Model Polymer Research Articles

Effects of spherical fillers reinforcement on the efficacy of thermal conductivity in epoxy and polyester matrices: Experimental validation and prediction using finite element method

AbstractThe creation of a theoretical heat conduction model for polymers embedded with spherical inclusions is described in this study. It also contains the experimental confirmation of the suggested correlation for utilizing the model to estimate the effective thermal conductivity (K) of such composites. According to ASTM‐E‐1530, composites are made with varying amounts of aluminium oxide and pine wood dust reinforced in polyester resin. The effective thermal conductivities (Keff) of the composites are then determined using the Unitherm TM model 2022. Ansys 19.R2 software is used to evaluate the effective thermal conductivity of these composites with a uniform filler distribution, while Digimat‐FE software is used determine the thermal conductivity values of such particle filled polymer composites with a random filler distribution. After comparison and validation with experimental data, these values are shown to be fairly good agreement with the theoretical values from the suggested correlation. The investigation is further expanded to determine the thermal conductivities for epoxy composites using wood apple shell dust and coir dust particle. Also epoxy and polyester composites reinforced with SiO2 and TiO2 have been investigated in the similar manner. The main thrust of this report to validate the numerical results of composites by varying numerous polymers. The thermal conductivity all the composites grow monotonically with increase in filler content. The thermal conductivity of silicon dioxide, titanium oxide, and aluminium oxide filled epoxy composites is measured as 1.5, 7, and 35 W/m‐K respectively.Highlights In this study spherical fillers are successfully used as a potential filler material in polyester composites The thermal conductivity predicted by proposed mathematical model of polyester is validated with measured value and found better agreement. The Ansys 19.R2 and digimat software are used to predict the thermal conductivity values of these composites. The mathematical model is further used to predict thermal conductivity of epoxy composites to check the accuracy of the model.

Discovery and computational modeling of adsorbent polymers that effectively immobilize SARS-CoV-2, with potential practical applications

Discovery and computational modeling of adsorbent polymers that effectively immobilize SARS-CoV-2, with potential practical applications

The importance of surface composition and wettability on the dissolution performance of high drug loading amorphous dispersion formulations

One of the limitations with an amorphous solid dispersion (ASD) formulation strategy is low drug loading. Hydrophobic drugs have poor wettability and require a substantial amount of polymer to stabilize the amorphous drug and facilitate release. Using grazoprevir and hypromellose acetate succinate as model drug and polymer respectively, the interplay between particle surface composition, particle wettability, and release performance was investigated. A hierarchical particle approach was used where the surfaces of high drug loading ASDs generated by either solvent evaporation or co-precipitation were further modified with a secondary excipient (i.e., polymer or wetting agent). The surface-modified particles were characterized for drug release, wettability, morphology, and surface composition using two-stage dissolution studies, contact angle measurements, scanning electron microscopy, and X-ray photoelectron spectroscopy, respectively. Despite surface modification with hydrophilic polymers, hierarchical cPAD particles did not consistently exhibit good release performance. Contact angle measurements showed that the secondary excipient had a profound impact on particle wettability. Particles with good wettability showed improved drug release relative to particles that did not wet well, even with similar drug loadings. These observations underscore the intricate interplay between particle wettability and performance in amorphous dispersion formulations and illustrate a promising hierarchical particle approach to formulate high drug loading amorphous dispersions with improved dissolution performance.

Flow dichroism of DNA can be quantitatively predicted via coarse-grained molecular simulations

We demonstrate the use of multiscale polymer modeling to quantitatively predict DNA linear dichroism (LD) in shear flow. LD is the difference in absorption of light polarized along two perpendicular axes and has long been applied to study biopolymer structure and drug-biopolymer interactions. As LD is orientation dependent, the sample must be aligned in order to measure a signal. Shear flow via a Couette cell can generate the required orientation; however, it is challenging to separate the LD due to changes in polymer conformation from specific interactions, e.g., drug-biopolymer. In this study, we have applied a combination of Brownian dynamics and equilibrium Monte Carlo simulations to accurately predict polymer alignment, and hence flow LD, at modest computational cost. As the optical and conformational contributions to the LD can be explicitly separated, our findings allow for enhanced quantitative interpretation of LD spectra through the use of an in silico model to capture conformational changes. Our model requires no fitting and only five input parameters: the DNA contour length, persistence length, optical factor, solvent quality, and relaxation time, all of which have been well characterized in prior literature. The method is sufficiently general to apply to a wide range of biopolymers beyond DNA, and our findings could help guide the search for new pharmaceutical drug targets via flow LD.

