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At least 253 records · Page 14

Polymer informatics: Current status and critical next steps

Artificial intelligence (AI) based approaches are beginning to impact several domains of human life, science and technology. Polymer informatics is one such domain where AI and machine learning (ML) tools are being used in the efficient development, design and discovery of polymers. Surrogate models are trained on available polymer data for instant property prediction, allowing screening of promising polymer candidates with specific target property requirements. Questions regarding synthesizability, and potential (retro)synthesis steps to create a target polymer, are being explored using statistical means. Data-driven strategies to tackle unique challenges resulting from the extraordinary chemical and physical diversity of polymers at small and large scales are being explored. Other major hurdles for polymer informatics are the lack of widespread availability of curated and organized data, and approaches to create machine-readable representations that capture not just the structure of complex polymeric situations but also synthesis and processing conditions. Methods to solve inverse problems, wherein polymer recommendations are made using advanced AI algorithms that meet application targets, are being investigated. As various parts of the burgeoning polymer informatics ecosystem mature and become integrated, efficiency improvements, accelerated discoveries and increased productivity can result. Here in this paper, we review emergent components of this polymer informatics ecosystem and discuss imminent challenges and opportunities.

36 MATERIALS SCIENCE↗

Impact of Molecular Design on Degradation Lifetimes of Degradable Imine-Based Semiconducting Polymers

Transient electronics are a rapidly emerging field due to their potential applications in the environment and human health. Recently, a few studies have incorporated acid-labile imine bonds into polymer semiconductors to impart transience; however, understanding of the structure–degradation property relationships of these polymers is limited. In this work, we systematically design and characterize a series of fully degradable diketopyrrolopyrrole-based polymers with engineered sidechains to investigate the impact of several molecular design parameters on the degradation lifetimes of these polymers. By monitoring degradation kinetics via ultraviolet–visible spectroscopy, we reveal that polymer degradation in solution is aggregation-dependent based on the branching point and M n , with accelerated degradation rates facilitated by decreasing aggregation. Additionally, increasing the hydrophilicity of the polymers promotes water diffusion and therefore acid hydrolysis of the imine bonds along the polymer backbone. The aggregation properties and degradation lifetimes of these polymers rely heavily on solvent, with polymers in chlorobenzene taking six times as long to degrade as in chloroform. We develop a new method for quantifying the degradation of polymers in the thin film and observe that similar factors and considerations (e.g., interchain order, crystallite size, and hydrophilicity) used for designing high-performance semiconductors impact the degradation of imine-based polymer semiconductors. We found that terpolymerization serves as an attractive approach for achieving degradable semiconductors with both good charge transport and tuned degradation properties. This study provides crucial principles for the molecular design of degradable semiconducting polymers, and we anticipate that these findings will expedite progress toward transient electronics with controlled lifetimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uncovering Backbone Conformation for Rigid DPP-Based Donor–Acceptor Conjugated Polymer Using Deuterium Labeling and Neutron Scattering

The conjugated polymer’s backbone conformation dictates the delocalization of electrons, ultimately affecting its optoelectronic properties. Most conjugated polymers can be viewed as semirigid rods with their backbone embedded among long alkyl side chains. Thus, it is challenging to experimentally quantify the conformation of a conjugated backbone. Here, we performed contrast variation neutron scattering on rigid conjugated donor–acceptor (D–A) diketopyrrolopyrrole (DPP) polymers with selectively deuterated side chains to measure the conjugated backbone conformation. We first synthesized DPPbased polymers with deuterated side chains, confirmed by NMR and FTIR. Using contrast variation neutron scattering, we found that the DPP-based conjugated polymers are much more rigid than poly(3-alkylthiophenes), with persistence length (L p ) at 16–18 nm versus 2–3 nm. More importantly, in contrast to the relatively flexible poly(3-alkylthiophenes) whose backbone is more flexible than the whole polymer, we found that the backbone of DPP-based polymers has the same L p value compared to the whole polymer chain. This indicates that side chain interference on backbone conformation is not present for the semirigid polymer, which is further confirmed by coarse-grained molecular dynamics (CG-MD) simulations. Our work provides a novel protocol to probe polymer’s backbone conformation and paradigm-shifting understanding of the backbone conformation of semirigid conjugated polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust chain aggregation of low-entropy rigid ladder polymers in solution

