Journal of polymer science. Part B, Polymer physics

ABSTRACTA series of liquid crystalline copolyesters (LCPs) with different concentrations of a photocrosslinking moiety have been synthesized by random polycondensation with 4,4′‐bis(6‐hydroxyhexyloxy)biphenyl, 2‐phenylsuccinic acid, and 4‐(6‐hydroxyhexyloxy)cinnamic acid (6HCA). Multifunctional monodomain liquid crystal networks (LCNs) with considerable and tunable actuation behavior are obtained by postphotocrosslinking. The influence of the photocrosslinking moiety on the phase transition behavior of the LCP and actuation behavior of the LCN has been investigated. The results suggest that incorporating 6HCA suppresses the smectic phase of the LCP and decreases the nematic‐isotropic phase transition temperature. Moreover, the starting actuation temperature of the LCN decreases from 55 to 40 °C as the 6HCA reached 50%. In addition, the actuation force and storage modulus of the LCN actuators are enhanced by incorporating a high concentration of 6HCA. A 1.64 MPa contractile force can be achieved, and it can lift burdens 1300 times heavier than its weight when 50% 6HCA is incorporated into the LCP. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 904–911

ABSTRACT The bioactive additive toolbox to functionalize supramolecular elastomeric materials expands rapidly. Here we have set an explorative step toward screening of complex combinatorial functionalization with antifouling and three peptide‐containing additives in a bisurea‐based supramolecular system. Thorough investigation of surface properties of thin films with contact angle measurements, X‐ray photoelectron spectroscopy and atomic force microscopy, was correlated to cell‐adhesion of endothelial and smooth muscle cells to apprehend their respective predictive values for functional biomaterial development. Peptides were presented at the surface alone, and in combinatorial functionalization with the oligo(ethylene glycol)‐based non‐cell adhesive additive. The bisurea‐RGD additive was cell‐adhesive in all conditions, whereas the endothelial cell‐specific bisurea‐REDV showed limited bioactive properties in all chemical nano‐environments. Also, aspecific functionality was observed for a bisurea‐SDF1α peptide. These results emphasize that special care should be taken in changing the chemical nano‐environment with peptide functionalization. © 2019 The Authors. Journal of Polymer Science Part B: Polymer Physics published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1725–1735

ABSTRACTThermomechanical properties of polymers highly depend on their glass transition temperature (T g). Differential scanning calorimetry (DSC) is commonly used to measure T g of polymers. However, many conjugated polymers (CPs), especially donor–acceptor CPs (D–A CPs), do not show a clear glass transition when measured by conventional DSC using simple heat and cool scan. In this work, we discuss the origin of the difficulty for measuring T g in such type of polymers. The changes in specific heat capacity (Δc p) at T g were accurately probed for a series of CPs by DSC. The results showed a significant decrease in Δc p from flexible polymer (0.28 J g−1 K−1 for polystyrene) to rigid CPs (10−3 J g−1 K−1 for a naphthalene diimide‐based D–A CP). When a conjugation breaker unit (flexible unit) is added to the D–A CPs, we observed restoration of the Δc p at T g by a factor of 10, confirming that backbone rigidity reduces the Δc p. Additionally, an increase in the crystalline fraction of the CPs further reduces Δc p. We conclude that the difficulties of determining T g for CPs using DSC are mainly due to rigid backbone and semicrystalline nature. We also demonstrate that physical aging can be used on DSC to help locate and confirm the glass transition for D‐A CPs with weak transition signals. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1635–1644

We develop thin films of blends of polystyrene (PS) with the thermoresponsive polymer poly(N-isopropylacrylamide) (PNIPAM) (PS/PNIPAM) and its diblock copolymer polystyrene-b-poly(N-isopropylacrylamide) (PS/PS-b-PNIPAM) in different blend ratios and we study their surface morphology and thermoresponsive wetting behaviour. The blends of PS/PNIPAM and PS/PS-b-PNIPAM are spin-casted on flat silicon surfaces with various drying conditions. The surface morphology of the films depends on the blend ratio and the drying conditions. The PS/PS-b-PNIPAM films do not show an increase of their water contact angles with temperature, as it is expected by the presence of the PNIPAM block. All PS/PNIPAM films show an increase in the water contact angle above the lower critical solution temperature of PNIPAM, which depends on the ratio of PNIPAM in the blend and is insensitive to the drying conditions of the films. The difference between the wetting behaviour of PS/PS-b-PNIPAM and PS/PNIPAM films is due to the arrangement of the PNIPAM chains in the film.