Effect of cationic surfactants on titration behavior of isotactic and atactic poly(methacrylic acid)

By forming strong complexes with oppositely charged polyelectrolytes, cationic surfactants significantly affect their solution properties. We investigated the effect of bound surfactant on the titration behavior of two isomer forms of poly(methacrylic acid), PMA, atactic and isotactic PMA, aPMA and iPMA, respectively, which are known for the cooperative change in chain conformation in water. The bound surfactant micelles increase the initial degree of ionization, α, of carboxyl groups on PMA, shift the conformational transition to higher α and make it narrower, and exclude the complexed chains from the solution. The titration curves were analyzed in the framework of the Henderson-Hasselbalch theory and the Gibbs free energy change of the conformational transition was calculated. The results were discussed in the context of a complex influence of surfactant on the PMA chain conformation in solution. It is proposed that the PMA-surfactant interaction changes from a so-called hydrophobic mode, which is responsible for the solubilization of the unionized and water-insoluble iPMA at low α, to a predominantly electrostatic one at high α, which leads to the precipitation of both aPMA and iPMA from solution. Constant pH simulations using simple coarse-grained models for the PMA polymers and individual surfactants were performed to rationalize the titration behavior of PMAs in the absence and presence of surfactant. By inducing an attractive interaction between PMA monomers, an excellent agreement between the experimental and numerical titration curves was obtained. Such agreement becomes poorer upon the addition of surfactant; however, the main features of the PMA titration curves are preserved, which supports the role of hydrophobic interactions in PMA-surfactant association at low pH values and that of electrostatics at higher pH.

Synthesis of condensed tannin model compounds regioselectively labeled with a 13C-stable isotope

Condensed tannins exhibit diverse bioactivities that render them promising for applications in the food and medical fields. For the analysis and monitoring of condensed tannins, 13C-labeled derivatives would provide a useful tool. In this study, condensed tannin polymers regioselectively labeled with a stable isotope were synthesized using 13C-labeled acetic acid or 13C-labeled dimethylformamide as the starting material. The resulting synthetic polymers were labeled with 13C at the C-4 or C-2 positions. A GPC analysis revealed that all model polymers comprised mainly tetramer to hexamer structures. According to the 13C-NMR data of the synthetic tannin models and natural condensed tannin obtained from sugi bark, the chemical structure of both compounds was very similar. Furthermore, compared with the natural condensed tannin and unlabeled synthetic polymer, the labeled compound showed more intense C-4 and C-2 13C signals, indicating that the 13C labeling proceeded regioselectively. These compounds are useful for analyzing the chemical reactions of condensed tannins and monitoring structural transformation processes in vivo.

Langevin Dynamics Study on the Driven Translocation of Polymer Chains with a Hairpin Structure.

The hairpin structure is a common and fundamental secondary structure in macromolecules. In this work, the process of the translocation of a model polymer chain with a hairpin structure is studied using Langevin dynamics simulations. The simulation results show that the dynamics of hairpin polymer translocation through a nanopore are influenced by the hairpin structure. Hairpin polymers can be classified into three categories, namely, linear-like, unsteady hairpin, and steady hairpin, according to the interaction with the stem structure. The translocation behavior of linear-like polymers is similar to that of a linear polymer chain. The time taken for the translocation of unsteady hairpin polymers is longer than that for a linear chain because it takes a long time to unfold the hairpin structure, and this time increases with stem interaction and decreases with the driving force. The translocation of steady hairpin polymers is distinct, especially under a weak driving force; the difficulty of unfolding the hairpin structure leads to a low translocation probability and a short translocation time. The translocation behavior of hairpin polymers can be explained by the theory of the free-energy landscape.

