blends with higher domain purity. Most importantly, despite its high crystallinity, PT5T‐2F can still produce reasonably small domain sizes in the polymer‐based blend. The results indicate that the difluorinated pentathiophene is a promising building block to construct donor polymers for nonfullerene organic solar cells.

Liu, Jing↗

Ionic/electronic conductivity regulation of n-type polyoxadiazole lithium sulfonate conductive polymer binders for high-performance silicon microparticle anodes

Low-cost silicon microparticles (SiMP), as a substitute for nanostructured silicon, easily suffer from cracks and fractured during the electrochemical cycle. A novel n-type conductive polymer binder with excellent electronic and ionic conductivities as well as good adhesion, has been successfully designed and applied for high-performance SiMP anodes in lithium-ion batteries to address this problem. Its unique features are attributed to the strong electron-withdrawing oxadiazole ring structure with sulfonate polar groups. The combination of rigid and flexible components in the polymer ensures its good mechanical strength and ductility, which is beneficial to suppress the expansion and contraction of SiMP s during the charge/discharge process. By fine-tuning the monomer ratio, the conjugation and sulfonation degrees of the polymer can be precisely controlled to regulate its ionic and electronic conductivities, which has been systematically analyzed with the help of an electrochemical test method, filling in the gap on the conductivity measurement of the polymer in the doping state. The experimental results indicate that the cell with the developed n-type polymer binder and SiMP (~0.5 μm) anodes achieves much better cycling performance than traditional non-conductive binders. It has been considered that the initial capacity of the SiMP anode is controlled by the synergetic effect of ionic and electronic conductivity of the binder, and the capacity retention mainly depends on its electronic conductivity when the ionic conductivity is sufficient. Here, it is worth noting that the fundamental research of this work is also applicable to other battery systems using conductive polymers in order to achieve high energy density, broadening their practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-cement composites with adhesion and re-adhesion (healing) to casing capability for geothermal wellbore applications

Deterioration of cement/casing adhesion in wellbore scenarios can result in unwanted and potentially harmful leakage with the potential of serious repair costs. In this work, we explore the use of self-healing polymers added to conventional wellbore cements as a way to bring about self-healing and readhering (to steel casing) properties to the composite material. The polymers are pH resistant and seem to improve the cement integrity after exposure to typical chemical and thermal stresses encountered under geothermal wellbore conditions. We find that addition of about 10-15 wt% of polymer to the cement visually increases its resistance to fracturing from exposure to geothermal conditions, while the adhesive strength of cement/stainless steel increases with curing time for a period of about 10 days. Self-healing capability was demonstrated by permeability analysis showing that polymer-cement composites reduce flow by 50-70% at cement bulk and at the cement/steel interface. Use of atomistic simulations imply that these polymers have good wetting properties on the steel surfaces. Analysis of the interactions between steel/polymer and cement/polymer show that they are complementary, resulting in a wider range of bonding patterns. Cracks are likely to expose under-coordinated sites that result in more bonding interactions, which agrees well with the permeability measurements showing high degree of healed cracks and healed (cement-steel) interfacial gaps together with an overall increased in structural integrity of these advanced polymer-cement composite materials.

Rod, Kenton A.↗

Effect of highly carboxylated colloidal polymers on cement hydration and interactions with calcium ions

Polymer latexes are often found to retard cement hydration. Interaction of polymer particles with Ca{sup 2+} in pore solution and adsorption of polymer on cement were proposed as possible mechanisms for the retardation effect. This paper aims at disclosing the retardation mechanism of colloidal polymers using a highly carboxylated polystyrene latex. Interaction between colloidal particles and Ca{sup 2+} was studied by post-treatment of the latex with Ca(NO{sub 3}){sub 2}. Techniques including calorimetry, adsorption test, ICP-OES, SEM, are involved to investigate effects of the post-treated latexes on hydrations of cement and C{sub 3}S. It is found that enrichment of Ca{sup 2+} on surface of colloidal particles doesn't contribute to the retardation effect of polymer on cement hydration. Furthermore, the acceleration effect of the two-step treated latex using Ca(NO{sub 3}){sub 2} and Na{sub 2}SiO{sub 3} suggests that nucleation inhibition of the adsorbed polymer layer on cement surface is the more conceivable mechanism responsible for the retardation effect of the highly carboxylated latex.

36 MATERIALS SCIENCE↗

Cation–polymer interactions and local heterogeneity determine the relative order of alkali cation diffusion coefficients in PEGDA hydrogels

Current research efforts are focused on endowing polymer membranes with ion–ion selectivity by incorporating ion–polymer interactions into materials to bias the selective partitioning and or diffusivity of one species over another. However, little is known about the impact of such interactions on the mechanisms of ion transport. In this study, we probe the influence of cation–polymer interactions on cation, anion, and salt diffusivity in a model membrane material, poly(ethylene glycol) diacrylate (PEGDA) by modeling concentrated polyethylene oxide solutions via molecular dynamics simulations. These results are compared to published experimental data for LiCl, NaCl, and KCl diffusion in PEGDA. Experimentally, the order of salt and cation diffusion coefficients for LiCl, NaCl, and KCl deviate from the order in aqueous solutions. Here, simulations identify these deviations to arise from cation–polymer coordination in the membrane. Both the fraction of bound cations and the average binding lifetime increases with decreasing cation hydration free energy (moving down the alkali series), leading to different diffusivity trends in the membrane compared to solution. However, to recover the experimentally observed order of diffusivities cations and salt in our simulations, we needed to incorporate membrane heterogeneity explicitly via a polymer charge scaling procedure. Together, our results indicate that cation–polymer interactions, as well as spatial heterogeneity within the membrane, play a critical role in dictating the observed order of alkali cation and salt diffusion coefficients in membranes.