The properties of thin supported polymer films can be dramatically impacted by the substrate upon which it resides. A simple way to alter the properties of the substrate (chemistry, rigidity, dynamics) is by coating it with an immiscible polymer. Here we describe how ultrathin (ca. 2 nm) hydrophilic polymer layers of poly(acrylic acid), PAA, and poly(styrenesulfonate), PSS, impact the aging behavior and the residual stress in thin films of poly(butylnorbornene-ran-hydroxyhexafluoroisopropyl norbornene), BuNB-r-HFANB. The aging rate decreases as the film thickness (h) is decreased, but the extent of this change depends on the adjacent layer. Even for the thickest films (h>500 nm), there is a decrease in the aging rate at 100 °C when BuNB-r-HFANB is in contact with PSS. In an effort to understand the origins of these differences in the aging behavior, the elastic modulus and residual stress (σR) in the films were determined by wrinkling as a function of aging time. The change in the elastic modulus during aging does not appear to be directly correlated with the densification or expansion of the films, but the aging rates appear to roughly scale as hσR 1/3. These results illustrate that the physical aging of thin polymer films can be altered by adjacent polymers.

ABSTRACTThe optimization of polymer barrier properties is currently of crucial importance for a wide range of applications from packaging to building or even energy applications. To meet the requirements of these applications, polymer matrices are often combined with impermeable (nano) fillers. Different nanofiller natures, shapes, and contents have been experimentally used and a large range of barrier materials has been obtained. In the meantime, several numerical approaches have been developed to model gas diffusion properties of nanocomposite materials. However, these approaches often considered bidimensional systems. The aim of this work is to develop 3D Finite Element Model which would be used to predict gas barrier properties of nanocomposites for disk‐shaped nanofillers. The model thus obtained is valid in a wide range of fillers volume fraction values as well as aspect ratios, which makes it possible to go from diluted regimes to semidiluted or even concentrated ones. Furthermore, an analytical equation which describes gas diffusion through nanocomposites films has been built and validated with our finite element modeling model. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 51–61

ABSTRACTThe ever‐growing catalog of monomers being incorporated into block polymers affords exceptional control over phase behavior and nanoscale structure. The segregation strength, χN, is the fundamental link between the molecular‐level detail and the thermodynamics. However, predicting phase behavior mandates at least one experimental measurement of χN for each pair of blocks. This typically requires access to the disordered state. We describe a method for estimating χN from small‐angle X‐ray scattering measurements of the interfacial width between lamellar microdomains, tx, in the microphase‐separated melt. The segregation strength is determined by comparing tx to self‐consistent field theory calculations of the intrinsic interfacial width, ti, as a function of the mean‐field χN. The method is validated using a series of independent experimental measurements of tx and χN, measured via the order–disorder transition temperature, TODT. The average absolute relative difference between χN calculated from tx and the value calculated from TODT is a modest 11%. Corrections for nonplanarity of the interfaces are investigated but do not improve the agreement between the experiments and theory. Published 2019. This article is a U.S. Government work and is in the public domain in the USA. J. Polym. Sci., Part B: Polym. Phys. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 932–940

ABSTRACTThe anisotropic properties of polyethylene terephthalate film resulting from its manufacturing process are quantitatively investigated in terms of its optical, mechanical, and photoelastic aspects. Transmission ellipsometers and a Jones‐matrix‐based analysis software together with a 4 × 4 Berreman‐matrix‐based analysis software are adopted to determine the wavelength‐dependent in‐plane birefringence, the principal refractive indices, and the orientation of the optical axis. Mechanical anisotropy is characterized in terms of the elastic compliance tensor components using the measured azimuthal angle‐dependent Young's modulus and Poisson's ratio. From the measured variation of the wavelength‐dependent in‐plane birefringence as a function of tensile stress, the dispersive photoelastic coefficients are obtained for a few sample azimuthal angles, and the components of the photoelastic tensor are determined. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 152–160