Conjugated polymers have been widely investigated where ladder-type conjugated polymers receive more attention due to their rigid backbones and extraordinary properties. However, the understanding of how the rigid conformation of ladder polymers translates to material properties is still limited. Here, we systematically investigated the solution aggregation properties of a carbazole-derived conjugated ladder polymer (LP) and its analogous non-ladder control polymer (CP) via light scattering, neutron scattering, and UV-vis absorption spectroscopy characterization techniques, revealing a highly robust, temperature-insensitive aggregation behavior of the LP. The experimental findings were further validated by computational molecular dynamics simulations. Here we found that the peak positions and intensities of the UV spectra of the LP remained constant between 20 °C and 120 °C in chlorobenzene solution. The polymer also showed a stable hydrodynamic radius measured by dynamic light scattering from 20 °C to 70 °C in the chlorobenzene solution. Using small-angle neutron scattering, no Guinier region was reached in the measured q range down to 0.008 Å –1 , even at elevated temperature. In contrast, the non-ladder control polymer CP was fully soluble in the chlorobenzene solvent without the observation of any notable aggregates. The Brownian dynamics simulation showed that during polymer aggregation, the entropy change of the LP was significantly less negative than that of the non-ladder control polymer. These findings revealed the low entropy nature of rigid conjugated ladder polymers and the low entropy penalty for their aggregation, which is promising for highly robust intermolecular interactions at high temperatures. Such a unique thermodynamic feature of rigid ladder polymers can be leveraged in the design and application of next-generation electronic and optoelectronic devices that function under unconventional high temperature conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MOF-Polymer Hybrid Materials: From Simple Composites to Tailored Architectures

Metal–organic frameworks (MOFs) are inherently crystalline, brittle porous solids. Conversely, polymers are flexible, malleable, and processable solids that are used for a broad range of commonly used technologies. The stark differences between the nature of MOFs and polymers has motivated efforts to hybridize crystalline MOFs and flexible polymers to produce composites that retain the desired properties of these disparate materials. Importantly, studies have shown that MOFs can be used to influence polymer structure, and polymers can be used to modulate MOF growth and characteristics. In this Review, we highlight the development and recent advances in the synthesis of MOF-polymer mixed-matrix membranes (MMMs) and applications of these MMMs in gas and liquid separations and purifications, including aqueous applications such as dye removal, toxic heavy metal sequestration, and desalination. Other elegant ways of synthesizing MOF-polymer hybrid materials, such as grafting polymers to and from MOFs, polymerization of polymers within MOFs, using polymers to template MOFs, and the bottom-up synthesis of polyMOFs and polyMOPs are also discussed. Furthermore, this review highlights recent papers in the advancement of MOF-polymer hybrid materials, as well as seminal reports that significantly advanced the field.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Design of Functional Polymers for Silica Scale Inhibition

Silica polymerization, which involves the condensation reaction of silicic acid, is a fundamental process with wide-ranging implications in biological systems, material synthesis, and scale formation. The formation of a silica-based scale poses significant technological challenges to energy-efficient operations in various industrial processes, including heat exchangers and water treatment membranes. Despite the common strategy of applying functional polymers for inhibiting silica polymerization, the underlying mechanisms of inhibition remain elusive. In this study, we synthesized a series of nitrogen-containing polymers as silica inhibitors and elucidated the role of their molecular structures in stabilizing silicic acids. Polymers with both charged amine and uncharged amide groups in their backbones exhibit superior inhibition performance, retaining up to 430 ppm of reactive silica intact for 8 h under neutral pH conditions. In contrast, monomers of these amine/amide-containing polymers as well as polymers containing only amine or amide functionalities present insignificant inhibition. Molecular dynamics simulations reveal strong binding between the deprotonated silicic acid and a polymer when the amine groups in the polymer are protonated. Notably, an extended chain conformation of the polymer is crucial to prevent proximity between the interacting monomeric silica species, thereby facilitating effective silica inhibition. Furthermore, the hydrophobic nature of alkyl segments in polymer chains disrupts the hydration shell around the polymer, resulting in enhanced binding with ionized silicic acid precursors compared to monomers. Finally, our findings provide novel mechanistic insights into the stabilization of silicic acids with functional polymers, highlighting the molecular design principles of effective inhibitors for silica polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Solution State Conformation and Aggregate Structure of Conjugated Polymers via Small Angle X-ray Scattering

