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At least 1,189 records · Page 66

Processing and Characterization of Basalt Fiber Reinforced Ceramic Composites for High Temperature Applications Using Polymer Precursors

The development of high temperature structural composite materials has been very limited due to the high cost of the materials and the processing needed. Ceramics can take much higher temperatures, but they are difficult to produce and form in bulk volumes. Polymer Derived Ceramics (PDCs) begin as a polymer matrix, allowing a shape to be formed and cured and then to be pyrolized in order to obtain a ceramic with the associated thermal and mechanical properties. The two PDCs used in this development are polysiloxane and polycarbosilane. Polysiloxanes contain a silicon oxycarbide backbone when pyrolized up to 1000 deg C. Polycarbosilane, an organosilicon polymer, contain a silicon-carbon backbone; around 1200 deg C, Beta-SiC begins to crystallize. The use of basalt in structural and high temperature applications has been under development for over 50 years, yet there has been little published research on the incorporation of basalt fibers as a reinforcement in composites. Basalt is a naturally occurring material found in volcanic rock. Continuous basalt fiber reinforced PDCs have been fabricated and tested for the applicability of this composite system as a high temperature structural composite material. Thermal and mechanical testing includes oxyacetylene torch testing and three point bend testing.

Polymer Derived Ceramics↗

Anomalous Transients in Chip Polymer Tantalum Capacitors

Contrary to MnO2 tantalum capacitors, transient processes in polymer tantalum capacitors after voltage application might result in anomalously high, ampere-level currents when a capacitor might appear as a short circuit for a time that is much greater than a transient time in MnO2 capacitors. In this work, conditions that cause anomalous transients in different types of polymer tantalum capacitors have been analyzed. Related phenomena that included increasing of capacitance and dissipation factors with voltage, parametric surge current test failures without damage to capacitors, and increasing leakage currents at low temperatures are described. It has been shown that anomalous transients increased substantially with applied voltage and with reduction of moisture content in capacitors caused by storage or operation at high temperatures and/or in vacuum. Different types of capacitors exhibited different level of transients and modification of conductive polymers or process of their application might decrease transient leakage currents substantially. For space applications, the risk of failures related to anomalous transients can be mitigated by special testing procedures to select parts with an acceptable level of transients and by voltage derating.

Tantalum Capacitors↗

Degradation of ESR in Polymer Tantalum Capacitors During High Temperature Storage

Replacement of MnO2 cathodes with conductive polymers in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. Due to degradation processes in conductive polymer materials, the existing quality assurance testing that has been developed for MnO2 capacitors is not sufficient to guarantee long-term stability of CPTCs. Insertion of CPTCs in hi-rel systems requires development of models that can predict degradation of the parts at operating conditions. In this work, variations of AC characteristics (capacitance, DF and ESR) in different types of capacitors from three manufacturers have been monitored during storage at temperatures from 100ºC to 175ºC for periods of up to 15,000 hours. Results show that the most sensitive to degradation parameter is ESR. Distributions of times to parametric failure during storage have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of degradation and prediction of times to failure at use temperatures. Mechanisms of degradation and the effect of packaging are discussed.

equivalent series resistance (ESR)↗

Effect of High Temperature Storage on AC Characteristics of Polymer Tantalum Capacitors

Replacement of MnO2 with conductive polymers as cathode materials in chip tantalum capacitors allows for a substantial reduction of the equivalent series resistance (ESR), improvement of frequency characteristics, and elimination of the possibility of ignition during failures. One of the drawbacks of chip polymer tantalum capacitors (CPTCs) is a relatively poor long-term stability at high temperatures. In this work, variations of capacitance, dissipation factor, and ESR in different types of capacitors including automotive grade parts from three manufacturers have been monitored during storage at temperatures from 100 ºC to 175 ºC for up to 18,000 hours. Results show that ESR is the most and capacitance the least sensitive parameter to degradation. Times to parametric failures have been simulated using a Weibull-Arrhenius model that allowed for assessments of activation energies of the degradation and prediction of times to failure at the use temperature. Degradation of CPTCs was explained by thermo-oxidative processes in conductive polymers that result in exponential increase of the resistivity with time of aging. This process starts after a certain incubation period that depends on packaging materials and design and corresponds to the time that is necessary to form delamination between the encapsulating molding compound and lead frame. The effectiveness of the existing qualification procedures to assure stable operation of CPTCs is discussed.

