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At least 253 records · Page 14

Polymer Conformations and Diffusion Through a Monolayer of Confining Nanoparticles

We present coarse-grained molecular dynamics simulations to probe chain-scale polymer conformations and diffusion between confining nanoparticles (NPs). By constructing a monolayer of hexagonally-packed NPs in a polymer melt with athermal interactions, we observe the magnitude and length-scale over which homogeneously confining NPs impact the polymer behavior, which provides fundamental insights into more complex polymer nanocomposites. We show that polymer conformations are more perturbed under strong confinement (i.e. when the interparticle distance, ID, is less than twice the polymer radius of gyration, 2R g ) as compared to around an isolated NP, and the effect depends on the ratio of R NP /R g rather than either independently. In fact, these conformations can be quantitatively replicated by executing a simple random walk in a similarly confining environment. We also show that polymer diffusion is slowed by the presence of NPs and the slowing persists far beyond the length-scale over which polymer conformations are perturbed. Although the slowing is strongest ~R g from the NPs, the diffusion coefficient is slower even beyond ~5R g from the NPs. Furthermore, by analyzing the directional van Hove distributions, we show polymer diffusion away from the NP monolayer is bulk-like while diffusion through the monolayer is slower with increasing NP confinement. Furthermore, these molecular dynamics simulations provide fundamental insights into the temporal and spatial effect of confining, athermal NPs on chain-scale polymer conformations and diffusion.

36 MATERIALS SCIENCE↗

High-Resolution Imaging of Unstained Polymer Materials

Electron microscopy has played an important role in polymer characterization. Traditionally, electron diffraction is used to study crystalline polymers while transmission electron microscopy is used to study microphase separation in stained block copolymers and other multiphase systems. We describe developments that eliminate the barrier between these two approaches - it is now possible to image polymer crystals with atomic resolution. The focus of this Review is on high-resolution imaging (30 Å and smaller) of unstained polymers. Recent advances in hardware allow for capturing numerous (as many as 105) low-dose images from an unperturbed specimen; beam damage is a significant barrier to high-resolution electron microscopy of polymers. Machine-learning-based software is then used to sort and average the images to retrieve pristine structural information from a collection of noisy images. Acknowledging the heterogeneity in polymer samples prior to averaging is essential. Molecular conformations in a wide range of amphiphilic block copolymers, polymerized ionic liquids, and conjugated polymers can be gleaned from two-dimensional projections (2D), three-dimensional (3D) tomograms, and four-dimensional (4D) scanning transmission electron microscopy (STEM) data sets where 2D diffraction patterns are taken as a function of position. Some methods such as phase contrast STEM have been used to image closely related materials such as metal-organic frameworks but not polymers. With improvements in hardware and software, such methods may soon be applied to polymers. Our goal is to provide a comprehensive understanding of the strategies toward the high-resolution imaging of radiation sensitive polymer materials at different length scales.

36 MATERIALS SCIENCE↗

Experimental Investigation on Separation Behavior of Heavy-Oil Emulsion for Polymer Flooding on Alaska North Slope

The first-ever field pilot on Alaska North Slope (ANS) to validate using polymer floods for heavy-oil enhanced oil recovery is currently ongoing. One of the major concerns of the operator is the effect of polymer on oil/water-separation efficiency after polymer breakthrough. This work investigates the influence of polymer on the separation behavior of heavy-oil emulsions and evaluates the performance of emulsion breakers (EBs). In this study, two types of heavy-oil emulsions were prepared and tested at 20 and 50% water cut (WC), respectively. The bottle test method was used in the experiments, in which the separated water volume with time, the separated water quality, and the volume fraction of phases were recorded. Results showed that polymer accelerated the oil/water separation acting as an emulsion inhibitor at 20% WC but tended to impede the water separation at 50% WC. Regardless of WC, polymer resulted in poor water quality and the formation of a stable intermediate oil in water (o/w) emulsion, because of the increased viscosity of the water phase. The performance of EBs showed a complex dependency on the WC, the type of demulsifier and dosage, and the polymer concentration. Despite the varied conditions encountered in the heavy-oil/water/polymer/demulsifier system, a compound EB achieved satisfactory demulsification performance, showing the highest potential for deployment in the current ANS polymer flooding pilot. Here, we systematically studied the potential influence of polymer breakthrough on the separation behavior of heavy-oil emulsion on ANS for the first time. The findings of this study will provide practical guidance in advance for produced fluid treatment of the ongoing first-ever polymer flooding pilot on ANS.

