Preparation and characterization of covalently bonded PVA/Laponite/HAPI nanocomposite multilayer freestanding films by layer‐by‐layer assembly

The layer‐by‐layer (LBL) assembly technique is an attractive method to make functional multilayer thin films and has been applied to fabricate a wide range of materials. LBL materials could improve optical transmittance and mechanical properties if the film components were covalently bonded. Covalently bonded nanocomposite multilayer films were prepared by employing hydrophilic aliphatic polyisocyanate (HAPI) as the reactive component, to react with Laponite and polyvinyl alcohol (PVA). FT‐IR spectra suggested that HAPI reacted with Laponite and PVA at ambient temperature rapidly. Ellipsometry measurement showed that the film thickness was in linear growth. The influences of HAPI on the optical, mechanical and thermal properties of the films were investigated by UV‐Vis spectroscopy, tensile stress measurement, DSC and TGA. The obtained results showed that the optical transmittance and mechanical strength were enhanced when the film components were covalently bonded by HAPI. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 545–551     

Shape‐memory effect in hyperbranched poly(ethyleneimine)‐modified epoxy thermosets

A series of shape‐memory epoxy thermosets were synthesized by crosslinking diglycidyl ether of bisphenol A with mixtures of commercially available hyperbranched poly(ethyleneimine) and polyetheramine. Thermal, mechanical and shape‐memory properties were studied and the effect on them of the content and structure of the hyperbranched polymer was discussed. Measurements showed that the glass transition temperature can be tailored from 60 °C to 117 °C depending on the hyperbranched polymer content, and all formulations showed an appropriate glassy/rubbery storage modulus ratio. Shape‐memory programming was carried out at TgE′ given the excellent mechanical properties of the materials, with maximum stress and failure strain up to 15 MPa and 60%, respectively. The resulting shape‐memory behavior was excellent, with maximum shape recovery and shape fixity of 98% as well as a fast shape‐recovery rate of 22%/min. The results show that hyperbranched poly(ethyleneimine) as a crosslinking agent can be used to enhance mechanical and shape‐memory properties with different effects depending on the crosslinking density. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 924–933     

Organic–inorganic bonding in chitosan–silica hybrid networks: Physical properties

Novel biomaterials are needed for bone tissue repair with improved mechanical performance compared to classical bioceramics. The objective of this work was to characterize a hybrid filler material, which is capable to coat as a thin film porous scaffolds improving their mechanical properties for bone tissue engineering. The hybrid filler material is a blend of chitosan and silica network formed through in situ sol–gel using tetraethylortosilicate and 3‐glycidoxypropyltrimethoxysilane (GPTMS) as silica precursors. The hypothesis was that the epoxy ring of GPTMS could react with the amino groups of chitosan in acidic media while it is also reacting the siloxane groups of hydrolyzed silica precursors. The formation of the hybrid organic–inorganic network was assessed by different physical techniques revealing changes in molecular mobility and hydrophilicity upon chemical reaction. Finally, the cytotoxicity of the samples was also evaluated by MTT assay. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1391–1400     

Correlation between mechanical adhesion and interfacial properties of starch/biodegradable polyester blends

Biopolymers are preferred ingredients for the manufacture of materials because they are based on abundantly available and renewable raw materials that have benign environmental problems associated with their production, fabrication, use, and disposal; however, the wide use of biopolymers in engineering applications has not been achieved, mainly because of the inferior quality of many biopolymer‐based products. To overcome this limitation, studies have been initiated on blends of biopolymers and biodegradable synthetic polymers. We used the contact angle of probe liquids to measure the surface energy of polystyrene, the biodegradable polyesters polycaprolactone, poly(hydroxybutyrate‐co‐hydroxyvalerate), polylactic acid, polybutylene adipate terephthalate, and adipic poly(hydroxy ester ether), and normal starch. The surface energies were used to estimate the starch/polymer interfacial energy and work of adhesion. The calculated starch/polyester work of adhesion showed mixed correlation with published starch/polyester mechanical properties, indicating that factors other than interfacial properties might be dominant in determining the mechanical properties of some starch/polyester blends. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 920–930, 2001     

Reversible plasticity shape memory polymers: Key factors and applications

Reversible plasticity shape memory (RPSM) polymers have been emerging as new smart materials with distinctions compared with conventional SMPs, such as easier shaping programming, stronger recovery stress, and higher recovery strain. For purposeful control of the structure, and therefore the physical and mechanical properties, a full understanding of the deformation habits of such materials under different conditions is essential. This perspective provides the context as to how the deformation temperature and fixing conditions influence the fixity and recovery behavior of RPSM polymers and what are the optimized conditions for RPSM. We hope that this will afford useful information for fabricating RPSM polymers with better memory properties and promote the technical development of new design methods of such materials for advanced applications © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1295–1299     

