Polymer Network Films Research Articles

Accordion‐like Actuators of Multiple 3D Patterned Liquid Crystal Polymer Films

This work describes the fabrication, characterization, and modelling of liquid crystalline polymer network films with a multiple patterned 3D nematic director profile, a stimuli‐responsive material that exhibits complex mechanical actuation under change of temperature or pH. These films have a discrete alternating striped or checkerboard director profile in the plane, and a 90‐degree twist through the depth of the film. When actuated via heating, the striped films deform into accordion‐like folds, while the film patterned with a checkerboard microstructure buckles out‐of‐plane. Furthermore, striped films are fabricated so that they also deform into an accordion shaped fold, by a change of pH in an aqueous environment. Three‐dimensional finite element simulations and elasticity analysis provide insight into the dependence of shape evolution on director microstructure and the sample's aspect ratio.

An annulus fibrosus closure device based on a biodegradable shape-memory polymer network

Injuries to the intervertebral disc caused by degeneration or trauma often lead to tearing of the annulus fibrosus (AF) and extrusion of the nucleus pulposus (NP). This can compress nerves and cause lower back pain. In this study, the characteristics of poly(d,l-lactide-co-trimethylene carbonate) networks with shape-memory properties have been evaluated in order to prepare biodegradable AF closure devices that can be implanted minimally invasively. Four different macromers with (d,l-lactide) to trimethylene carbonate (DLLA:TMC) molar ratios of 80:20, 70:30, 60:40 and 40:60 with terminal methacrylate groups and molecular weights of approximately 30 kg mol−1 were used to prepare the networks by photo-crosslinking. The mechanical properties of the samples and their shape-memory properties were determined at temperatures of 0 °C and 40 °C by tensile tests- and cyclic, thermo-mechanical measurements. At 40 °C all networks showed rubber-like behavior and were flexible with elastic modulus values of 1.7–2.5 MPa, which is in the range of the modulus values of human annulus fibrosus tissue. The shape-memory characteristics of the networks were excellent with values of the shape-fixity and the shape-recovery ratio higher than 98 and 95%, respectively. The switching temperatures were between 10 and 39 °C. In vitro culture and qualitative immunocytochemistry of human annulus fibrosus cells on shape-memory films with DLLA:TMC molar ratios of 60:40 showed very good ability of the networks to support the adhesion and growth of human AF cells. When the polymer network films were coated by adsorption of fibronectin, cell attachment, cell spreading, and extracellular matrix production was further improved. Annulus fibrosus closure devices were prepared from these AF cell-compatible materials by photo-polymerizing the reactive precursors in a mold. Insertion of the multifunctional implant in the disc of a cadaveric canine spine showed that these shape-memory devices could be implanted through a small slit and to some extent deploy self-sufficiently within the disc cavity.

Development of novel chitosan-poly(N,N-diethylacrylamide) IPN films for potential wound dressing and biomedical applications

Novel interactive and thermoresponsive interpen- etrating polymer network (IPN) films, which are transparent, permeable to oxygen, and have the potential to be easily stripped from a wound bed, were synthesised using rapid photopolymerisation and crosslinking of DEAAm in the pres- ence of chitosan. This study provides the first evaluation and optimisation of a UV-polymerised chitosan-PDEAAm IPN composite film for application in wound dressings. FTIR spec- troscopy and DSC analysis were used to initially characterise the resulting films. Modulated differential scanning calorimetry results showed that the dressings exhibited lower critical solu- tion temperatures in the desired range, while the samples were also observed to undergo temperature-dependent swelling be- haviour. This thermosensitive property would potentially allow the dressings to be easily detachable, which would enable frequent dressing changes if desired without causing further injury to healing tissues. Furthermore, the water content values recorded are in the typical and desired ranges for commercial wound dressings.