36 MATERIALS SCIENCE↗

Recent trends in all-organic polymer dielectrics for high-temperature electrostatic energy storage capacitors

Electrostatic energy storage (EES) capacitors are critical for renewable energy and high-power systems, driving the search for dielectric materials that combine superior electrical insulation, mechanical flexibility, low density, cost-effectiveness, and processability. Polymer-based dielectrics have emerged as leading candidates, particularly for high electric field applications. However, conventional polymers often fail to meet the demands of high-temperature environments due to increased electrical conductivity and reduced discharged energy density at elevated temperatures, resulting in energy loss and reduced performance. High glass transition temperature (T g) polymers show promise but require further optimization to enhance their energy storage capabilities under thermal and electrical stress. This review provides a comprehensive update on recent advancements in high-T g polymer-based dielectrics for EES capacitors, focusing on both intrinsic polymers and all-organic composites. It outlines key design principles, critical performance parameters, and innovative strategies—such as nanofiller doping, layered architectures, physical blending, and chemical crosslinking—to improve electrical, thermal, and mechanical properties. The review also highlights emerging trends, including the integration of machine learning algorithms to explore novel polymer structures and expand the chemical design space. By bridging the gap between academic research and industrial application, this review aims to accelerate the development of next-generation dielectric materials capable of balancing multiple performance metrics for high-temperature EES capacitors.

Xie, Zongliang↗

Thermomechanical residual stress evaluation in multi-crystalline silicon solar cells of photovoltaic modules with different encapsulation polymers using synchrotron X-ray microdiffraction

Photovoltaic (PV) module reliability issues, due to silicon cell cracking, are gaining more and more attention due to increasing demand for solar power and reduction of cell thickness to reduce cost. Recent reports show significant effect of encapsulation polymer material on cell cracks leading to the idea of tailoring encapsulation materials for more reliable PV modules. This paper investigates the effect of encapsulation modulus on the cell residual stress using Synchrotron scanning X-ray microdiffraction (µSXRD), which has been proven to be an effective technique to probe the stress in silicon solar cells, especially once they are encapsulated. The post lamination residual stress in the encapsulated multi-crystalline silicon (mc-Si) solar cells was reported for the first time using µSXRD in this manuscript and provide quantitative evaluation of the effect of encapsulation modulus on the cell residual stress. Further, simple approximate finite element (FE) model was also developed to evaluate the effect of the encapsulation polymer on the cell stress. The FE simulations predict the trend of the stress variation with encapsulation polymer modulus very well. Dynamic mechanical analysis and rheological testing of the encapsulation polymers was also performed to correlate the polymer behaviour with the experimental and simulated stresses. Both experimental and simulation results show a similar trend of significant cell stress variation with encapsulation polymer modulus. In the case of external loading, the temperature of load application is observed to be very significant as it dictates the elastic state of the encapsulant, leading to critical conclusion that the encapsulant needs to be selected based on elastic behaviour over the temperature history of the encapsulant during module fabrication and operation. Furthermore, the results and discussion presented are expected to be very useful for development of more reliable PV modules.

14 SOLAR ENERGY↗

Networks and interfaces as catalysts for polymer materials innovation

Autonomous experimental systems offer a compelling glimpse into a future where closed-loop, iterative cycles—performed by machines and guided by artificial intelligence (AI) and machine learning (ML)—play a foundational role in materials research and development. This perspective draws attention to the roles of networks and interfaces—of and between humans and machines—for the purpose of generating knowledge and accelerating innovation. Polymers, a class of materials with massive global impact, present a unique opportunity for the application of informatics and automation to pressing societal challenges. To develop these networks and interfaces in polymer science, the Community Resource for Innovation in Polymer Technology (CRIPT)—a polymer data ecosystem based on novel polymer data model, representation, search, and visualization technologies—is introduced. The ongoing co-design efforts engage stakeholders in industry, academia, and government to uncover rapidly actionable, high-impact opportunities to build networks, bridge interfaces, and catalyze innovation in polymer technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tuning the Mechanical Properties of a Polymer Semiconductor by Modulating Hydrogen Bonding Interactions