ABSTRACTWe demonstrate the directional alignment of perpendicular‐lamellae domains in fluorinated three‐armed star block polymer (BP) thin films using solvent vapor annealing with shear stress. The control of orientation and alignment was accomplished without any substrate surface modification. Additionally, three‐armed star poly(methyl methacrylate‐block‐styrene) [PMMA‐PS] and poly(octafluoropentyl methacrylate‐block‐styrene) were compared to their linear analogues to examine the impact of fluorine content and star architecture on self‐assembled BP feature sizes and interdomain density profiles. X‐ray reflectometry results indicated that the star BP molecular architecture increased the effective polymer segregation strength and could possibly facilitate reduced polymer domain spacings, which are useful in next‐generation nanolithographic applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1663–1672

ABSTRACTPrinting of high‐resolution three‐dimensional nanostructures utilizing two‐photon polymerization has gained significant attention recently. In particular, isopropyl thioxanthone (ITX) has been implemented as a photoinitiator due to its capability of initiating and depleting polymerization on demand, but new photoinitiating materials are still needed in order to reduce the power requirements for the high‐throughput creation of 3D structures. To address this point, a suite of new thioxanthone‐based photoinitiators were synthesized and characterized. Then two‐photon polymerization was performed using the most promising photoinitiating molecule. Importantly, one of the initiators, 2,7‐bis[(4‐(dimethylamino)phenyl ethynyl)‐9H‐thioxanthen‐9‐one] (BDAPT), showed a fivefold improvement in the writing threshold over the commonly used ITX molecule. To elucidate the fundamental mechanism, the excitation and inhibition behavior of the BDAPT molecule were evaluated using density functional theory (DFT) calculations, low‐temperature phosphorescence spectroscopy, ultra‐fast transient absorption spectroscopy, and the two‐photon Z‐scan spectroscopic technique. The improved polymerization threshold of this new photoinitiator presents a clear pathway for the modification of photoinitiators in 3D nanoprinting. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1462–1475

ABSTRACT The mean‐field theory of Flory–Stockmayer for randomly branched polymers in the regime of strong chain overlap is extended to a calculation of M Z via the recursive method of Miller and Macosko. The formalism includes condensation polymers, copolymers, chain stoppers, bifunctional diluents to control the chain length between branch points, multiple branching agents, and arbitrary stoichiometries. M Z closely approximates the largest branched polymer in the system and is therefore a key parameter describing static scaling behavior near the gel point. Nonuniversal static scaling of M Z is illustrated with examples from the literature. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57 , 1415–1422