Donor-acceptor (D-A) conjugated polymers are high-performance organic electronic materials that exhibit complex aggregation behavior. Understanding the solution state conformation and aggregation of conjugated polymers is crucial for controlling morphology during thin-film deposition and the subsequent electronic performance. However, a precise multiscale structure of solution state aggregates is lacking. Here, we present an in-depth small-angle X-ray scattering (SAXS) analysis of the solution state structure of an isoindigo-bithiophene-based D-A polymer (PII-2T) in chlorobenzene and decane as our primary system. Modeling the system as a combination of hierarchical fibrillar aggregates mixed with dispersed polymers, we extract information about conformation and multiscale aggregation and also clarify the physical origin of features often observed but unaddressed or misinterpreted in small-angle scattering patterns of conjugated polymers. The persistence length of the D-A polymer extracted from SAXS agrees well with a theoretical model based on the dihedral potentials. Additionally, we show that the broad high q structure factor peak seen in scattering profiles can be attributed to lamellar stacking occurring within the fibril aggregates and that the low q aggregate scattering is strongly influenced by the polymer molecular weight. Overall, the SAXS profiles of D-A polymers in general exhibit a sensitive dependence on the co-existence of fibrillar aggregate and dispersed polymer chain populations. We corroborate our findings from SAXS with electron microscopy of freeze-dried samples for direct imaging of fibrillar aggregates. Finally, we demonstrate the generality of our approach by fitting the scattering profiles of a variety of D-A polymers based on thieno-isoindigo (PTII-2T), diketopyrrolopyrrole (DPP2T-TT, DPP-BTZ, PDPP2FT-C- 16 ), naphthalenediimide (P(NDI2OD-T2)), and a conjugated block copolymer P3HT-b-DPPT-T. The results presented here establish a picture of the D-A polymer solution state structure and provide a general method of interpreting and analyzing their scattering profiles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of Rigidity–Hydration Coupling on Size-Dependent Diffusion in Hydrated Polymer Membranes

Selective ion transport in polymer membranes depends critically on how penetrant motion couples to polymer dynamics and hydration. Yet, the mechanistic interplay between polymer rigidity, water content, and penetrant size remains poorly understood, especially in the regime where the penetrant diameter, polymer Kuhn length, and correlation length are comparable. Here, we employ coarse-grained molecular dynamics simulations to systematically investigate penetrant diffusion in hydrated polymer networks across a broad range of water volume fractions, chain rigidities, and penetrant sizes. The results reveal a transition from a decoupled regime, where small penetrants diffuse nearly independently of polymer relaxation, to a coupled regime in which large penetrants require cooperative polymer motion for transport. Increasing polymer rigidity amplifies the sensitivity of diffusivity to hydration, particularly at low water content, leading to pronounced deviations from Stokes−Einstein scaling. Comparison with scaling theories and free-volume models shows that classical nanoparticle-based frameworks fail to capture this intermediate regime. To address this gap, we extend the Yasuda model to incorporate polymer rigidity through a single parameter that quantifies the dynamic contribution of chain stiffness to free-volume fluctuations. The resulting model collapses diffusivity data across all sizes, water contents, and rigidities, providing a unified description of penetrant transport in hydrated polymer matrices. Furthermore, these findings establish polymer rigidity as a key, tunable determinant of diffusion and offer a framework for interpreting size-dependent transport in ion-selective membranes.

diffusion↗

Ion Transport in Batteries with Polymer Electrolytes

We discuss polymer electrolytes for use in rechargeable lithium batteries. Polymer electrolytes have the potential to enable batteries with lithium metal anodes. These batteries have significantly higher theoretical energy densities than current lithium-ion batteries. We consider binary mixtures of polymers and salts. We also cover more complex systems such as polymer electrolytes swollen with a solvent (gel polymer electrolytes) and microphase separated polymer electrolytes. By covalently attaching the anions to the chains in a polymer solid, one obtains a single-ion conductor. We mainly focus on experiments wherein the polymer electrolyte is placed between two lithium metal electrodes. These experiments enable the determination of three transport parameters, ionic conductivity, salt diffusion coefficient, and transference number, and the thermodynamic factor. The properties of dry polymer electrolytes are contrasted with those of gel polymer electrolytes. The gel systems exhibit higher conductivity while the dry systems exhibit superior mechanical properties. We discuss interfacial impedance when lithium metal is contacted with polymer electrolytes and the importance of coulombic efficiency.

Yu, Xiaopeng↗

Machine learning inversion from small-angle scattering for charged polymers

We develop Monte Carlo simulations for uniformly charged polymers and a machine learning algorithm to interpret the intra-polymer structure factor of the charged polymer system, which can be obtained from small-angle scattering experiments. The polymer is modeled as a chain of fixed-length bonds, where the connected bonds are subject to bending energy, and there is also a screened Coulomb potential for charge interaction between all joints. The bending energy is determined by the intrinsic bending stiffness, and the charge interaction depends on the interaction strength and screening length. All three contribute to the stiffness of the polymer chain and lead to longer and larger polymer conformations. The screening length also introduces a second length scale for the polymer besides the bending persistence length. To obtain the inverse mapping from the structure factor to these polymer conformation and energy-related parameters, we generate a large data set of structure factors by running simulations for a wide range of polymer energy parameters. We use principal component analysis to investigate the intra-polymer structure factors and determine the feasibility of the inversion using the nearest neighbor distance. We employ Gaussian process regression to achieve the inverse mapping and extract the characteristic parameters of polymers from the structure factor with low relative error.