Effect of active loop extrusion on the two-contact correlations in the interphase chromosome.

The population-averaged contact maps generated by the chromosome conformation capture technique provide important information about the average frequency of contact between pairs of chromatin loci as a function of the genetic distance between them. However, these datasets do not tell us anything about the joint statistics of simultaneous contacts between genomic loci in individual cells. This kind of statistical information can be extracted using the single-cell Hi-C method, which is capable of detecting a large fraction of simultaneous contacts within a single cell, as well as through modern methods of fluorescent labeling and super-resolution imaging. Motivated by the prospect of the imminent availability of relevant experimental data, in this work, we theoretically model the joint statistics of pairs of contacts located along a line perpendicular to the main diagonal of the single-cell contact map. The analysis is performed within the framework of an ideal polymer model with quenched disorder of random loops, which, as previous studies have shown, allows us to take into account the influence of the loop extrusion process on the conformational properties of interphase chromatin.

Studies on the Termination Behavior of Styrenic Free‐Radicals

AbstractIn order to provide more evidence to understand the termination mechanism in styrene free‐radical polymerization, (1‐bromoethyl) benzene and polystyrene with bromide end group (PSt‐Br) synthesized by atom transfer radical polymerization (ATRP) were used as the model compound and model polymer to study the termination behavior of styrenic radical by atom transfer radical coupling (ATRC), and then the NMR chemical shifts of the head‐to‐head enchainment from coupling termination were obtained. SEC and different NMR measurement methods were used to analyze and characterize the products. It is confirmed that there is no bimolecular disproportionation termination between styrenic free radicals, but only coupling termination to form the head‐to‐head enchainment. The proton and carbon chemical shifts of the head‐to‐head enchainment from coupling termination for (1‐bromoethyl) benzene are 2.7–2.86 ppm and ~47.3 ppm. As for the polystyrene through ATRC from PSt‐Br, the corresponding chemical shifts are 2.61–3.29 ppm and ~46.4 ppm, respectively, they are almost the same as the data in our previous paper (~3.05 ppm, ~46.6 ppm) for polystyrene initiated by BPO, proving that the chain termination in free‐radical polymerization of styrene initiated by BPO occurs through primary termination between chain radical and primary radical rather than bimolecular termination between chain radicals.

Bayesian calibration and uncertainty quantification of a rate-dependent cohesive zone model for polymer interfaces

This study presents a rate-dependent cohesive zone model for the fracture of polymeric interfaces and performs a Bayesian calibration, an uncertainty quantification, and a sensitivity analysis for the model. The proposed cohesive zone model accounts for both reversible elastic and irreversible rate-dependent separation sliding deformation at the interface. The viscous dissipation due to the irreversible opening at the interface is modeled using elastic-viscoplastic kinematics that incorporates the effects of strain rate. Inverse calibration of parameters for such complex models through trial and error is challenging due to the large number of parameters of the model. Moreover, the calibrated parameter values are often non-unique and uncertain when the available experimental data is limited. To tackle this challenge, we employ a Bayesian calibration approach to identify parameters from experimental data, the resulting parameters significantly enhance the accuracy of the model. To quantify the uncertainty associated with the inverse parameter estimation, a modular Bayesian approach is employed to calibrate the unknown model parameters, accounting for the parameter uncertainty of the cohesive zone model. The advantages of the Bayesian calibration over a deterministic parameter fit are demonstrated. Further, to quantify the model uncertainties, such as incorrect assumptions or missing physics, a discrepancy function is introduced, which significantly improves the model’s prediction. Finally, the total uncertainty of the model is quantified in a predictive setting. A sensitivity analysis is performed to assess how changes in the input variables of the model affect the peak load, facilitating the identification of a concise set of highly influential parameters. The present approach can be used for calibration and uncertainty quantification for other complex computational mechanics models. It should also facilitate the designing of interface materials under uncertainty.