Quantification of Protein Adsorption on Polyglycerol-based Polymer Network Films

ABSTRACTNeutral, hydrophilic, polymer-based architectures are widely investigated for a wide range of biomedical applications from drug-conjugates to delivery systems and scaffolds for regenerative therapies. In most cases, it is crucial that biomaterials provide a blank, inert background in order to hinder unspecific cell-material interactions so that protein mediated biological events leading to foreign body reactions are prevented. Hydrophilic polyglycerol-based polymer network films are a recently developed class of amorphous macroscopic materials, which offer great versatility in design and control of resultant properties. In this study, protein adsorption on polyglycerol-based polymer network films is investigated by using Micro BCA protein assay for three types of proteins having critical roles in the human body, and various copolymer networks with differing sidechains and crosslink densities.

Conjugated Polymer Network Films of Poly(p-phenylene vinylene) with Hole-Transporting Carbazole Pendants: Dual Photoluminescence and Electrochromic Behavior

A series of poly(p-phenylene vinylene) (PPV) copolymers functionalized with hole-transport and electrochemically active carbazole units as pendant moieties is reported. These polymers exhibit photoluminescence properties by virtue of the PPV analogous backbone. They were also designed as precursor polymer bearing the electroactive carbazole group to form conjugated polymer network (CPN) films by electrodeposition. The electrochemical polymerization of the pendant units eventually lead to a dual property electro-optically active thin film - photoluminescence (PL) behavior that can be attenuated with CPN formation, and a reversible doping and dedoping processes at controlled potentials that lead to an electrochromic behavior. This reveals the ability to incorporate complementary optical and electro-optical properties within the same film using the CPN approach. It should be possible to design and synthesize other PPV π-conjugated polymers with efficient pendant hole-transport groups exhibiting tunable PL and electrochromism with cross-linking.

PH-, Sugar-, and Temperature-Sensitive Electrochemical Switch Amplified by Enzymatic Reaction and Controlled by Logic Gates Based on Semi-Interpenetrating Polymer Networks

Phenylboronic acid (PBA) moieties are grafted onto the backbone of poly(acrylic acid) (PAA), forming the PAA-PBA polyelectrolyte. The semi-interpenetrating polymer network (semi-IPN) films composed of PAA-PBA and poly(N,N-diethylacrylamide) (PDEA) were then synthesized on electrode surface with entrapped horseradish peroxidase (HRP), designated as PDEA-(PAA-PBA)-HRP. The films demonstrated reversible pH-, fructose-, and thermo-responsive on-off behavior toward electroactive probe K(3)Fe(CN)(6) in its cyclic voltammetric (CV) response. This multiswitchable CV behavior of the system could be further employed to control and modulate the electrochemical reduction of H(2)O(2) catalyzed by HRP immobilized in the films with K(3)Fe(CN)(6) as the mediator in solution. The responsive mechanism of the system was also explored and discussed. The pH-sensitive property was attributed to the electrostatic interaction between the PAA component of the films and the probe at different pH; the thermo-responsive behavior originated from the structure change of PDEA hydrogel component of the films with temperature; the fructose-sensitive property was ascribed to the structure change of the films induced by the complexation between the PBA constituent and the sugar. This smart system could be used as a 3-input logic network composed of enabled OR (EnOR) gates in chemical or biomolecular computing by combining the multiresponsive property of the films and the amplification effect of bioelectrocatalysis and demonstrated the potential perspective for fabricating novel multiswitchable electrochemical biosensors and bioelectronic devices.

Polyglycerol-based polymer network films for potential biomedical applications

Synthetic polymeric materials are established as being central to many modern approaches to medical treatments such as biomaterial induced tissue regeneration or drug eluting implants. Cytocompatible, antifouling materials, based on hydrophilic polymers such as poly(ethylene glycol), have been widely studied as a ‘blank canvas’ substrate; it is possible to apply various bioactive ligands to elicit specific tissue and cell responses. In recent years, branched polyglycerols have gained attention as a viable alternative to PEG as a protein-resistance providing chemical moiety. To this end we have embarked on the preparation of bulk polyglycerol-based films, which are readily synthesized from abundant starting materials, with the aim of evaluating their as yet undiscovered potential as macroscopic biomaterials. Herein we report syntheses, as well as mechanical, and rheological properties of a series of polyglycerol-based polymer networks. Polymeric films produced are highly crosslinked, have high thermal stability, and are flexible with thermal glass transition temperatures below body temperature.