Morphology and bridging properties of (AB)n multiblock copolymers

Motivated by recent experiments (Spontak, R. J.; Smith, S. D. J Polym Sci Part B: Polym Phys 2001, 39, 947) on morphological and mechanical properties of multiblock copolymers (AB)_n, we theoretically elucidate the links between microscopically determined properties, such as the bridging fraction of chains, and mechanical properties of these materials. We do this by applying self‐consistent mean‐field theory to determine morphological aspects such as period and interfacial width and calculate the bridging fractions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 104–111, 2003     

Environmentally Stable Polymer Gels with Super Deformability and High Recoverability Enhanced by Sub‐5 nm Particles in the Nonvolatile Solvent

It remains challenging to satisfy the combined performances for hydrogels with excellent mechanical behavior, high deformability, and super recoverability under harsh environmental conditions. In this study, we first established a strong polymer network via the crosslinking of polymer chains on the surfaces of sub‐5‐nm calcium hydroxide nanospherulites in ethylene glycol solvent. The organic gel expressed excellent mechanical properties such as a recoverable compressive engineering stress of 249 MPa and an elongation stress of 402 KPa, which was attributed to the uniform nanosized crosslinking structure as characterized by SEM. Moreover, the nonvolatile solvent remained in the gel, meaning that the sample can resist a wide temperature range of ?56 to 100 °C without losing the elastic properties. This novel organic gel could provide promising routes to develop the ideal elastic carriers for wearable devices, smart skin sensors, and damping materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 713–721     

Flexible,stretchable, and patchable organic devices integrated on freestanding polymeric substrates

We present a novel technique for realizing an electrical circuit composed of organic devices on a highly flexible, stretchable, and patchable freestanding substrate, using a photo‐curable polyurethaneacrylate (PUA) mixture. Substrate structure was designed under consideration of enhanced mechanical strength in addition to flexibility, stretchability, and adhesive properties. The designed components facilitate the fabrication of highly flexible and stretchable electrodes without additional photolithography or patterning processes, and the fabricated organic circuits are substantially free from structural stress and strain induced from the substrate deformation. High flexibility and adhesive properties also enable mounting of the organic circuits onto nonflat surfaces with conformal contact. In addition, high light transmissivity of PUA suggests strong potential for a wide range of optoelectronic applications. We anticipate that these results will be applied to the development of various flexible, stretchable, and patchable organic devices, which can lead to further applications in many fields of science and engineering. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 453–460     

Cure kinetics modeling and thermomechanical properties of cycloaliphatic epoxy‐anhydride thermosets modified with hyperstar polymers

Hyperstar polymers (HSPs) with hyperbranched aromatic polyester core and arms consisting of block copolymers of poly(methyl methacrylate) and poly(hydroxyethyl methacrylate) have been used as polymeric modifiers in cycloaliphatic epoxy‐anhydride formulations catalyzed with tertiary amines, with the purpose of enhancing the impact strength of the resulting materials without compromising other thermal and mechanical properties.> In this work, the effect of these polymeric modifiers on the curing kinetics, processing, thermal‐mechanical properties and thermal stability has been studied using thermal analysis techniques such as DSC, TMA, DMA, and TGA. The morphology of the cured materials has been analyzed with SEM. The curing kinetics has been analyzed by isoconversional procedures and phenomenological kinetic models taking into account the vitrification during curing, and the degradation kinetics has been analyzed by means of isoconversional procedures, summarizing the results in a time‐temperature‐transformation (TTT) diagram. The results show that HSPs participate in the crosslinking process due to the presence of reactive groups, without compromising significantly their thermal‐mechanical properties. The modified materials show a potential toughness enhancement produced by the formation of a nano‐grained morphology. The TTT diagram is shown to be a useful tool for the optimization of the curing schedule in terms of curing completion and safe processing window, as well as for defining storage stability conditions. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1227–1242     

Fabrication of silk fibroin film with properties of thermal insulation and temperature monitoring

Silk fibroin exhibits excellent mechanical properties, good biocompatibility, and biodegradability combined with benign processing conditions, attracting considerable research interest for the application as biomedical materials. Among the diverse forms of sponges, hydrogels, films, and mats manufactured from silk fibroin, films are especially appealing due to the high water and oxygen permeability, good cell attachment, and low immunogenicity. Fabrication of silk fibroin films with novel properties has been successfully developed simply by incorporating various functional components into it. In the present study, the properties of thermal insulation and temperature monitoring for the silk fibroin film are demonstrated for the first time through the incorporation of thermochromic microcapsules within it. Moreover, the silk fibroin film is also endowed with improved mechanical properties in terms of tension strength and elongation at break because of the reinforcing effect of thermochromic microcapsules. The silk fibroin film fabricated with novel features in this study can be a good candidate for the application of wound dressings, tissue engineering scaffolds, and bio‐related devices in the future. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1846–1852     