54 ENVIRONMENTAL SCIENCES↗

Robust Molecular Predictive Methods for Novel Polymer Discovery and Applications

Polymeric materials are ubiquitous in modern society and they play an instrumental role in almost all industries, undoubtedly including the energy and environment sectors. Increased demand of energy and awareness to sustainability both necessitates the development of novel polymers with enhanced properties. Unfortunately, their structural and behavioral complexity render such discovery challenging and impeded. To address this problem, scientists are developing various computational modeling techniques and leveraging their power to depict the relationship between structural characteristics of polymers and their properties (such as rheological behaviors), and use such prediction to guide the design and syntheses of novel polymeric materials with enhanced performances. Unfortunately, predicting the relationships between polymer structure and composition with rheological properties via atomistic modeling is still a major challenge because of the extended time and length scales involved. Studying dynamic shear viscosity and linear viscoelasticity using molecular models requires capabilities that have been elusive, including representation of large molecular weight chains with an effective internal scale capable of describing entanglement, shear-rates that are in the s-1 scale with accurate quantitative stresses, and chemically-realistic combinations of both homogeneous and heterogeneous systems. Motivated by these unmet challenges, the overall technical objective of this DOE-STTR Phase II project is to develop robust molecular predictive methods for advanced polymer discovery and applications and especially for designing and demonstrating the “smart” polymer-based waterflooding enhanced oil recovery (EOR) process. In particular, we apply state-of-the-art molecular modeling methods developed by our academic partner, Materials Stimulation Center (MSC) at California Institute of Technology (Caltech), to facilitate and accelerate the experimental discovery processes. During the Phase I of this project, we had focused on development and demonstration of the molecular modeling methods to describe rheological properties of non-Newtonian polymer fluids, and to improve our fundamental understandings of shear-thickening mechanism and kinetics. In Phase II, we further apply the theoretical models to guide our experimental programs to improve our design of smart rheology modifier (SRM) polymers and their optimization for EOR. Specifically, we have three objectives in the Phase II study: (1) to further improve out computational modeling methods, coupling with the advanced machine learning algorithms; (2) to develop cost-effective and efficient SRM-flooding process suitable for EOR applications under typical reservoir conditions; and (3) to further explore the application of our molecular predictive models for innovative material discovery in other industrial applications. The recent development of our multiscale predictive framework allows the successful prediction of rheological properties from the chemical structure for polymers of experimentally relevant molecular weights, and provides an in-silico machine learning engine for screening novel compositions and structures with optimized non-Newtonian response, required for both shear-thinning and shear-thickening applications. Our framework provides: (1) procedures and tools for systematic coarsening from atomistic models and reverse mapping of coarse-grain models to atomistic, (2) unique ab initio methods to characterize the atomistic origin of colloidal and interfacial interactions and phenomena, (3) systematic structure and composition builders based on practical descriptors that drive rheological changes in polymer melts and diluted polymer mixtures, (4) a rheological properties engine capable of predicting viscosity in the zero-shear limit and under realistic dynamic conditions (for shear-rates commensurate with experiments) for large heterogeneous systems, (5) coarse-grain force fields with improved non-bond descriptions based on accurate quantum mechanics, (6) an in-silico screening machine learning engine that feeds from the systematic model builders to cover the descriptors search space, computes the rheological properties from converged trajectories spanning sub-milliseconds and ranks them for each structure/composition using an automated viscosity-vs-shear rate fitness function that can be tuned for shear-thickening, shear-thinning and other rheological responses.