Preparation and Properties of Interpenetrating Polymer Network Films from Prevulcanized Natural Rubber Latex/Chitosan Blends

The acidfied sulfur-prevulcanized natural rubber (NR) latex was mixed with 1～20 parts per hundred rubber (phr) of a 2wt% solution of chitosan (CS) in 1wt% acetic acid, then cast to preapare a series of NR/CS semi-interpenetrating polymer network (semi-IPN) films; the NR/CS semi-IPN films were further treated with 0.5wt% glutaraldehyde（GA）solution for respectively 1, 3 and 6h to obtain NR/CS IPN films. The mechanical properties and swelling behavours in various media of water, toluene and reference olis of IRM901 and IRM 903 of these films were studied and compared with those pure sulfur-prevulcanized natural rubber latex (SNRL) film. Results showed that, NR/CS IPN films with better mechanical properties could be obained by treating the 24h-leached NR/CS semi-IPN films than by treating directly the unleached ones with 0.5wt% GA solution; the tear strength, 300% modulus, Shore A hardness, hydrophilicity and resistance to non-polar solvents and oil of the SNRL films increased with the incorporation of CS, while the NR/CS IPN films exhibited better than the NR/CS semi-IPN films, especially in tear strength enhancement; the tensile strength and elongation at break of NR/CS semi-IPN and IPN films gradually decreased with the increase in CS content. However, most of the elasticity of pure NR vulcanizate could be reserved, when the CS content was not greater than 15 phr.

Electropolymerizable Terthiophene-Terminated Poly(aryl ether) Dendrimers with Naphthalene and Perylene Cores

We describe the synthesis and characterization of a new series of poly(aryl ether) dendrimers with both donor and acceptor moieties. By incorporating p-type terthiophene and n-type perylene and naphthalene diimides into one molecule, we have achieved a dual electrochromic material. These dendrimers were designed to act as electrochemically active precursor polymers, which bear the electroactive terthiophene group that can be cross-linked electrochemically to form conjugated polymer network (CPN) films. Characterization of the optical and redox properties shows that it is possible to incorporate donor and acceptor moieties in the same molecule with retention of doping properties. The films made by electrochemical polymerization are highly active in both the p- and n-doping processes and have been investigated by spectroelectrochemical methods.

Intercalative Poly(carbazole) Precursor Electropolymerization within Hybrid Nanostructured Titanium Oxide Ultrathin Films

A protocol for nanostructuring and electropolymerization of a hybrid semiconductor polycarbazole-titanium oxide ultrathin film is described. Ultrathin (<100 nm) films based on polycarbazole precursor polyelectrolytes and titanium oxide (TiOx) have been fabricated by combining the layer-by-layer (LbL) and surface sol-gel layering techniques. Film growth was followed and confirmed through UV-vis spectroscopy, ellipsometry and quartz crystal microbalance with dissipation (QCM-D). Subsequent anodic electrochemical oxidation of the carbazole pendant units afforded a conjugated polymer network (CPN) film within intercalating TiOx layers of cross-linked and π-conjugated carbazole units. Cyclic voltammetry (CV), UV-vis, and fluorescence spectroscopy measurements confirmed this process. The LbL-driven polyelectrolyte deposition process resulted in a quantified electrochemical response, proportional to the number of layers, while the TiOx acted as a dielectric spacer limiting electron transfer kinetics and attenuating energy transfer in fluorescence. Electro-optical properties were compared with other polycarbazole thin film materials with respect to bandgap energy (Eg). The straightforward protocol in film nanostructuring and barrier/dielectric properties of the inorganic oxide slab (denoted here as, TiOx) should enable applications in organic light-emitting diodes (OLEDs), dielectric mirrors, planar waveguides, and photovoltaic devices for these hybrid ultrathin films.