Biomimetic triblock and multiblock copolymers containing l‐Phenylalanine moieties showing healing and enhanced mechanical properties

Triblock and multiblock copolymers of methyl acrylate containing short blocks of the hydrogen bonding monomer N‐acryloyl‐l ‐phenylalanine were prepared via reversible addition–fragmentation chain transfer polymerization in two steps using a bifunctional trithiocarbonate for the triblock copolymer and a polyfunctional trithiocarbonate for the multiblock copolymer. The polymer materials were investigated via tensile testing showing that the hydrogen bonding monomer induces a pronounced increase in toughness. The toughness of the material is further enhanced when going from triblock to multiblock topology. Both types of copolymer display a very strong healing effect, with the samples' toughness (which is increased by drawing) becoming even larger after breaking and healing. Already, a very small content of only 0.1 mol % of N‐acryloyl‐l ‐phenylalanine improves the mechanical properties of these thermoplastic elastomers significantly. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2809–2819     

Apparent depth‐dependent modulus and hardness of polymers by nanoindentation: Investigation of surface detection error and pressure effects

Nanoindentation is a widely used technique to characterize the mechanical properties of polymeric materials at the nanoscale. Extreme surface stiffening has been reported for soft polymers such as poly(dimethylsiloxane) (PDMS) rubber. Our recent work [J. Polym. Sci. Part B Polym. Phys. 2017 , 55, 30–38] provided a quantitative model which demonstrates such extreme stiffening can be associated with experimental artifacts, for example, error in surface detection. In this work, we have further investigated the effect of surface detection error on the determination of mechanical properties by varying the sample modulus, instrument surface detection criterion, and probe geometry. We have examined materials having Young's moduli from ∼2 MPa (PDMS) to 3 GPa (polystyrene) using two different nanoindentation instruments (G200 and TI 950) which implement different surface detection methods. The results show that surface detection error can lead to apparent large stiffening. The errors are lower for the stiffer materials, but can still be significant if care is not taken to establish the range of the surface detection error in a particular experimental situation. We have also examined the effect of pressure beneath the probe on the nanoindentation‐determined modulus of polystyrene with different probe geometries. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 414–428     

Thermal kinetics and thermo‐mechanical properties of graphene integrated fluoroelastomer

In this work, the thermal properties of a fluoroelastomer enhanced by graphene were systematically investigated. Although graphene oxide (GO) is the most popular and cheapest source for graphene, its chemical and thermal properties were quite different from reduced graphene oxide (RGO). By comparing their influences on the thermal properties of elastomer, the effects from chemical structures and morphologies of graphene were analyzed. As the vulcanization and decomposition determine the properties of the elastomer proved by significantly different thermo‐mechanical properties of the fluoroelastomer reinforced by GO and RGO presented, this work provides a method to ultimate utilize graphene to reinforce elastomer. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1691–1700     

A soft lithography method to generate arrays of microstructures onto hydrogel surfaces

Materials bearing microscale patterns on the surface have important biomedical applications such as scaffolds in tissue engineering, drug delivery systems, sensors, and actuators. Hydrogels are an attractive class of materials that has excellent biocompatibility, biodegradability, and tunable mechanical properties that meet the requirements of the aforementioned applications. Generating patterns of intricate microstructures onto the hydrogel surfaces, however, is challenging due to properties such as the crosslinking density, low mechanical strength, adhesion, or chemical incompatibility of hydrogels with various molds. Here, we report the use of a soft lithography technique to successfully transfer arrays of micropillars onto a poly(2‐hydroxyethyl methacrylate)‐based hydrogel. The swelling of the hydrogel in solvents, such as phosphate‐buffered saline, deionized water, 60% ethanol, and absolute ethanol, facilitates the reproducible replication of the pattern. Furthermore, the micropillar pattern promotes the attachment of HeLa cells onto this hydrogel which is not inherently adhesive when unpatterned. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1144–1157     

Approaches to polymeric mechanochromic materials

Mechanochromic materials respond to mechanical stimuli with a change of their optical properties. Such materials are of interest for many technological applications and support fundamental research as they help improving the understanding of stress transfer in polymeric objects and aid in the identification of the processes that lead to mechanical failure. In this highlight, different approaches are discussed that permit the design of polymeric materials, which signal mechanical stresses through a chromic response. This highlight emphasizes materials that exhibit mechanically induced changes of their intrinsic absorption or emission properties. These responses almost exclusively originate from changes of molecular structure, conformational rearrangements, or disruption of intermolecular interactions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 640–652     

Preparation and characterization of novel transparent plasticized poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) gel