high temperature storage (HTS)↗

UV Curing Polymers For Radiation Shielding Applications

The scope of the current research is to develop polymers that will be durable under space conditions. In space, polymers can undergo thermal, mechanical, and oxidative degradation depending on which direction in space they are rotated (ram, wake, zenith, or nadir). Polymers can also be synthesized using techniques such as UV-radiation curing1,2 and cross-linking. In the current project, three organic molecules, acrylamide, styrene-butadiene, and triethylene glycol divinyl ether, were studied using computational software called OLTARIS3 (On-Line Tool for the Assessment of Radiation In Space) developed by NASA Langley to predict the degree of radiation shielding. All three molecules showed shielding before 60 g/cm2 areal density.

UV Curing↗

Ion-Conducting Thermoresponsive Films Based on Polymer-Grafted Cellulose Nanocrystals

Mechanically robust, thermo-responsive, ion-conducting nanocomposite films are prepared from poly(2-phenylethyl methacrylate) grafted cellulose nanocrystals (MxG-CNC-g-PPMA). One-component nanocomposite films of the polymer grafted nanoparticle (PGN) MxG-CNC-g-PPMA are imbibed with 30 wt% imidazolium-based ionic liquid, to produce flexible ion-conducting films. These films with 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[H]) not only displays remarkable improvements in toughness (>25 times) and tensile strength (>70 times) relative to the corresponding nanocomposites consisting of the ionic liquid imbibed in the two component CNC/PPMA nanocomposite, but also shows higher ionic conductivity than the corresponding neat PPMA with the same wt.% of ionic liquid. Notably, the one-component film containing 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (MxG-CNC-g-PPMA/[E]) exhibits temperature responsive ionic conduction. The ionic conductivity decreases at around 60°C as a consequence of the lower critical solution temperature (LCST) phase transition of the grafted polymer in the ionic liquid, which leads to phase separation. Moreover, holding the MxG-CNC-g-PPMA/[E] film at room temperature for 24 hours returns the film to its original homogenous state. These materials exhibit properties relevant to thermal cutoff safety devices (e.g., thermal fuse) where a reduction in conductivity above a critical temperature is needed.

36 MATERIALS SCIENCE↗

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗

Morphology and Dynamics of Bottlebrush Polymers

This thesis makes significant advances to the understanding of bottlebrush polymers. While bottlebrushes have received much attention due to the recent discovery of their unprecedented properties, including supersoftness, ultra-low viscosity, and hyperelasticity, this thesis is the first fundamental investigation at the molecular level that comprises structure and dynamics. Neutron scattering experiments, detailed within, reveal spherical or cylindrical shapes, instead of a random coil conformation. Another highlight is the analysis of the fast dynamics at the sub nm-length scale. The combination of three neutron spectrometers and the development of a new analysis technique enabled the calculation of the mean-square displacement over seven orders of magnitude in time scale. This unprecedented result can be applied to a broad class of samples, including polymers and other materials. The thesis is accessible to scientists from other fields, provides the reader with easily understandable guidelines for applying this analysis to other materials, and has the potential to make a significant impact on the analysis of neutron scattering data.

36 MATERIALS SCIENCE↗

Damage to Polystyrene Polymer Film by Shock Wave Induced Bubble Collapse

Metallic surfaces that are in contact with solutions are commonly used in numerous applications where these surfaces can be damaged by shock wave induced bubble collapse. Use of polymer films that coat such surfaces to prevent them from damage requires a better understanding of how much harm collapsing bubbles produce in the films. In this study, we report the results from coarse-grained molecular dynamics simulations to study the damage to polystyrene (PS) films coating a hard surface. The damage was caused by a collapsing nanobubble located in the proximity of the film and interacting with an impinging shock wave. This collapse produces a high-speed water jet that impacts the PS film with a greater force than the shock front and creates cavities/pits in the PS film. We observed that polymer molecules located in the jet vicinity undergo conformational extension in the direction perpendicular to the jet motion, while chain molecules in the rest of the film undergo compression. Furthermore, we also observed that damage to the film is sensitive to the strength of the shock wave.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Porous Polymers as Universal Reversal Agents for Heparin Anticoagulants through an Inclusion–Sequestration Mechanism

