Journal of Polymer Science Part B: Polymer Physics

Cover image for Vol. 54 Issue 6

Early View (Online Version of Record published before inclusion in an issue)

Online ISSN: 1099-0488

Associated Title(s): Journal of Polymer Science Part A: Polymer Chemistry

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  1. 1 - 33
  1. Full Papers

    1. Recovery stress and work output in hyperbranched poly(ethyleneimine)-modified shape-memory epoxy polymers

      David Santiago, Albert Fabregat-Sanjuan, Francesc Ferrando and Silvia De la Flor

      Article first published online: 3 FEB 2016 | DOI: 10.1002/polb.24004

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      Hyperbranched-modified shape-memory epoxy polymers are studied in order to determine their potential use as thermomechanical actuators. Shape memory effect is analysed under fully and partially constrained conditions to evaluate the recovery stress and mechanical work generated. Results revealed rapid recovery stress generation, very high recovery stresses (up to 7 MPa) and extremely high work densities (up to 750 kJ/m3). The network structure of shape-memory polymers was found to be a key factor for actuator-like applications.

    2. Molecular dynamics simulations of cation-controlled aggregation in fluorene–triarylamine copolymers

      Meilin Li and Stefan Adams

      Article first published online: 3 FEB 2016 | DOI: 10.1002/polb.23998

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      Molecular dynamics simulations of sulfonated fluorene–triarylamine hole conductor polymers containing a wide range of monovalent cations show that the variation in the degree of cation clustering with cation size controls polymer morphology, cation mobility and the time evolution of the energy landscape for charge transport. The resulting MD trajectories for each BAFS–cation system are analyzed with respect to the influence of the cation type on the ionic aggregation and related structural features that may affect the conduction mechanism.

    3. Phase separation in dilute polymer solutions at high-rate extension

      Andrey V. Subbotin and Alexander N. Semenov

      Article first published online: 3 FEB 2016 | DOI: 10.1002/polb.24005

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      Flow-induced demixing in polymer solutions is a widely known phenomenon observed both in shear and extension flows, particularly high-rate uniaxial extension of polymer solutions often accompanied by decomposition of polymeric filament from the solvent. We study the phase separation in polymer solutions under extension flow arisen above the coil to stretched coil transition. Based on the free energy analysis we show that the flow-induced orientation of polymer segments can drastically reduce the energy of their steric repulsion. As a result attraction between the chains gains more importance, and this effect leads to segregation of polymer from the solvent if the strain rate exceeds some critical value.

  2. Reviews

    1. You have free access to this content
      A review of shape memory polymers bearing reversible binding groups

      Christopher L. Lewis and Elizabeth M. Dell

      Article first published online: 1 FEB 2016 | DOI: 10.1002/polb.23994

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      Reversible binding groups (RBGs) can be strategically used to engineer shape memory polymers (SMPs) with new and exciting properties. SMPs bearing both supramolecular and dynamic covalent RBGs will be reviewed with an emphasis on hydrogen bonding, ionic interactions, metal–ligand coordination, and dynamic covalent exchange and addition reactions.

  3. Full Papers

    1. Effects of amorphous poly(3-hexylthiophene) on active-layer structure and solar cells performance

      Chung-Hao Liu, Wei-Hsuan Tseng, Chih-Yang Cheng, Chih-I Wu, Pi-Tai Chou and Shih-Huang Tung

      Article first published online: 30 JAN 2016 | DOI: 10.1002/polb.23999

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      For bulk heterojunction polymer/fullerene solar cells, it has been known that high polymer crystallinity that facilitates the charge carrier transport through the route of π-π stacking is crucial for achieving a high power conversion efficiency. This work emphasizes the importance of amorphous phase and demonstrates that a small amount of amorphous regiorandom P3HT can retard the phase separation between P3HT and PCBM, thus leading to an improvement of solar cell stability.