02 PETROLEUM↗

Collective Nanoparticle Dynamics Associated with Bridging Network Formation in Model Polymer Nanocomposites

The addition of nanoparticles (NPs) to polymers is a powerful method to improve the mechanical and other properties of macromolecular materials. Such hybrid polymer–particle systems are also rich in fundamental soft matter physics. Among several factors contributing to mechanical reinforcement, a polymer-mediated NP network is considered to be the most important in polymer nanocomposites (PNCs). Here, we present an integrated experimental–theoretical study of the collective NP dynamics in model PNCs using X-ray photon correlation spectroscopy and microscopic statistical mechanics theory. Silica NPs dispersed in unentangled or entangled poly(2-vinylpyridine) matrices over a range of NP loadings are used. Static collective structure factors of the NP subsystems at temperatures above the bulk glass transition temperature reveal the formation of a network-like microstructure via polymer-mediated bridges at high NP loadings above the percolation threshold. The NP collective relaxation times are up to 3 orders of magnitude longer than the self-diffusion limit of isolated NPs and display a rich dependence with observation wavevector and NP loading. A mode-coupling theory dynamical analysis that incorporates the static polymer-mediated bridging structure and collective motions of NPs is performed. It captures well both the observed scattering wavevector and NP loading dependences of the collective NP dynamics in the unentangled polymer matrix, with modest quantitative deviations emerging for the entangled PNC samples. Here, we identify an unusual and weak temperature dependence of collective NP dynamics, in qualitative contrast with the mechanical response. Hence, the present study has revealed key aspects of the collective motions of NPs connected by polymer bridges in contact with a viscous adsorbing polymer medium and identifies some outstanding remaining challenges for the theoretical understanding of these complex soft materials.

36 MATERIALS SCIENCE↗

Unravelling the Role of Electron Acceptors for the Universal Enhancement of Charge Transport in Quinoid-Donor-Acceptor Polymers for High-Performance Transistors

The quinoid-donor-acceptor (Q-D-A) strategy has recently emerged as a promising approach for constructing high mobility semiconducting polymers. In order to fully explore the potential of this strategy in improving the charge transport and elucidating the structure-property-performance relationships in Q-D-A polymers, a series of new polymers with different electron acceptor units and backbone coplanarity have been synthesized and characterized. In this work, all of the resulting Q-D-A polymers exhibit much more planar backbone conformations in comparison to their donor-acceptor (D-A) counterparts. Moreover, organic field-effect transistors based on Q-D-A polymers exhibit excellent effective hole mobilities in a range of 0.44 to 3.35 cm 2 V –1 s –1 , most of which are orders of magnitude higher than those of their corresponding D-A polymers. Notably, the hole mobility of 3.35 cm 2 V –1 s –1 is among the highest for the quinoidal-aromatic polymers characterized by conventional spin-coating methods. Furthermore, the role of electron acceptors in Q-D-A polymers has been comprehensively investigated. Polymers with stronger acceptor units are more inclined to deliver edge-on lamellas, high film crystallinity, small effective hole masses, and decent operational stability. The detailed structure-property-device performance relationship will pave the way toward high performance semiconducting polymers using the potent Q-D-A strategy.

36 MATERIALS SCIENCE↗

Direct Evidence of Graphene-Induced Molecular Reorientation in Polymer Films

For the first time, direct evidence of graphene-induced molecular reorientation in polymer films using polarization modulated infrared reflection absorption spectroscopy (PMIRRAS) are presented. By creating favorable electrostatic interactions, graphene-polymer interfaces can be controlled by varying polymer and solvent composition. After trans of unmodified graphene from copper onto a polymer substrate, polymer chain rearrangement relative to the orientation at the polymer-copper interface is observed using PM-IRRAS. Transfer success is characterized using both optical transmission measurements and Raman spectroscopy to quantify the transfer fidelity, i.e. graphene coverage fraction. Taken together, oxygencontaining poly(ethylene-co-vinyl acetate) shows more polymer chain rearrangement and better graphene coverage compared to oxygen-free polyethylene. Polymer composition seems to dominate graphene-polymer interactions while solvent choice has a smaller effect on transfer quality. These results are the first direct measurement of this effect and point towards the possibility of engineering graphene-polymer interactions for specific applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene‐Based Organic Photovoltaics

Abstract Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐ alt ‐(3,3″′‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2″′‐quaterthiophen‐5,5‐diyl)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.