Pd @ PEG-PU polymer networks: A convenient catalyst for hydrogenation and Suzuki coupling reactions

Polyethyleneglycol-polyurethane (PEG-PU) polymer network films with sodium tetrachloropalladate were fabricated by solution casting technique. The incorporated palladium ions were reduced using sodium borohydride to obtain zero-valent (metallic) palladium in the films. These films were characterized by X-ray diffraction, Fourier transform-infra red spectroscopy, atomic absorption spectroscopy and X-ray photoelectron spectroscopy for their structure and chemical composition. The films containing palladium metal are found to be highly efficient toward hydrogenation of a number of unsaturated organic compounds and Suzuki coupling reactions of haloarenes. The novelty of this catalyst system is the incorporation of palladium in the polymer network that renders the catalyst system's reusability because there is no leaching of the metal from the polymer matrix and as the catalyst system is in the form of a compact film it can be easily separated from the reaction mixture and can be reused.

Cellulose–chitosan interpenetrating polymer network for electro‐active paper actuator

AbstractIn this article, the cellulose‐chitosan interpenetrating polymer network (IPN) films were prepared and fabricated as the electro‐active paper actuator. The characteristics of the cellulose–chitosan IPN films were examined by SEM, FT‐IR, XRD, DSC, and tensile test. The performance of the IPNs based actuator was evaluated in terms of bending displacement with respect to the actuation frequency, voltages, humidity levels, chitosan content, and time variation. It was observed that with chitosan content increasing in the IPNs, the crystallinity decreased and the network became denser, which caused the Young's modulus to increase. Chitosan content in IPNs also significantly affected the bending performance. The optimum IPN weight ratio of cellulose and chitosan was 60 : 40. The maximum bending displacement of 7.2 mm was found at 80% relative humidity level. In terms of durability, the bending lifetime at 70% humidity level was about 10 h with 17% performance degradation. More issues on the actuator performance and durability are addressed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Synthesis and characterization of polyurethane hybrids: Influence of the polydimethylsiloxane linear chain and silsesquioxane cubic structure on the thermal and mechanical properties of polyurethane hybrids

AbstractThe structural effects of polydimethylsiloxane (PDMS) or polyhedral oligosilsesquioxanes (POSSs) on the thermomechanical properties of polyurethane (PU) networks were studied. An ester–amine‐functionalized silsesquioxane and a PDMS macromer were synthesized, and the macromer (10 wt %) was crosslinked with the PU prepolymer to obtain PU networks. The synthesized macromers and hybrids were characterized with Fourier transform infrared, 1H‐NMR, 13C‐NMR, and 29Si‐NMR spectroscopy techniques. The influence of POSS cubes on the thermal and mechanical properties of the polymer network films was studied comparatively with the similarly functionalized PDMS linear chain via thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA) measurements. The degradation pattern of the POSS‐incorporated PU nanocomposites was almost the same as that of the PU network synthesized from the linear PDMS macromer. The differences in the char yields and activation energies of the hybrids reflected the enhancement of the thermal properties of the nanohybrids. The TGA and DSC curves of the macromers suggested that the thermal properties of the macromers not only depended on either the PDMS or POSS inorganic core but also depended on the organic peripheral attached to the inorganic core. The glass‐transition temperatures of the nanohybrids were higher than those of the linear‐PDMS‐incorporated hybrids. The storage modulus values increased 3‐fold upon the incorporation of POSS rigid groups into the PU hybrids in comparison with the flexible PDMS‐chain‐incorporated PU hybrids. The DMA measurements showed a long‐range rubbery plateau region for all the PU hybrids, with high storage modulus and tan δ values showing the structural homogeneity of the crosslinked networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Grafting Hole-Transport Precursor Polymer Brushes on ITO Electrodes: Surface-Initiated Polymerization and Conjugated Polymer Network Formation of PVK