    2. On clarification of haze in polypropylene

      K. Bernland, J. G. P. Goossens, P. Smith and T. A. Tervoort

      Article first published online: 19 JAN 2016 | DOI: 10.1002/polb.23992

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      A scanning electron micrograph showing the shish-kebab morphology of clarified isotactic polypropylene (i-PP) using a new clarifying agent, 1,3,5-tris(2,2-dimethylpropionylamino)benzene. The right insert shows the corresponding small-angle light scattering pattern, depicting a rod-like scattering pattern. It was found that the observed complete loss of spherulitic morphology is responsible for the dramatically increased transparency of the i-PP (left insert).

    3. Photophysical behavior of block copolymers containing EDOT, thiophene, and benzodiathiazole units linked to fluorene

      Cristiano Zanlorenzi, Sandra M. Cassemiro, Isabel R. Grova and Leni Akcelrud

      Article first published online: 19 JAN 2016 | DOI: 10.1002/polb.23993

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      Two blocked conjugated copolymers based on Fluorene-Tiofene (FTh) and Fluorene-benzotiadiazole (FBz) are synthesized, containing a Fluorene-EDOT (FEDOT) as a common base. Experimental and theoretical calculations were performed to understand the electronic behavior observed. The degree of electronic coupling between the monomeric units in each block depended on the donor-acceptor character between the components of each block, resulting in retaining or electronic coupling, and consequently determines the nature of the electronic transitions in both.

    4. Phase separation and permeability in polyisobutylene-based miktoarm star polymers

      Katrina M. Knauer, Yaling Zhu, Robson F. Storey and Sarah E. Morgan

      Article first published online: 18 JAN 2016 | DOI: 10.1002/polb.23996

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      Miktoarm star polymer thermoplastic elastomer films display unexpected morphological transitions as a function of PAA volume fraction. At low concentrations, the PAA phase resides within PS cylinders, despite the fact that the PAA is not directly attached to the PS block. At higher concentrations the PAA forms a separate phase, and a gyroid-like morphology develops. Thermal annealing demonstrated the thermodynamic stability of the microstructures, indicating their potential for design of new structures with desired performance capabilities.

    5. Selective swelling induced pore generation of amphiphilic block copolymers: The role of swelling agents

      Nina Yan and Yong Wang

      Article first published online: 18 JAN 2016 | DOI: 10.1002/polb.23997

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      The swelling-induced pore formation of amphiphilic block copolymers is remarkably influenced by the molecular structures of alcoholic swelling agents, including numbers of carbon atoms and hydroxyl groups. Monohydric alcohols with longer aliphatic chains exhibit a stronger ability to induce pore formation. High-carbon alcohols including n-propanol, n-butanol, and n-hexanol produce cylindrical micelles upon prolonged exposure while methanol, glycol, and glycerol do not make pores although they also induce the surface segregation of P2VP blocks.

  4. Communications

    1. Influence of molecular weight and degree of segregation on local segmental dynamics of ordered block copolymers

      Vaidyanathan Sethuraman, Victor Pryamitsyn and Venkat Ganesan

      Article first published online: 15 JAN 2016 | DOI: 10.1002/polb.23985

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      Experimental studies using block copolymer electrolyte materials have observed intriguing dependence of the ionic conductivities on the polymer molecular weight and the degree of segregation between the blocks. Ion conductivities in block copolymer phases are expected to be related to the local dynamics of the conducting phase in ordered morphologies. Molecular dynamics simulations are employed in this study to understand the influence of degree of segregation and molecular weight on local polymer dynamics.

  5. Full Papers

    1. Microstructural behavior and failure mechanisms of organic semicrystalline thin film blends

      Bingxiao Zhao, Omar Awartani, Brendan O'Connor and Mohammed A. Zikry

      Article first published online: 13 JAN 2016 | DOI: 10.1002/polb.23991

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      To understand and predict the fundamental mechanisms affecting failure, a multiphase, microstructurally based formulation and nonlinear finite-element fracture methodology are used to investigate the heterogeneous deformation and failure modes of organic semicrystalline thin film blends. This study provides fundamental understanding of local failure mechanisms, demonstrates the possible mechanical degradation due to physical morphological changes, and the proposed predictive framework can be used to improve film ductility and strength for failure-resistant flexible electronics applications.