The beauty of polymer physics lies in its practicality and its pervasiveness. It can explain why some batteries work better than others, why thin films have different properties than their bulk counterparts, and how conductivity can be improved by proper stacking of polymer chains. As we approach the end of the first century of modern polymer science, we continue to witness remarkable progress and important developments in the field. With this in mind, we present a special issue of the Journal of Polymer Science, Part B: Polymer Physics highlighting recent advances in the physics of polymer systems. The issue consists of a collection of papers from some of the best minds in polymer physics – our Editorial Advisory Board. The Review by Loo and Balsara provides a comprehensive overview of literature data on the thermodynamic properties of salt-containing polymer blends and copolymers. Adding salt to a polyelectrolyte solution has significant effects on diffusion behaviors. Muthukumar shows that coupled dynamics of polymer segments, counterions, and coions from added salt lead to an intermediate diffusive mode in between the classical ordinary and extraordinary diffusive modes in polyelectrolyte solutions. Two-dimensional (2D) conducting polymers have been widely applied in flexible electronics, ion-exchange membranes, biotechnology and energy devices. In a forward-looking Perspective, Park and co-workers highlight most recent synthetic advances in 2D polymers with large lateral sizes and outline potential challenges and future avenues related to their commercialization. With progress in computational modeling techniques comes better methods to design and manufacture polymeric materials. As DNA and RNA are increasingly used in bio- and nano-technology applications, it is crucial to understand how polymer-solvent interactions impact their melting temperature when they are conjugated with polymers. Prhashanna and Jayaraman investigate these systems using coarse-grained molecular simulations, comparing melting behavior of charged/stiff oligonucleic acids with neutral/flexible ones. Dutcher and co-workers use principal component analysis and machine learning concepts to distinguish polyethylene pipe formulations by examining the contribution of individual IR bands, which will ultimately allow for better optimization of pipe performance and durability. Predicting the behavior and experimental features of complex polymer systems requires a deep understanding of the underlying theory. Polymer blends are well-studied but are known to exhibit anomalies in their dynamics at different length and time scales. Colmenero presents a memory function formalism to explain this behavior, which considers the effect of the collective dynamics on the chain dynamics of a tagged polymer chain. With an appropriate contact mechanics model, atomic force microscopy (AFM) enables quantitative evaluation of surface interactions and elasticity. Nishi and co-workers present new easy-to-use methods to derive the elastic modulus of a soft and adhesive material from an AFM force curve. Experimental insight into crystallization and phase behavior, the glass transition, and polymer chain dynamics provides new opportunities to precisely tune material properties. Choudhary and Crosby use evaporative self-assembly based on stop-and-go flow-coating to form mesoscale nanoribbons. Different control parameters influence the final size, geometry, and mechanical properties of the nanoribbon helices. Shull and co-workers present the optimization of the quartz crystal microbalance as a high frequency direct measurement technique. A high frequency shear wave is excited through a deposited thin film, and the viscoelastic properties of the film are obtained in excellent agreement with values obtained by traditional techniques. When hydrogenated polynorbornene (hPN) is synthesized through ring-opening metathesis polymerization, the hydrogenation route employed can significantly influence the chain microstructure, and thereby its crystal structure and stability. Klein and Register show that the content of trans units influences both the low-temperature crystal structure and the polymorphic transition temperature of hPN, presenting another tool to control phase behavior. Physical aging represents the slow structural evolution of the nonequilibrium glassy material toward equilibrium. Traditionally, physical aging in bulk polymers is associated with local segmental motions and is independent of molecular weight. The physical aging rate of thin films has been found to be reduced from that of the bulk due to the presence of the free surface and the enhanced mobility it imparts. Thees and Roth discover an unexpected molecular weight dependence exhibited by the physical aging response of thin polystyrene films, indicating that chain connectivity and entropy modify the gradient in dynamics near interfaces in polymer glasses. Supramolecular associative polymer networks consist of (macro)molecular building blocks associated by physical transient bonds. The dynamic mechanical properties of supramolecular associative polymer networks depend on interchain entanglements, chemical structures and the content of associative groups. Seiffert and co-workers study the interplay of interchain entanglement, interchain transient association, and aggregation of the associative groups into clusters and their effects on the dynamic mechanics of a library of supramolecular associative polymer networks. The results enrich the assortment of available approaches to stimuli-responsive materials. We hope you will enjoy reading this diverse lineup of papers showcasing the vibrant polymer physics research from our editorial advisory board. We are grateful to all those who contribute to the success of JPSB: our authors, our reviewers, our board members, and of course, our readers. Thank you for your continued support!

ABSTRACTBulk heterojunctions (BHJs) based on semiconducting electron–donor polymer and electron–acceptor fullerene have been extensively investigated as potential photoactive layers for organic solar cells (OSCs). In the experimental studies, poly‐(3‐hexyl‐thiophene) (P3HT) polymers are hardly monodisperse as the synthesis of highly monodisperse polymer mixture is a near impossible task to achieve. However, the majority of the computational efforts on P3HT: phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM)‐based OSCs, a monodisperse P3HT is usually considered. Here, results from coarse‐grained molecular dynamics simulations of solvent evaporation and thermal annealing process of the BHJ are shared describing the effect of variability in molecular weight (also known as polydispersity) on the morphology of the active layer. Results affirm that polydispersity is beneficial for charge separation as the interfacial area is observed to increase with higher dispersity. Calculations of percolation and orientation tensors, on the other hand, reveal that a certain polydispersity index ranging between 1.05 and 1.10 should be maintained for optimal charge transport. Most importantly, these results point out that the consideration of polydispersity should be considered in computational studies of polymer‐based OSCs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 895–903