Heparins are widely used anticoagulants for surgical procedures and extracorporeal therapies. However, all of them have bleeding risks. Protamine sulfate, the only clinically approved antidote for unfractionated heparin (UFH), has adverse effects. Moreover, protamine can only partially neutralize low-molecular-weight heparins (LMWHs) and is not effective for fondaparinux. In this report an inclusion–sequestration strategy for efficient neutralization of heparin anticoagulants by cationic porous supramolecular organic frameworks (SOFs) and porous organic polymers (POPs) is reported. Isothermal titration calorimetric and fluorescence experiments show strong binding affinities of these porous polymers toward heparins, whereas dynamic light scattering and zeta potential analysis confirm that the heparin sequences are adsorbed into the interior of the porous hosts. Activated partial thromboplastin time, anti-FXa, and thromboelastography assays indicate that their neutralization efficacies are higher than or as high as that of protamine for UFH and generally superior to protamine for LMWHs and fondaparinux, which is further confirmed by tail-transection model in mice and ex vivo aPTT or anti-FXa analysis in rats. Acute toxicity evaluations reveal that one of the SOFs displays outstanding biocompatibility. This work suggests that porous polymers can supply safe and rapid reversal of clinically used heparins, as protamine surrogates, providing an improved approach for their neutralization.

36 MATERIALS SCIENCE↗

Molecular Structure and Conformational Design of Donor‐Acceptor Conjugated Polymers to Enable Predictable Optoelectronic Property

Abstract Tuning the optoelectronic properties of donor‐acceptor conjugated polymers (D‐A CPs) is of great importance in designing various organic optoelectronic devices. However, there remains a critical challenge in precise control of bandgap through synthetic approach, since the chain conformation also affects molecular orbital energy levels. Here, D‐A CPs with different acceptor units are explored that show an opposite trend in energy band gaps with the increasing length of oligothiophene donor units. By investigating their chain conformation and molecular orbital energy, it is found that the molecular orbital energy alignment between donor and acceptor units plays a crucial role in dictating the final optical bandgap of D‐A CPs. For polymers with staggered orbital energy alignment, the higher HOMO with increasing oligothiophene length leads to a narrowing of the optical bandgap despite decreased chain rigidity. On the other hand, for polymers with sandwiched orbital energy alignment, the increased band gap with increasing oligothiophene length originates from the reduction of bandwidth due to more localized charge density distribution. Thus, this work provides a molecular understanding of the role of backbone building blocks on the chain conformation and bandgaps of D‐A CPs for organic optoelectronic devices through the conformation design and segment orbital energy alignment.

Cao, Zhiqiang↗

Lewis Acid‐Activated Charge Trapping in Dielectric Polymers for Superior High‐Temperature Electrostatic Energy Storage

Dielectric polymer capacitors are essential for electrostatic energy storage but suffer from charge transport-induced energy losses, particularly at elevated temperatures where thermally activated charge carriers exacerbate conduction. Conventional mitigation strategies rely on introducing heterogeneous interfaces to create charge traps, complicating scalable film fabrication. A homogeneous molecular trapping mechanism would circumvent these complexities, yet remains underexplored. Herein, a charge trapping strategy is devised by modifying the lowest occupied molecular orbitals of dielectric polymers through Lewis acid-base adduct formation. The use of tris(pentafluorophenyl)boron (BCF) as a Lewis acidic molecular additive introduces deeper charge traps in commercial polyetherimide (PEI) while retaining homogeneity. With only 0.5 wt.% loading, the PEI-BCF film exhibits greatly improved breakdown strength, achieving an ultrahigh discharged energy density of 7.3 J cm-3 with excellent cycle stability at 200 °C. This work establishes a facile molecular approach to decoupling charge trapping from heterogeneous interfaces, enabling high-energy-density polymer capacitors operable under extreme thermal conditions.