Density-Nematic Coupling in Isotropic Solution of DNA: Multiscale Model.

Monte Carlo simulations of isotropic solutions of double-stranded DNA (deoxyribonucleic acid) are performed using the well-established oxDNA model. By comparing the fluctuation amplitudes with theoretical predictions, the parameters of a generic macroscopic model of an isotropic linear polymer solution/melt are determined. A multiscale continuum field model is thus obtained, corresponding to the full specificity of the isotropic phase of double-stranded DNA in the usual B-form as perceived at the macroscopic level. Present research is particularly focused on the coupling between spatial concentration/density variations of the polymer and the emerging nematic orientation order of the chains. This rather unfamiliar, only recently described phenomenon, inherent to linear polymers, is outlined and interpreted. Quantitative predictions are provided for the degree of nematic order induced by concentration gradients in isotropic solutions of double-strandedDNA.

Evaluating impact damage on carbon fiber-reinforced polymer plates utilizing zero-group-velocity Lamb waves

This paper presents an effective method for evaluating the impact damage of composite plates using zero-group-velocity (ZGV) Lamb waves. A finite element (FE) model of the carbon fiber-reinforced polymer (CFRP) plate is established to analyze in detail the propagation characteristics of the S1-ZGV Lamb wave mode with a specified propagation direction. The study investigates the changes in the S1-ZGV mode with varying damage levels, characterized by a decrease in elastic moduli. Results indicate that as the damage level increases, the corresponding S1-ZGV frequency and amplitude decrease proportionally. The spectral amplitude (SA) at the initial S1-ZGV frequency exhibits a consistent and significant decrease with increasing damage levels, offering a reliable method for accurately assessing damage in CFRP plates. Additionally, the S1-ZGV mode of the CFRP plate is experimentally excited using the pitch-catch technique with air-coupled ultrasonic transducers to explore the variations in the S1-ZGV mode with different impact damages. Experimental findings show that the SA of the S1-ZGV mode at the initial S1-ZGV frequency decreases monotonically and sensitively with an increasing number of impacts. These experimental results correlate with the FE analysis, validating the effectiveness of accurately evaluating impact damage in CFRP plates based on the SA of S1-ZGV modes.

Molecular dynamics simulation of salt diffusion in constituting phosphazene-based polymer electrolyte

A growing demand to visualize polymer models in liquid poses a computational challenge in molecular dynamics (MD) simulation, as this requires emerging models under suitable force fields (FFs) to capture the underlying molecular behaviour accurately. In our present study, we have employed TIP3P potential on water and all atomistic optimized potentials for liquid simulations FFs to study the liquid electrolyte behavior of phosphazene-based polymer by considering its potential use in lithium-ion polymer batteries. We have explored the polymer's local structure, chain packing, wettability, and hydrophobic tendencies against the silicon surface using a combination of a pseudocontinuum model in MD simulation, and surface-sensitive sum frequency generation (SFG) vibrational spectroscopy. The finding yields invaluable insights into the molecular architecture of phosphazene. This approach identifies the importance of hydrophobic interactions with air and hydrophilic units with water molecules in understanding the behavior and properties of phosphazene-based polymers at interfaces, contributing to its advancements in materials science. The MD study uniquely captures traces of the polymer-ion linkage, which is observed to become more pronounced with the increase in polymer weight fraction. The theoretical observation of this linkage's influence on lithium-ion diffusion motion offers valuable insights into the fundamental physics governing the behavior of atoms and molecules within phosphazene-based polymer electrolytes in aqueous environments. Further these predictions are corroborated in the molecular-level depiction at the air-aqueous interface, as evidenced from the OH-oscillator strength variation measured by the SFG spectroscopy.The fundamental findings from this study open new avenues for utilizing MD simulation as a versatile methodology to gain profound insights into intermolecular interactions of polymer. It could be useful in the application of biomedical and energy-related research, such as polymer lithium-ion batteries, fuel cells, and organic solar cells.