ABSTRACTAdaptive properties and complex shapes of modern day soft matter components create a challenge for materials applications where mechanical properties of intricate fabricated components cannot be determined from conventional invasive and destructive mechanical tests. In particular, challenges arising from variable mechanical properties of polydimethylsiloxanes (PDMSs) constantly attract wide‐scale attention in the fields of material sciences, biological systems, and microfluidics. Herein, a noninvasive and nondestructive strain‐induced infrared spectroscopic method (S‐FTIR) is developed. S‐FTIR is a method that maps thermo‐mechanical response of PDMS to its strain‐induced spectral fingerprint. From the results of this study, strong correlations of up to 95% between spectral fingerprint of PDMS and its corresponding nonlinear thermo‐mechanical response is seen. Given the nature of these results, it is expected that S‐FTIR will provide an interesting new analytical approach to understand soft materials and allow for the characterization of micro and nanoscale devices composed of these polymeric materials as well. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 359–367

ABSTRACT The dynamics of novel ionomers based on a low‐molecular‐weight polybutadiene with zinc acrylate moieties were investigated as a function of the number of ionic bonds by using a combination of calorimetry, dielectric broadband spectroscopy and rheology. We find that the ionic bonds have profound effects on the mechanical properties, including the introduction of a sol–gel transition. However, all techniques consistently indicate that the segmental dynamics of the polymer chains remain largely unaffected, and only very small changes in the glass transition were observed. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57 , 1074–1079

ABSTRACTThree different perfluorinated type polymers as anion exchange membranes for electrochemical applications were studied. They have a sulfonamide linkage to a spacer methylene chain attached to a tri‐methyl ammonium cation, specifically using a three carbon spacer chain (PFAEM_H_C3), and methylated imide polymers with three (PFAEM_CH3_C3) and six carbon spacer chain (PFAEM_CH3_C6). There are significant number of zwitterionic side chains in the PFAEM_H_C3 polymer and very few in the PFAEM_CH3_C3 or the PFAEM_CH3_C6 polymer. They have similar halide conductivity, but the PFAEM_CH3_C6 showed highest OH− conductivity, 122 mS cm−1 at 80 °C and 95% RH. The larger spacer chain polymer, PFAEM_CH3_C6 has a higher water uptake value (λ = 9) compared to PFAEM_CH3_C3(λ = 7) at 60 °C and 95% RH in the Cl− form. Therefore, it has a larger domain spacing of 4.9 nm versus 4.1 nm from small angle X‐ray scattering data. The polymer was characterized by FTIR and DFT was used to fully assign the spectra. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 700–712

ABSTRACTSoft tissues, such as fat and skin, present high flexibility and are capable of withstanding large deformation in various functions. Hydrogels that can resemble the mechanical performance of soft tissue are unique and widely demanded. In this study, micellar hydrogels based on biocompatible poly(l‐glutamic acid) (PLGA) were designed with the enhanced capacity to bear large deformation. Amphipathic triblock copolymer poly(ethylene glycol) acrylate‐co‐poly(ε‐caprolactone)‐co‐poly (ethylene glycol) acrylate (APEG‐PCL‐APEG) with two terminal double bonds was synthesized and self‐assembled into micelles. At the same time, graft copolymers, poly(l‐glutamic acid)‐g‐hydroxyethyl methacrylate (PLGA‐g‐HEMA) with double bonds were synthesized. APEG‐PCL‐APEG micelles and PLGA‐g‐HEMA were mixed to construct micellar hydrogel via radical polymerization. The crystalline structure and hydrophobic aggregation of copolymers (APEG‐PCL‐APEG) were found to associate with PCL molecular weight. Due to the hydrophobic stress dissipation and crystalline structure of the micelles, the softness and toughness of hydrogels were promoted, exhibiting a 25% increase in ultimate strain. Moreover, the micellar hydrogels were able to load proteins with long‐term retention. In addition, under dynamic mechanical stimulation, the release of proteins could be accelerated. Besides, the micellar hydrogels also supported rabbit adipose‐derived stem cells (rASCs) growth, thus exhibiting the potential toward soft tissue engineering. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1115–1125