We have utilized surface-initiated polymerization (SIP) to functionalize the conducting transparent electrode, indium tin oxide (ITO) with polyvinylcarbazole (PVK) brushes. Atomic force microscopy (AFM) imaging revealed smooth domains of grafted PVK and the composition, confirmed by X-ray photoelectron spectroscopy (XPS) measurements. The PVK is an electrochemically cross-linkable precursor by virtue of the pendant carbazole group and thus capable of forming conjugated polymer network (CPN) films. The electrochemical behavior and oligocarbazole CPN formation were evaluated by cyclic voltammetry (CV) measurements. The covalent linkage of the PVK brush allowed for a direct electroluminescent device preparation on SIP modified ITO in which PVK acts as a hole-transporting layer. In this case, the polyfluorene copolymer can be easily spin-casted on top of the grafted PVK without dissolution problems. This resulted in an improved polymer light-emitting diode (PLED) device behavior where the EL polymer layer can be simply solution cast on the modified ITO irrespective of solubility.

Preparation and characterization of interpenetration polymer network films based on poly(vinyl alcohol) and poly(acrylic acid) for drug delivery

AbstractA series of full interpenetrating polymer network (full‐IPN) films of poly(acrylic acid) (PAA)/poly (vinyl alcohol) (PVA) were prepared by radical solution polymerization and sequential IPN technology. Attenuated total reflectance‐Fourier transform infrared spectroscopy, swelling properties, mechanical properties, morphology, and glass transition temperature of the films were investigated. FTIR spectra analysis showed that new interaction hydrogen bonds between PVA and PAA were formed. Swelling property of the films in distilled water and different pH buffer solution was studied. Swelling ratio increased with increasing PAA content of IPN films in all media, and swelling ratio decreased with increasing PVA crosslink degree. Tensile strength and elongation at break related not only to the constitution of IPNs but also to the swelling ratio of IPNs. Mechanical property of glutaraldehyde (0.5%) for poly(vinyl alcohol) crosslinking was better than that of glutaraldehyde (1.0%). DSC of the IPN films showed only a single glass transition temperature (Tg) for each sample, and Tg data showed a linear relationship with network composition. Morphology was observed a homogeneous structure, indicating the good compatibility and miscibility between PAA and PVA. Potential application of the IPN films in controlled drug delivery was also examined using crystal violet as a model drug. The release rate of the drug was higher at 37°C than 25°C for all IPNs and also increased slightly with decreasing of poly(acrylic acid) content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Ultrathin Conjugated Polymer Network Films of Carbazole Functionalized Poly(p-Phenylenes) via Electropolymerization

Ultrathin films of a cross-linked and chemically distinct conjugated poly(p-phenylene) network via electropolymerization are described. The amphiphilic network precursor was synthesized by incorporating the alkoxy carbazole group (-O(CH2)5Cb) to a poly(p-phenylene) (C6PPPOH) backbone. In order to investigate the combined thin film electrochemical and photophysical properties of poly(p-phenylene)s and polycarbazole conjugated polymers, C6PPPC5Cb was deposited on substrates using the Langmuir Blodgett Kuhn (LBK) method. The monolayer isotherm of the polymer, C6PPPC5Cb, showed a liquid expanded region slightly different from the parent polymer C6PPPOH. Multilayers (up to 30 layers) were transferred to different substrates such as quartz, gold coated LaSFN9 and ITO substrates for analysis. For conversion to a conjugated polymer network (CPN) film, the electroactive carbazole group was electropolymerized using cyclic voltammetry (CV) resulting in polycarbazole linking units. The differences in the film properties and corresponding changes in the electrochemical behavior indicate the importance of film thickness and electron/ion transport process in cross linked network films. From the electrochemical studies, the scan rate was found to have a considerable effect on electropolymerization with higher oxidation and reduction peak values found for the rigid network polymer compared to the uncrosslinked polymers.