Conjugation breakers (CBs) with different H-bonding chemistry and linker flexibility are designed and incorporated into a Diketopyrrolopyrrole (DPP)-based conjugated polymer backbone. The effects of H-bonding interactions on polymer semiconductor morphology, mechanical properties and electrical performance are systematically investigated. We observe that CBs with H-bonding self-association constant >0.7 or denser packing tendency are able to induce higher polymer chain aggregation and crystallinity in as-casted thin film, resulting in higher modulus and crack on-set strain. Additionally, the rDoC (relative degree of crystallinity) of the stretched thin film with the highest crack on-set strain only suffers a small decrease, suggesting the main energy dissipation mechanism is the breakage of H-bonding interactions. By contrast, other less stretchable polymer films dissipate strain energy through the breakage of crystalline domains, indicated by drastic decrease in rDoC. Furthermore, we evaluate their electrical performance under mechanical strain in fully stretchable field-effect transistors. The polymer with the highest crack on-set strain has the least degradation in mobility as a function of strain. Overall, these observations suggest that we can aptly tune the mechanical properties in polymer semiconductors by modulating intermolecular interactions, such as H-bonding chemistry and linker flexibility. Such understanding provides molecular design guidelines for future stretchable semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Precise Control of Noncovalent Interactions in Semiconducting Polymers for High-Performance Organic Field-Effect Transistors

Performed through side-chain engineering or by incorporating intramolecular locking units, the directionality and dynamic nature of noncovalent interactions are particularly attractive for the design of novel semiconducting materials in a wide variety of applications. This work investigates the nature and position of hydrogen bonding (intra- versus intermolecular), with the objective of developing a rational approach to the design of new semiconducting materials with improved properties in the solid state. To control the polymer chains’ self-assembly, a π-conjugated polymer incorporating a moiety capable of generating intramolecular hydrogen bonding is evaluated against a polymer that allows for intermolecular hydrogen bonding. Characterization through various techniques, optical spectroscopies, grazing incidence wide-angle x-ray scattering, and solution small-angle neutron scattering showed that intramolecular hydrogen bonds resulted in materials with improved crystallinity and higher effective conjugation in the solid state. Additionally, the effect of the noncovalent interaction configuration on the optoelectronic properties was analyzed in organic field-effect transistor fabrication. Devices prepared from the materials with intramolecular hydrogen bonds showed significantly higher performance, with three orders of magnitude higher charge mobility than their counterparts fabricated from polymers with intermolecular hydrogen bonds. These results confirm the importance of chemical design on polymer structures and offer a novel route for the design of high-efficiency semiconducting polymers for next-generation electronics.

36 MATERIALS SCIENCE↗

Impact of Cation Insertion on Semiconducting Polymer Thin Films toward Electrochemical Energy Conversion

Semiconducting polymers are being explored for electrochemical and photoelectrochemical energy transformation and storage applications. For these applications, it is critical to understand how ion insertion from the electrolyte into polymer electrodes modulates the polymer electronic structure and electron doping levels. Here, this study explores electrochemical cation insertion in the n-type conjugated redox polymer P90, composed of alternating naphthalene diimide (NDI) acceptor and bithiophene (T2) donor units, where the NDI units are functionalized with heptaethylene glycol (HEG, 90%) and 2-octyl dodecyl (OD, 10%) side chains. By combining in situ techniques (UV-vis absorption and Raman spectroscopies with electrochemistry), structural analysis using ex situ grazing-incidence wide-angle X-ray scattering (GIWAXS), and density functional theory (DFT) calculations, we reveal that dications enable negative polaron and bipolaron formation in the P90 at less reducing potentials while supporting more bipolaron formation than the monocations; moreover, larger dications with smaller hydrated radii increase the maximum P90 electron doping level. We also determine that the monocations lead to more thermodynamically stabilized polarons compared with the dications. These findings highlight the critical role of cation identity in tuning electrochemical charging, charge stabilization, and electronic structure of n-type conjugated redox polymers, providing guidance on the rational design of polymer-based (photo)electrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Residual Solvent Molecules Facilitating the Infiltration Synthesis of ZnO in a Nonreactive Polymer

Infiltration synthesis, the atomic-layer-deposition-based organic–inorganic material hybridization technique that enables unique hybrid composites with improved material properties and inorganic nanostructures replicated from polymer templates, is shown to be driven by the binding reaction between reactive chemical groups of polymers and perfusing vapor-phase material precursors. Here in this paper, we discover that residual solvent molecules from polymer processing can react with infiltrating material precursors to enable the infiltration synthesis of metal oxides in a nonreactive polymer. The systematic study, which combines in situ quartz crystal microgravimetry, polarization-modulated infrared reflection–absorption spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy, shows that the ZnO infiltration synthesis in nominally nonreactive SU-8 polymer is mediated by residual processing solvent cyclopentanone, a cyclic ketone whose Lewis-basic terminal carbonyl group can react with the infiltrating Lewis-acidic Zn precursor diethylzinc (DEZ). In addition, we find favorable roles of residual epoxy rings in the SU-8 film in further assisting the infiltration synthesis of ZnO. Lastly, the discovered rationale not only improves the understanding of infiltration synthesis mechanism, but also potentially expands its application to more diverse polymer systems for the generation of unique functional organic–inorganic hybrids and inorganic nanostructures.

36 MATERIALS SCIENCE↗