Transparent plasticized gels with good mechanical, optical, and dielectric properties have important applications in various fields. We prepared a new gel using a poly(butylene terephthalate)‐co‐poly(alkylene glycol terephthalate) (PBT‐co‐PAGT) copolymer and a plasticizer, dibutyl adipate (DBA). This method improved the polymer crystallinity, and suppressed particle formation in cast‐films when the polymer was dissolved in 1,1,1,3,3,3‐hexafluoro‐2‐propanol, followed by solvent evaporation, and enabled uniform swelling of the polymer network by the plasticizer to form a transparent and flexible gel. The dielectric constants of the developed PBT‐co‐PAGT/DBA gels are much higher than those of PBT‐co‐PAGT films at low frequency. We believe that these PBT‐co‐PAGT/DBA gels could be used as photovoltaic, dielectric, and actuator materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 829–832     

Photo‐induced thiol‐ene polysulfide‐crosslinked materials with tunable thermal and mechanical properties

Photo‐induced thiol‐ene crosslinked polymeric networks have been extensively explored in constructing a variety of new materials with enhanced mechanical properties for optical, biomedical, and sensing applications. Toward the broad applications, however, tunable mechanical properties are greatly desired. Here, an effective approach utilizing high‐molecular‐weight methacrylate copolymers having pendant thiol and vinyl groups (MCPsh and MCPenes) to modulate thermal and mechanical properties of photo‐induced thiol‐ene crosslinked materials is reported. The MCP copolymers are synthesized by an industrially friendly polymerization method, followed by post‐modification including either a facile coupling reaction or reductive cleavage. Upon UV irradiation, thiol‐ene reactive blends of MCPsh and MCPenes yield highly crosslinked materials through the formation of flexible sulfide linkages. These polysulfide‐crosslinked materials based on rigid MCP backbones exhibit enhanced mechanical properties. Further, their thermal and mechanical properties are tuned by modulating monomer compositions of MCPs as well as varying numbers of pendant SH or vinyl groups (i.e., extent of crosslinking densities). This approach is versatile and effective for development of high performance polymeric materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3060–3068     

Nanocomposite smart hydrogels with improved responsiveness and mechanical properties: A mini review

Responsive hydrogels have the ability to change their volume, transparency, or other properties in response to external chemical and/or physical stimuli. The responsiveness properties including responsive rate and degree, as well as mechanical properties such as Young's modulus, toughness, breaking strength, and breaking strain are crucial parameters of the smart hydrogels that determine the scope of hydrogel applications such as soft actuators, artificial muscles, and tissue engineering scaffolds. In this paper, the development of the nanocomposite smart hydrogels, which can achieve both improved responsiveness and mechanical properties, is reviewed. First, the fabrication approaches for building the nanocomposite networks by doping organic or inorganic nanomaterials via crosslinking or blending strategies are introduced. Then, the mechanisms used to improve both responsiveness and mechanical properties of nanocomposite responsive hydrogels are discussed. Finally, the perspectives as well as current challenges of such nanocomposite responsive hydrogels are addressed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1306–1313     

Transient bioelectronics: Electronic properties of silver microparticle‐based circuits on polymeric substrates subjected to mechanical load

Transient soft bioelectronics are capable of forming conformal contacts with curvilinear surfaces of biological host tissues and organs. Such systems are often subject to continuous static and dynamic loads from the biological host. In this article, we present investigation of electronic attributes of transient soft bioelectronic circuits subjected to mechanical force and influence of substrate's transiency on the transiency of the whole device; also, characterize and quantify loss of functionality in triggered devices. Variations in the electrical conductivity of circuits as a function of applied mechanical load was used as a means to deduce electronic characteristics under stress. The experimental results suggest that there exists a correlation between electronic properties of circuits and applied mechanical strain; no clear correlation was, however, observed between electronic properties of circuits and frequency of the applied dynamic load. Control over transiency rate of identical circuits utilizing the transiency characteristics of the poly(vinyl alcohol)l‐based substrates is also studied and demonstrated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1603–1610     

New nanohybrids of poly(ε‐caprolactone) and a modified Mg/Al hydrotalcite: Mechanical and thermal properties

Novel composites based on poly(ε‐caprolactone) (PCL) and an organically modified layer double hydroxide (LDH) obtained using the melt‐extrusion technique have been characterized through structural, thermal, and mechanical analyses. Although exfoliation has not been achieved and despite the very low content of filler (from 1 to 3% by weight), significant enhancements are obtained in the physical and mechanical properties of the composites with respect to neat PCL. As a consequence, LDHs can substitute other nanofillers, in particular, cationic clays for polymeric matrices. They can be modified by a large number of organic anions, generally more numerous than the cationic ones, and can be mixed in very simple ways with polymers. This makes such nanofillers suitable to obtain new hybrid materials for a series of applications, from active food packaging to intelligent materials for biomedical device, for example, controlled drug release. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 945–954, 2007