Some manufacturing processes of polymeric materials, such as injection moulding or film blowing, cause the final product to be highly anisotropic. In this study, the mechanical behaviour of drawn Polyethylene (PE) tapes is investigated via micro-mechanical modelling. An elastoviscoplastic micro-mechanical model, developed within the framework of the so-called composite inclusion model, is presented to capture the anisotropic behaviour of oriented semi-crystalline Polyethylene. Two different phases namely, amorphous and crystalline (both described by elasto-viscoplastic constitutive models), are considered at the micro-structural level. The initial oriented crystallographic structure of the drawn tapes is taken into account. It was previously shown that by only considering the oriented crystallographic structure, it is not possible to capture the macroscopic anisotropic behaviour of drawn tapes. The main contribution of this study is the development of an anisotropic model for the amorphous phase within the micro-mechanical framework. An EGP (Eindhoven Glassy Polymer) based model including different sources of anisotropy namely, anisotropic elasticity, internal stress in the elastic network and anisotropic viscoplasticity, is developed for the amorphous phase and incorporated into the micro-mechanical model. Comparisons against experimental results reveal remarkable improvements of the model predictions (compared to micro-mechanical model predictions including isotropic amorphous domains) and thus the signi cance of the amorphous phase anisotropy on the overall behavior of drawn PE tapes.

ABSTRACT The potential to improve mechanical, structural, and mechanochemical properties of charge‐functionalized poly( N,N ‐dimethylaminoethyl methacrylate) (PDMAEMA)‐based hybrid cryogels is investigated. The simple and versatile synthesis of hybrid cryogels with high strength and toughness using cationic DMAEMA and ionic comonomer 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid has been proposed via in situ free‐radical crosslinking (cryo)polymerization by which the properties of virgin polymer can be modulated to required applications by incorporation of inorganic filler kaolin (KLN). Two factors affecting swelling and elasticity of hybrid gels (referred as PDA/KLN m ), KLN content and gel preparation temperature, are studied. The optimum KLN concentration for desired swelling and modulus of elasticity is determined as 0.80% (w/v). Effective crosslinking density of hybrid hydrogels increases with KLN addition and this dependence is expressed by a quadratic polynomial as a function of KLN concentration. The results show that obtained hybrid gels with multiresponsive properties could be regarded as “smart materials” in sensing and actuation applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1758–1778

ABSTRACTUnderstanding the deformational and failure behaviors of thermoplastic semicrystalline polymers is crucial due to the practical usages in various engineering applications. Taking isotactic polypropylene (iPP) as a semicrystalline polymer model system, atomistically informed coarse‐grained (CG) molecular dynamics (MD) simulations are employed to investigate the creep behavior of iPP. The simulations reveal that there exists a threshold stress of about 20.0 MPa, above which the maximum strain of iPP within the simulation time span increases dramatically. From the strain‐time analysis, it is observed that the iPP exhibits an initial elastic deformation stage and a subsequent plastic stage at lower stress levels, while a three‐stage creep behavior including a third fracture stage is observed at higher stress levels. Specifically, at lower stress levels, the bonded energy increases continuously as the chains stretch steadily, while the nonbonded energy shows an initial increase followed by a steady decrease due to the interchain sliding. At higher stress levels, both bonded and nonbonded energies change dramatically at the third stage, resulting from accelerated chain stretching, unfolding, sliding, and breaking. This study provides physical insight into the creep behavior of iPP at a fundamental molecular level and highlights the important role of microstructural evolution of chains in the deformation of semicrystalline polymer materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 1779–1791