    2. You have free access to this content
      Body temperature triggered shape-memory polymers with high elastic energy storage capacity

      Yuan Meng, Jisu Jiang and Mitchell Anthamatten

      Article first published online: 13 JAN 2016 | DOI: 10.1002/polb.23990

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      Shape-memory polymers (SMPs) that respond near body temperature are attracting broad interest, especially in the biomedical fields. A semi-crystalline SMP's melting transition temperature is tuned by incorporating non-crystalline molecular linker groups and by altering the network prepolymer molecular weight. Optimized networks exhibit melting temperatures between room temperature and the human body temperature, and, upon triggering, the networks are capable of releasing large amounts of elastic energy. This straightforward technology could benefit numerous biomedical applications. Photo by J. Adam Fenster, University of Rochester.

  6. Reviews

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      Porous shape memory polymers: Design and applications

      Sayyeda M. Hasan, Landon D. Nash and Duncan J. Maitland

      Article first published online: 10 JAN 2016 | DOI: 10.1002/polb.23982

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      Shape memory polymers (SMPs) are smart materials that switch between shapes and have gained interest in a wide range of commercial and medical industries. This review discusses porous SMPs and their applications with a focus on fabrication techniques, characterization methods, and the various modes of actuation. Porous SMPs have a strong potential of revolutionizing the industries that can benefit from self-actuating systems and are beginning to gain preference compared to traditional polymer systems.

  7. Full Papers

    1. Design of bicontinuous donor/acceptor morphologies for use as organic solar cell active layers

      Dylan Kipp, Rafael Verduzco and Venkat Ganesan

      Article first published online: 9 JAN 2016 | DOI: 10.1002/polb.23988

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      The device performance of organic solar cells has been speculated to depend sensitively on the active layer morphology. Desirable morphological characteristics include nanoscale domain sizes, high interfacial areas, percolating domains, and compositionally pure domains. Here, simulations are used to study the phase behavior of a blend of conjugated polymer donors, fullerene acceptors, and all-conjugated BCP additives. The blend conditions that give rise to bicontinuous donor/acceptor morphologies with the desired characteristics are identified.

    2. Hydrodynamic properties and conformation of poly(3-hexylthiophene) in dilute solutions

      Alexander V. Yakimansky, Stanislav V. Bushin, Marina A. Bezrukova, Alexey A. Lezov, Alexander S. Gubarev, Elena V. Lebedeva, Lilija I. Akhmadeeva, Anna N. Podseval'nikova, Nikolaj V. Tsvetkov, Guy Koeckelberghs and Andre Persoons

      Article first published online: 9 JAN 2016 | DOI: 10.1002/polb.23986

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      In this work, the conformational analysis of poly(3-hexylthiophene) in dilute solutions was performed using a series of polymer homologues in a wide range of molecular weights. The projection of the monomer unit in the direction of the main polymer chain (λ = 0.37 nm) was determined experimentally for the first time. The equilibrium rigidity (А = 6.7 nm) and hydrodynamic diameter of the polymer chain (d = 0.6 nm) were also quantified.

    3. Prediction of viscoelastic properties with coarse-grained molecular dynamics and experimental validation for a benchmark polyurea system

      Vipin Agrawal, Kristin Holzworth, Wiroj Nantasetphong, Alireza V. Amirkhizi, Jay Oswald and Sia Nemat-Nasser

      Article first published online: 8 JAN 2016 | DOI: 10.1002/polb.23976

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      A coarse-grained model is developed to bridge length and time scales between molecular dynamics (MD) simulations and experiments to predict the viscoelastic response of polyurea. With a systematically coarse-grained model calibrated from atomistic simulations, stress relaxation curves are predicted from coarse-grained molecular models to millisecond time scales and validated with experimental measurements. The combination of reduced degrees of freedom, a larger stable simulation time step and accelerated dynamics yields a computational speedup on the order of 5–6 orders over atomistic MD simulations.