Scaling Limit of Multi-Type Invariant Measures via the Directed Landscape

Abstract This paper studies the large scale limits of multi-type invariant distributions and Busemann functions of planar stochastic growth models in the Kardar–Parisi–Zhang (KPZ) class. We identify a set of sufficient hypotheses for convergence of multi-type invariant measures of last-passage percolation (LPP) models to the stationary horizon (SH), which is the unique multi-type stationary measure of the KPZ fixed point. Our limit theorem utilizes conditions that are expected to hold broadly in the KPZ class, including convergence of the scaled last-passage process to the directed landscape. We verify these conditions for the six exactly solvable models whose scaled bulk versions converge to the directed landscape, as shown by Dauvergne and Virág. We also present a second, more general, convergence theorem with future applications to polymer models and particle systems. Our paper is the first to show convergence to the SH without relying on information about the structure of the multi-type invariant measures of the prelimit models. These results are consistent with the conjecture that the SH is the universal scaling limit of multi-type invariant measures in the KPZ class.

A 3D finite strain constitutive model for shape memory polymers combined viscoelasticity and storage strain

A 3D finite strain constitutive model combined viscoelasticity and storage strain for shape memory polymers (SMPs) is proposed. SMPs are phenomenally regarded as a homogeneous material of the viscoelastic glassy phase and hyperelastic rubbery phase in this model. Based on energy decomposition, the constitutive equation is derived using Clausius inequality and unified Helmholtz free energy. Then, an analytical expression for storage strain is presented, significantly simplifying the prediction of shape memory recovery process. The model is implemented in MATLAB and the commercial finite element software package ABAQUS using the UMAT subroutine. Our additional DMA tests and experimental data from the literature for various SMPs with different shape structures are used to verify the proposed model. All simulation results demonstrate the effectiveness of the proposed model in predicting the shape memory effect and complex thermomechanical behaviors of various SMPs.

Nanosecond chain dynamics of single-stranded nucleic acids

The conformational dynamics of single-stranded nucleic acids are fundamental for nucleic acid folding and function. However, their elementary chain dynamics have been difficult to resolve experimentally. Here we employ a combination of single-molecule Förster resonance energy transfer, nanosecond fluorescence correlation spectroscopy, and nanophotonic enhancement to determine the conformational ensembles and rapid chain dynamics of short single-stranded nucleic acids in solution. To interpret the experimental results in terms of end-to-end distance dynamics, we utilize the hierarchical chain growth approach, simple polymer models, and refinement with Bayesian inference to generate structural ensembles that closely align with the experimental data. The resulting chain reconfiguration times are exceedingly rapid, in the 10-ns range. Solvent viscosity-dependent measurements indicate that these dynamics of single-stranded nucleic acids exhibit negligible internal friction and are thus dominated by solvent friction. Our results provide a detailed view of the conformational distributions and rapid dynamics of single-stranded nucleic acids.

High Antifouling Performance of Weakly Hydrophilic Polymer Brushes: A Molecular Dynamics Study.

The antifouling performance of polymer brushes usually improves with increasing hydrophilicity of the grafted polymer. However, in some cases, less hydrophilic polymers show comparable or better antifouling performance than do more hydrophilic polymers. We investigate the mechanism of this anomalous behavior using molecular dynamics (MD) simulations of coarse-grained (CG) models of weakly and strongly hydrophilic polymers. The antifouling performance is evaluated from the potential of mean force of a model protein. The strongly hydrophilic polymer exhibits a better antifouling performance than the weakly hydrophilic polymer when the substrate of the polymer brush is repulsive. However, when the substrate is sufficiently attractive, the weakly hydrophilic polymer brush becomes more effective than the strongly hydrophilic brush in a certain range of grafting density. This is because the weakly hydrophilic polymer chains form a tightly packed layer that prevents the adsorbate molecule from contacting the substrate. We also perform all-atom (AA) MD simulations for several standard polymers to examine the correspondence with the CG polymer models. The weakly hydrophilic CG polymer is found to be similar to poly[N-(2-hydroxypropyl)methacrylamide] and poly(2-hydroxyethyl methacrylate), both of which have a hydroxyl group in a monomer unit. The strongly hydrophilic CG polymer resembles zwitterionic poly(carboxybetaine methacrylate). A discussion referring to the adsorption free energies of proteins on surfaces calculated in previous AA MD studies suggests that the higher antifouling performance of less hydrophilic polymer brushes can be realized for various combinations of protein and surface.