36 MATERIALS SCIENCE↗

History Matching and Prediction of a Polymer Flood Pilot in Heavy Oil Reservoir on Alaska North Slope

The first-ever polymer flood pilot to enhance heavy oil recovery on Alaska North Slope is ongoing. After more than 3 years of polymer injection, significant benefit has been observed from the decrease in water cut from 65% to less than 15% in the project producers. The primary objective of this study is to develop a robust history-matched reservoir simulation model capable of predicting future polymer flood performance. In this work, the reservoir simulation model has been developed based on the geological model and available reservoir and fluid data. In particular, four high transmissibility strips were introduced to connect the injector-producer well pairs, simulating short-circuiting flow behavior that can be explained by viscous fingering and reproducing the water cut history. The strip transmissibilities were manually tuned to improve the history matching results during the waterflooding and polymer flooding periods, respectively. It has been found that higher strip transmissibilities match the sharp water cut increase very well in the waterflooding period. Then the strip transmissibilities need to be reduced with time to match the significant water cut reduction. The viscous fingering effect in the reservoir during waterflooding and the restoration of injection conformance during polymer flooding have been effectively represented. Based on the validated simulation model, numerical simulation tests have been conducted to investigate the oil recovery performance under different development strategies, with consideration for sensitivity to polymer parameter uncertainties. The oil recovery factor with polymer flooding can reach about 39% in 30 years, twice as much as forecasted with continued waterflooding. Besides, the updated reservoir model has been successfully employed to forecast polymer utilization, a valuable parameter to evaluate the pilot test’s economic efficiency. All the investigated development strategies indicate polymer utilization lower than 3.5 lbs/bbl in 30 years, which is less than that of the same polymer used in a polymer pilot in Argentina.

Wang, Xindan↗

Origin of Mechanical Enhancement in Polymer Nanoparticle (NP) Composites with Ultrahigh NP Loading

Polymer nanoparticle composites (PNCs) with ultrahigh loading of nanoparticles (NPs) (>50%) have been shown to exhibit markedly improved strength, stiffness, and toughness simultaneously compared to the neat systems of their components. Recent experimental studies on the effect of polymer fill fraction in these highly loaded PNCs reveal that even at low polymer fill fractions, hardness and modulus increase significantly. In this work, we aim to understand the origin of these performance enhancements by examining the dynamics of both polymer and NPs under tensile deformation. We perform molecular dynamics simulations of coarse-grained, glassy polymer in random-close-packed NP packings with a varying polymer fill fraction. We characterize the mechanical properties of the PNC systems, compare the NP rearrangement behavior, and study the polymer segmental and chain-level dynamics during deformation below the polymer glass transition. Finally, our simulation results confirm the experimentally observed increase in modulus at low polymer fill fractions, and we provide evidence that the source of mechanical enhancement is the polymer bridging effect.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An unprecedented quinoid–donor–acceptor strategy to boost the carrier mobilities of semiconducting polymers for organic field-effect transistors

Quinoidal–aromatic conjugated polymers hold great application potential in organic field-effect transistors (OFETs). However, the development of high mobility quinoidal–aromatic conjugated polymers still lags behind the more popular donor–acceptor (D–A) conjugated polymers, mainly owing to the lack of a rational design strategy and efficient building block. Herein, a novel quinoid–donor–acceptor (Q–D–A) strategy is demonstrated to modulate the energy-level and boost the charge carrier transport mobility of conjugated polymers as opposed to the D–A system. On the basis of this strategy, a quinoidal–aromatic conjugated polymer, namely PAQM-BT, is designed and synthesized. With the combined use of quinoid, donor and acceptor units in the backbone, the resulting Q–D–A polymer PAQM-BT displays the narrowest bandgap with the deepest-lying lowest unoccupied molecular orbital (LUMO) energy level, highest backbone coplanarity, enhanced thin-film crystallinity and smallest effective hole mass ($m^*_h$) in comparison with the corresponding D–A polymer PT3B1 and quinoid–donor (Q–D) polymer PAQM-3T. Benefitting from the more effective intra- and inter-chain charge transport, as corroborated by experiment and theoretical calculations, OFET devices based on PAQM-BT exhibit a highly boosted hole mobility of up to 5.10 cm 2 V -1 s -1 , which is one and four orders of magnitude higher than that of PAQM-3T and PT3B1, respectively, and is among the highest for quinoidal–aromatic conjugated polymers. Finally, the potent Q–D–A strategy not only allows the energy level to be modulated but also leads to effective charge carrier transport, opening up possibilities to the development of high mobility quinoidal–aromatic conjugated polymers based on a variety of quinoids, donors, and acceptors.

36 MATERIALS SCIENCE↗

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↗