Yi, Xueping↗

Effects of 2D filler on rheology of additive manufacturing polymers: Simulation and experiment on polyetherketoneketone-mica composites

Polymeric composites have attracted increasing interest in fundamental studies and industrial applications due to their often-superior characteristics over conventional pure polymers. In this work, we studied the relationship between the rheological properties, critical in processing methods such as additive manufacturing, and the structure of a polymer-2D filler system by experiment and simulation methods. Considering the high performance polymer polyetherketoneketone (PEKK) with 2D filler (mica) composite as an example, the effects of filler size, filler content, surface chemistry and shear rate were systematically investigated. Here, it is demonstrated that the interaction between the polymer and 2D filler brings two different consequences on tuning the viscosity of polymer-filler composite. The stronger interaction increases the shear stress of the polymer-2D filler composite system, leading to higher viscosity. On the other hand, the stronger interaction can promote more absorption of polymer chains on the surface, which makes the local polymer network disentangled and decreases the continuous viscosity from the polymer network. This work provides a fundamental understanding on the relationship between macroscopic rheological properties and the structural properties and energetics at molecular level of polymer-2D filler composite.

36 MATERIALS SCIENCE↗

Creation of Polymer Datasets with Targeted Backbones for Screening of High-Performance Membranes for Gas Separation

A simple approach was developed to computationally construct a polymer dataset by combining simplified molecular-input line-entry system (SMILES) strings of a targeted polymer backbone and a variety of molecular fragments. This method was used to create 14 polymer datasets by combining seven polymer backbones and molecules from two large molecular datasets (MOSES and QM9). Polymer backbones that were studied include four polydimethylsiloxane (PDMS) based backbones, poly(ethylene oxide) (PEO), poly(allyl glycidyl ether) (PAGE), and polyphosphazene (PPZ). The generated polymer datasets can be used for various cheminformatics tasks, including high-throughput screening for gas permeability and selectivity. This study utilized machine learning (ML) models to screen the polymers for CO2/CH4 and CO2/N2 gas separation using membranes. Several polymers of interest were identified. Here the results highlight that employing an ML model fitted to polymer selectivities leads to higher accuracy in predicting polymer selectivity compared to using the ratio of predicted permeabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

How Do Ionic Liquids “Fold” Ionenes? Computational and Experimental Analysis of Imidazolium Polymers Based on Ether and Alkyl Chain Variations Dissolved in an Ionic Liquid

Molecular dynamics (MD) simulations and complementary experiments are used here to understand the inter- and intramolecular structure and conformational properties of ionenes (i.e., cationic polymers formed from condensation reactions) dissolved in an ionic liquid (IL), 1-ethyl-3-methylimidazolium bistriflimide [C 2 mim + ][Tf 2 N - ]. The simulated structural properties are benchmarked against experimental analyses of these same polymers, mainly using dynamic light scattering (DLS) experiments. Four different imidazolium ionenes are considered, corresponding to variations in the chemistry and structure of the repeat units including: (1) poly (decylimidazolium) (PD 10 ); (2) poly (tetraethyleneglycolimidazolium) (PE 10 ); (3) alternating copolymer (P(ED) 5 ); and (4) a block copolymer (PE 5 D 5 ). Detailed computational analyses of the polymer structure and conformational properties were performed, including the radius of gyration, end-to-end distance, torsional distributions, and site-site and spatial distribution functions. Overall, there is a competition between intramolecular associations between the imidazolium groups and the ether sites in the polymers versus the intermolecular interactions of the polymer imidazolium groups with the surrounding anion molecules. The polymer with only ether linkages (PE 10 ) results in the most intramolecular interactions, leading to significant coiling behavior and chain contraction. These strong interactions reduce chain flexibility, but they also result in much more linear chain configurations and alignment of the imidazolium groups. The polymer structure is strongly affected as the concentration of alkyl groups is increased, and we find that the polymer architecture (alternating versus block copolymer) also has an important influence. Furthermore, these detailed observations are important for understanding the connection between the molecular design of imidazolium polymers and their emergent structural properties, which could lead to unique opportunities for creating polymer composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TransPolymer: a Transformer-based language model for polymer property predictions

Accurate and efficient prediction of polymer properties is of great significance in polymer design. Conventionally, expensive and time-consuming experiments or simulations are required to evaluate polymer functions. Recently, Transformer models, equipped with self-attention mechanisms, have exhibited superior performance in natural language processing. However, such methods have not been investigated in polymer sciences. Herein, we report TransPolymer, a Transformer-based language model for polymer property prediction. Our proposed polymer tokenizer with chemical awareness enables learning representations from polymer sequences. Rigorous experiments on ten polymer property prediction benchmarks demonstrate the superior performance of TransPolymer. Moreover, we show that TransPolymer benefits from pretraining on large unlabeled dataset via Masked Language Modeling. Experimental results further manifest the important role of self-attention in modeling polymer sequences. We highlight this model as a promising computational tool for promoting rational polymer design and understanding structure-property relationships from a data science view.