    4. Simulation of pulse responses of lithium salt-doped poly ethyleneoxide

      Ao Liu, Fei Zeng, Yuandong Hu, Siheng Lu, Wenshuai Dong, Xiaojun Li, Chiating Chang and Dong Guo

      Article first published online: 8 JAN 2016 | DOI: 10.1002/polb.23983

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      Pulse responses of lithium-doped poly ethyleneoxide complexes are studied. It is found that redistribution of ions results in accumulation of charge and establishes a reverse inbuilt electric field controlling the discharging process and the frequency response. The charging current's wave shape is controlled mainly by the diffusion process. The weights of calculated discharging and charging current agree well with the experimental results.

    5. Tuning the π-π stacking distance and J-aggregation of DPP-based conjugated polymer via introducing insulating polymer

      Liang Chen, Haiyang Wang, Jiangang Liu, Rubo Xing, Xinhong Yu and Yanchun Han

      Article first published online: 8 JAN 2016 | DOI: 10.1002/polb.23984

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      Blending with polystyrene (PS) is beneficial for the disentanglement of poly[[2,5-bis(2-octyldodecyl)−2,3,5,6-tetrahydro-3,6-dioxopyrrolo[3,4-c]pyrrole-1,4-diyl]-alt–[[2,2’-(2,5-thiophene)bis-thieno[3,2-b]thiophen]-5,5’-diyl]] (PDPPTT-T) chains. This disentanglement of PDPPTT-T aids in the formation of fibrillar morphology, where fibrils grow along the molecular backbones. The disentanglement of PDPPTT-T causes the molecules to adjust their conformation to improve J-aggregation and decrease the π–π stacking distance.

    6. A predictive parameter for the shape memory behavior of thermoplastic polymers

      Rui Xiao, Christopher M. Yakacki, Jingkai Guo, Carl P. Frick and Thao D. Nguyen

      Article first published online: 5 JAN 2016 | DOI: 10.1002/polb.23981

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      An experimental and modeling study of the effect of programming conditions on the shape memory behaviors of amorphous thermoplastic polymers is presented. The model predictions showed excellent agreement with the experiments regarding the stress response and shape memory response. The results show that the relaxation modulus at the end of the programming process was a predictor of the recovery speed and recoverable strain ratio. This provides a design metric to optimize the shape programming process for shape recovery.

    7. Molecular-level structures at poly(4-vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

      Mingcong Wang, Bolin Li, Zhan Chen and Xiaolin Lu

      Article first published online: 30 DEC 2015 | DOI: 10.1002/polb.23978

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      In PAA solution (top), PAA chains are adsorbed onto the P4VP surface and water molecules interact with the adsorbed PAA chains. In HCl solution (bottom), the P4VP surface is protonated and water molecules interact with the charged surface. Molecular-level structures of such different interfaces can be probed by SFG.

    8. Influence of different alkyl-methylimidazolium tetrafluoroborate ionic liquids on the structure of pebax® films. Consequences on thermal, mechanical, and water sorption and diffusion properties

      S. Magana, O. Gain, F. Gouanvé and E. Espuche

      Article first published online: 22 DEC 2015 | DOI: 10.1002/polb.23977

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      This work addresses the optimization of the water transport properties of a copolymer film due to the introduction of ionic liquid (IL) moieties. The polymer/ionic liquid miscibility is investigated for a large range of compositions. The impact of ionic liquid content and its alkyl chain length is also studied in terms of the film morphology and their thermal stability, thermomechanical properties and water diffusion and sorption properties. The best properties are achieved for low length of the ionic liquid alkyl chain and totally miscible systems.