Stress path-based compressive strength model of FRP-confined recycled aggregate concrete

The compressive strength model of fibre-reinforced polymer (FRP) confined recycled aggregate concrete (RAC) is important in practical engineering designs. The existing research has showed that the compressive strength of FRP-confined RAC can be predicted by the models for FRP confined natural aggregate concrete (NAC). However the accuracy of existing compressive strength models for FRP-confined NAC vary greatly because of the unclear understanding of the confinement mechanisms. Previous research has shown that the axial stress of confined concrete tends to be path-dependent. In this study, a confining stress path-based compressive strength model of FRP-confined RAC is proposed based on theoretical analyses of the confining stress path of FRP-confined RAC. In the proposed model, an effect index is determined to express the influence of confining stress path on the compressive strength. The relationship between the effect index and confinement ratio and that between lateral stress dominant index and confinement ratio are obtained. The proposed model is verified by comparison with previous experimental test results and those predicted by existing representative models. It is found that the compressive strength of FRP-confined RAC is path-dependent for small confinement ratios (less than 0.43) and path-independent for large confinement ratios (larger than 0.43).

Entanglement Kinetics in Polymer Melts Are Chemically Specific.

We investigate the universality of entanglement kinetics in polymer melts. We compare predictions of a recently developed constitutive equation for disentanglement to molecular dynamics simulations of both united-atom polyethylene and Kremer-Grest models for polymers in shear and extensional flow. We confirm that entanglements recover on the retraction time scale, rather than the reptation time scale. We find that the convective constraint release parameter β is independent of molecular weight, but that it increases with the ratio of Kuhn length bK to packing length p as β ∼ (bK/p)α, with an exponent α = 1.9, which may suggest that disentanglement rate correlates with an increase in the tube diameter. These results may help shed light on which polymers are more likely to undergo shear banding.

Modulation of Tannic Acid on the Cholesteric Structure of Cellulose Nanocrystals.

The chiral nematic phase structure, formed by the self-assembly of cellulose nanocrystals (CNCs) in an aqueous suspension and maintained in a solid film, shows great potential for optical applications. To achieve complex structures in optical devices, it is crucial to subject CNCs to specific shearing processes, such as spinning and printing. Understanding the structural and property changes of the CNC liquid crystal phase in these processes is of utmost importance. In this study, we investigated the effect of adding tannic acid (TA) on the rheological properties and cholesteric phase structures of CNCs/TA mixed suspensions. By calculating the surface site interaction points, we observed that TA can adsorb onto the surface of CNC rods in suspensions through hydrogen bonding. Through characterization techniques, such as polarized optical microscopy, rheology, and synchrotron SAXS, we examined the effects of TA addition on the microstructure and rheological properties of the CNC liquid crystal phase and clarified the change relating to the system composition. Under the same CNC concentration, the volume fraction of the anisotropic phase, the pitch, and the rod spacing of the cholesteric phase were not significantly affected by the addition of TA. However, the system viscosity was significantly reduced with the appropriate amount of TA (2 wt %), in a wide range of CNC concentrations (up to 15 wt % CNCs). The flow indexes (n) in Region I and Region III of steady-state shear curves of CNCs/TA systems (11-15 wt % CNCs) were compared. Moreover, we introduced the well-established theoretical models for liquid crystal polymers to tentatively interpret Region I of the CNCs/TA cholesteric phase and realized that increased numbers of smaller cholesteric-phase domains in the CNCs/TA system and interfacial modification by TA may contribute to the fluidity change. The feature of the domain texture of CNCs/TA systems is verified by polarized optical microscopy observations.