36 MATERIALS SCIENCE↗

Coarsening dynamics of ternary polymer solutions with mobility and viscosity contrasts

Using phase-field simulations, we investigate the bulk coarsening dynamics of ternary polymer solutions undergoing a glass transition for two models of phase separation: diffusion only and with hydrodynamics. The glass transition is incorporated in both models by imposing mobility and viscosity contrasts between the polymer-rich and polymer-poor phases of the evolving microstructure. For microstructures composed of polymer-poor clusters in a polymer-rich matrix, the mobility and viscosity contrasts significantly hinder coarsening, effectively leading to structural arrest. For microstructures composed of polymer-rich clusters in a polymer-poor matrix, the mobility and viscosity contrasts do not impede domain growth; rather, they change the transient concentration of the polymer-rich phase, altering the shape of the discrete domains. This effect introduces several complexities to the coarsening process, including percolation inversion of the polymer-rich and polymer-poor phases—a phenomenon normally attributed to viscoelastic phase separation.

Chemistry↗

Designing polymer coatings for lithium metal protection

Abstract Protection of lithium metal has been one of the great challenges to realize a long-life, high-energy-density battery. Polymer coatings on lithium metal surface have been proven to be an effective protection method in terms of improved morphology, higher coulombic efficiency, and a longer cycle life. However, there is a variety of design principles of polymer coatings proposed by the research community, and the influence of polymer swelling in liquid electrolytes remains poorly understood. Herein we use crosslinking density and solvent–polymer interaction to quantitatively explain the mechanical property and the ion-transport property of polymer coatings when swollen in liquid electrolytes. Low crosslinking density is beneficial for reducing the rigidity and enhancing the viscosity of the polymer. Ion conductivity increases with the swelling ratio, and activation energy of lithium-ion transport increases in a polar polymer with strong ion–polymer coupling. We propose that polymer coatings must be combined with the emerging electrolytes with unconventional solvent compositions to realize a practical high-performance lithium metal battery. This study can provide design guidelines for polymer coatings through the optimized interactions with upcoming high-performance electrolytes.

Materials Science↗

A Computational Fluid Dynamic Study on Polymer Heat Exchangers

Polymer heat exchangers have been developed for the applications involving weight restrictions or chemical compatibility and fouling issues owing to the low density, anticorrosive properties, and low thermal expansion of polymers. Recently development of additive manufacturing also brings new opportunities to make polymer heat exchangers with desired design that was hard to realize before. However, due to the lower thermal conductivity polymer composite, the overall heat transfer performance is still a challenge in the polymer heat exchanger technology. In present work, a computational fluid dynamic (CFD) model has been developed to study the overall heat transfer performance of additively manufactured polymer heat exchangers. The CFD results offer an insight of fluid flow and temperature distribution in the polymer heat exchangers. This study provides a guidance not only on the polymer material selection but also on the design of polymer heat exchangers. The conclusions will be helpful to design a polymer heat exchanger whose overall heat transfer performance is comparable to a metal heat exchanger.

Zhang, Mingkan↗

Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

59 BASIC BIOLOGICAL SCIENCES↗

Shape memory polymers

New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

Wilson, Thomas S.↗

High optical transparency polymer aerogels using low refractive index monomers

A method of producing a polymer aerogel includes dissolving precursors into a solvent, wherein the precursors include monomers, crosslinkers, a controlling agent and an initiator to form a precursor solution, wherein at least one of the monomers or at least one of the crosslinkers has a refractive index of 1.5 or lower, polymerizing the precursor solution to form a gel polymer, and removing the solvent from the gel polymer to produce the polymer aerogel. A method of producing a polymer aerogel include dissolving precursors into a solvent, wherein the precursors include monomers, crosslinkers, a controlling agent and an initiator to form a precursor solution, polymerizing the precursor solution to form a gel polymer, removing the solvent from the gel polymer to produce the polymer aerogel, and reducing a refractive index of one of either the gel polymer or the polymer aerogel.

Bulger, Eli↗