Fan, Lu↗

Polymer Passivated All Inorganic Micro‐Structured CsPbI x Br y Perovskite Toward Highly Efficient Photodetectors

Abstract Solution‐processed inorganic perovskites cause chemical and structural defects unfavorable for photodetector application. Using a binary solvent, defects in CsPbI x Br y (CPIB) perovskite are passivated with poly 4‐vinylpyridine (PVP) and Poly methyl methacrylate (PMMA) polymers. X‐ray photoelectron spectroscopy and FTIR spectra reveal a Lewis base‐acid interaction between Pb 2+ and polymer, confirming the passivation of CPIB perovskite. Scanning electron microscopy analysis shows a dual‐surface morphology with microribbons and microcrystals in perovskites. After PMMA treatment, CPIB perovskite exhibits a blue shift in the bandgap (1.8 to 1.95 eV), while the PVP induced a redshift, reducing the bandgap to 1.7 eV. Blue shift in PL analysis indicates modification of grain boundaries. A higher lifetime obtained for CPIB/PVP confirms the restraint of non‐radiative recombinations. Photodetectors are fabricated with pristine CPIB, CPIB/PVP, and CPIB/PMMA perovskites. The passivated CPIB/PVP‐based photodetector exhibits a quick rise time of ≈23 ms and a decay time of ≈17 ms. It also demonstrates a remarkable photoresponsivity of 23 mA W −1 , an internal quantum efficiency of 4.9%, and a detectivity of 15.0 × 10 10 Jones at 10 mW cm −2 light intensity. This approach shows the potential for environmentally stable polymers to passivate inorganic perovskites for high photodetection performance.

Shah, Shruti↗

Solid‐Adsorbed Polymer‐Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non‐Aqueous Li Batteries

Abstract Polymers are known to adsorb spontaneously from liquid solutions in contact with high‐energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in‐depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. These findings point to a simple, versatile approach for extending the lifetime of batteries.

Jin, Shuo↗

Hybrid Monomer Design Synergizing Property Trade‐offs in Developing Polymers for Circularity and Performance

Abstract Current search for more sustainable plastics seeks to redesign polymers possessing both chemical recyclability to monomer for a circular plastics economy and desirable performance that can rival or even exceed today's non‐recyclable or hard‐to‐recycle petroleum‐based incumbents. However, within a traditional monomer framework it is challenging to optimize, concurrently , contrasting polymerizability/depolymerizability and recyclability/performance properties. Here, we highlight the emerging hybrid monomer design strategy to develop intrinsically circular polymers with tunable performance properties, aiming to unify desired, but otherwise conflicting, properties in a single monomer. Conceptually, this design hybridizes parent monomer pairs of contrasting, mismatching, or matching properties into offspring monomers that not only unify the above‐described conflicting properties but also radically alter the resultant polymer properties far beyond the limits of what either parent homopolymers or their copolymers can achieve.

Shi, Changxia↗

Solid–Adsorbed Polymer–Electrolyte Interphases for Stabilizing Metal Anodes in Aqueous Zn and Non–Aqueous Li Batteries

Polymers are known to adsorb spontaneously from liquid solutions in contact with high-energy substrates to form configurationally complex, but robust phases that often exhibit higher durability than might be expected from the individual physical bonds formed with the substrate. Rational control of the physical, chemical, and transport properties of such interphases has emerged as a fundamental opportunity for scientific and technological advances in energy storage technology but requires in-depth understanding of the conformation states and electrochemical effect of the adsorbed polymers. Here, we analyze the interfacial adsorption of oligomeric polyethylene glycol (PEG) chains of moderate sizes dissolved in protic and aprotic liquid electrolytes and find that there is an optimum polymer molecular weight of approximately 400 Da at which the highest columbic efficiency is achieved for both Zn and Li deposition. Furthermore, these findings point to a simple, versatile approach for extending the lifetime of batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer Single‐Chain Nanoparticles: Shaping Solid Surfactants

Polymer single-chain nanoparticles (SCNPs) have found a wide range of applications spanning catalysts, sensors and nanomedicine. The generation of structured SCNPs from star-shaped polymers with diverse architectures and functionalities affords a new avenue to expand the emerging research area. The large-scale synthesis of structured SCNPs is described by the electrostatics-mediated intramolecular crosslinking of three types of 3-armed star-shaped polymers (T-P4VP, T-PS-b-P4VP, and T-P4VP-b-PS), whose configuration is tunable from spherical to cage-shaped to dumbbell-shaped and star-shaped. The structured SCNPs are amphiphilic and can be used as solid surfactants to stabilize different types of emulsions.

Li, Shuailong↗