    9. Dewetting behavior of Langmuir−Blodgett films of polystyrene-b-poly(methyl methacrylate) induced by solvent vapor annealing

      Tao Wu, Gangyao Wen and Changchun Huang

      Article first published online: 18 DEC 2015 | DOI: 10.1002/polb.23979

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      The dewetting behavior of Langmuir–Blodgett (LB) films induced by solvent vapor annealing is investigated by atomic force microscopy for the first time. With the annealing of acetone vapor, the LB films undergo the swelling and coalescing of aggregates, the formation of bicontinuous patterns, the formation of droplets, and the periodic evolution of droplets. The last stage is a novel phenomenon observed for the first time and quite different from the single droplet evolution of spin-coated films.

  8. Communication

    1. Strikingly improved toughness of nonpolar rubber by incorporating sacrificial network at small fraction

      Xuhui Zhang, Zhenghai Tang, Jing Huang, Tengfei Lin and Baochun Guo

      Article first published online: 18 DEC 2015 | DOI: 10.1002/polb.23980

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      INSPIRED by the concept of sacrificial bonding associated with biological materials, the sacrificial networks are constructed, for the first time, in a diene-based rubber via traditional processing. The “brittle” epoxidized natural rubber network is incorporated as the sacrificial network to toughen the weak styrene-butadiene rubber, resulting in strikingly improved toughness at a small fraction of the sacrificial network.

  9. Full Papers

    1. Young's modulus and loss tangent measurement of polydimethylsiloxane using an optical lever

      Edoardo Rubino and Tindaro Ioppolo

      Article first published online: 15 DEC 2015 | DOI: 10.1002/polb.23972

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      In thisarticle, the Young's modulus and the loss tangent of polydimethylsiloxane (PDMS) are obtained in the frequency range between 10 and 1500 Hz using an optical technique. The first three mechanical modes of a vibrating PDMS beam are detected by measuring the tip rotational displacement using an optical lever. The experiments are carried out for 10:1 and 20:1 volume mixing ratio between the polymer base and the curing agent.

    2. Morphology and properties of globular polymeric materials in the solid state: A composite material of DNA with a cationic surfactant

      Emmanuel C. Ossai, Yuka Tomimori, Shota Ohki, Koki Okada, Takeshi Yonekura, Kazuya Furusawa and Naoki Sasaki

      Article first published online: 1 DEC 2015 | DOI: 10.1002/polb.23968

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      Inter-chain entanglements give crucial characteristics to polymeric solid materials, though it is still hard to obtain a desired amount of them. In order to control the entanglements as a property-regulating parameter, globular polymeric films with very few entanglements were fabricated making use of the stable globules of DNA-cationic surfactant complex. Morphological studies of the films revealed that they were composed of particles containing several DNA-CTA globule molecules.

    3. Multiple dynamic regimes in colloid-polymer dispersions: New insight using X-ray photon correlation spectroscopy

      Sunita Srivastava, Suhasini Kishore, Suresh Narayanan, Alec R. Sandy and Surita R. Bhatia

      Article first published online: 1 DEC 2015 | DOI: 10.1002/polb.23973

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      Colloidal particle and cluster interactions can be tuned by varying polymer properties, such as chain length and concentration. This study uses X-ray photon correlation spectroscopy to investigate different dynamic regimes in systems containing colloidal disks and weakly adsorbing polymers, and highlights the influence of the dynamics observed in each region on the resulting macroscopic properties of the system.

    4. Structure–property relationship in high urethane density polyurethanes

      Borja Fernández-d'Arlas and Arantxa Eceiza

      Article first published online: 28 NOV 2015 | DOI: 10.1002/polb.23969

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      The impact of short glycol structure on the structure and properties of polyurethanes is studied by analyzing the influence of the primary (chain conformation) and secondary structures (amorphous and crystalline phases) on the crystallinity and mechanical properties of high urethane density polymers based on aliphatic 1,6-hexamethylene diisocyanate. This provides insight into the role of segmental architecture influence on the self-assembling and mechanical performance of high urethane density polyurethanes.

    5. Bioactive composites fabricated by freezing-thawing method for bone regeneration applications

      Maria Canillas, Gabriel G. de Lima, Miguel A. Rodríguez, Michael J. D. Nugent and Declan M. Devine

      Article first published online: 28 NOV 2015 | DOI: 10.1002/polb.23974

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      A composite cryogel that produces high strength composites materials which can control the release of antimicrobial agents is the aim of this work. The constructs presents stronger values than similar materials in the literature and contain porous structure which is beneficial for vascular invasion and bone ingrowth. Since the fabrication method does not require any toxic elements, presents good biocompatibility and ability to control swelling, this system have great potential in the field of orthopaedics.

    6. Controlled dispersion of polystyrene-capped Au nanoparticles in P3HT:PC61BM and consequences upon active layer nanostructure

      Dennis P. Butcher Jr., Robert C. Wadams, Lawrence Drummy, Hilmar Koerner, Chris Bailey, Frank Scheltens, David Mccomb, Laura Fabris, Michael F. Durstock and Christopher Tabor

      Article first published online: 26 NOV 2015 | DOI: 10.1002/polb.23962

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      Au nanoparticles with a polymer coating assemble into three-dimensional ordered structures, dependent upon processing conditions, which impact film structure and the electronic and optical properties when placed into an organic photovoltaic active layer. The accompanying figure provides a three-dimensional reconstruction of polymer coated Au nanoparticles within the active layer of an organic photovoltaic active layer film.

    7. Effect of constrained annealing on the mechanical properties of electrospun poly(ethylene oxide) webs containing multiwalled carbon nanotubes

      Jiaxing Bao, Laura I. Clarke and Russell E. Gorga

      Article first published online: 24 NOV 2015 | DOI: 10.1002/polb.23960

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      Annealing near Tm under a minor constraint (the presence of paper frame) leads to fiber alignment which resulted in significant increases in modulus as the fibers, the aligned molecules within them, and well-dispersed MWNT if present became oriented along the tension axis. In particular, constrained annealing at temperatures just below the melting point resulted in fiber alignment due to the imposed tension when the mat was unable to spontaneously shrink.

    8. Revisiting the crystallization of poly(2-alkyl-2-oxazoline)s

      A. Levent Demirel, Pınar Tatar Güner, Bart Verbraeken, Helmut Schlaad, Ulrich S. Schubert and Richard Hoogenboom

      Article first published online: 24 NOV 2015 | DOI: 10.1002/polb.23967

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      Differential scanning calorimetry is used to investigate the crystallization of poly(2-alkyl-2-oxazoline)s as a function of alkyl side chain length. Different crystallization behaviors—no, cold, and normal crystallization—are observed and attributed to different polymer chain mobility, in line with the Tg dependence of alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length results in double melting peaks in PButOx.

    9. How molecular internal-geometric parameters affect PB-PEO polymersome size in aqueous solution

      Joachim Habel, Anayo Ogbonna, Nanna Larsen, Lars Schulte, Kristoffer Almdal and Claus Hélix-Nielsen

      Article first published online: 12 NOV 2015 | DOI: 10.1002/polb.23954

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      The diameter size distributions of polymersomes based on polybutadiene polyethylene oxide with high f / low Mn and mixed diameters, high f / high Mn and mainly large diameters, and low f and mainly small diameters were measured using dynamic light scattering and freeze-fracture transmission electron microscopy. In the last region, the poylmersomes are highly polydisperse, containing many highly varying diameters. Furthermore, there is a tendency towards increased diameter with increasing f and Mn. These findings can facilitate the cost-efficient upscaling of polymersome production.

  10. Perspectives

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      Reversible plasticity shape memory polymers: Key factors and applications

      Xuhui Zhang, Zhenghai Tang and Baochun Guo

      Article first published online: 28 SEP 2015 | DOI: 10.1002/polb.23916

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      Reversible Plasticity Shape Memory (RPSM) polymers, a new type of shape memory polymer (SMP), exhibit a simplified fixing process, high recovery stress, and enhanced deformability compared with conventional SMPs. This Perspective discusses how the deformation temperature and fixing conditions influence the fixity and recovery behavior of RPSM polymers and how to optimize the conditions for RPSM, providing general information for the design and application of such novel materials.

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