Hydrogel-elastomer composite biomaterials: 2. Effects of aging methacrylated gelatin solutions on the preparation and physical properties of interpenetrating polymer networks

This study was conducted to understand the effects of aging methacrylated gelatin solutions on the properties of gelatin-HydroThane Interpenetrating Polymer Network (IPN) films. The latter were prepared from methacrylated gelatin solutions that were either freshly made or stored at different concentrations and temperatures for various periods. The morphology, swelling stability and mechanical properties of the IPNs were then accordingly characterized. The IPNs prepared with aged solutions showed a reduced phase separation; changed from a network-like structure to a continuous phase structure; and demonstrated higher swelling stabilities and higher elasticity under optimal aging conditions, compared to the IPN prepared with a fresh methacrylated gelatin solution. An increase in viscosity and a change in phase transition of aged methacrylated gelatin solutions were also observed, presumably due to the physical structuring of methacrylated gelatin chains (e.g., by the formation of a helix structure), thus altering the resulting IPN characteristics. A better understanding of the effects of aging methacrylated gelatin solution on the formation and properties of gelatin-HydroThane IPNs should enable us to further develop our composite biomaterials for different dressing applications.

Superlattices of organic/inorganic semiconductor nanostructures from liquid-crystal templates

A lyotropic liquid-crystal-templated superlattice of inorganic CdSe semiconductor nanostructures within an organic semiconductor polymer-network film was fabricated by a self-assembly process. The film is characterized with small-angle x-ray diffraction experiments and ultraviolet-visible absorption measurements. Empirical pseudopotential calculations of the effective CdSe nanocrystal band gap show that the experimental observations are consistent with the formation of CdSe nanostructures inside lyotropic liquid-crystal nanotubes. A potential application of these nanocomposite supramolecular arrays is demonstrated via a photoconductive device.

Quantitative Electrochemical and Electrochromic Behavior of Terthiophene and Carbazole Containing Conjugated Polymer Network Film Precursors: EC-QCM and EC-SPR

A comparative analysis of the copolymerization behavior between an electro-active terthiophene and a carbazole moiety of a conjugated polymer precursor was investigated using electrochemical and hyphenated electrochemical methods. Five different precursor polymers were first synthesized and characterized using NMR, IR, and GPC. The polymers include homopolymers of individual electro-active groups (P3T, P-CBZ) and different compositions of 25, 50, and 75% (P3TC-25, P3TC50, and P3TC-75) with respect to the two electro-active groups. Since the oxidation potentials of terthiophene and carbazole lie very close to each other, highly cross-linked copolymer films of varying extent were produced depending on the composition. The copolymerization extent was found to be dependent primarily on the amount of the terthiophene, which in this case provided for a more efficient carbazole polymerization and copolymerization than with just carbazole alone (homopolymer). The extent of copolymerization, electrochromic properties, and viscoelastic changes was quantitatively investigated using a number of hyphenated electrochemistry techniques: spectro-electrochemistry, electrochemical quartz crystal microbalance studies (EC-QCM), and electrochemical surface plasmon resonance spectroscopy (EC-SPR). Each technique revealed a unique aspect of the electrocopolymerization behavior that was used to define structure-property relationships and the deposition/copolymerization mechanism.

Distortion and unwinding of the helical structure in polymer-stabilized short-pitch ferroelectric liquid crystal

We report the effect of an anisotropic polymer network formed from an achiral photoreactive monomer in a short-pitch chiral SmC* phase on the distortion and the unwinding of the helical structure of the ferroelectric phase. The electro-optical behaviour and ferroelectric properties were experimentally determined for films containing various polymer concentrations. The critical field, E(u), for the transition from the distorted structure to the homogeneous state was measured as a function of polymer concentration. A linear increase of E(u) versus polymer concentration was observed, showing that the helical structure of the short-pitch SmC* phase was stabilized by the polymer network. This behaviour was expected to be a consequence of the increase of the apparent elastic constants of the ferroelectric liquid crystal stabilized by the anisotropic polymer network films. The polymer network morphology was investigated using atomic-force microscopy, revealing a twisted structure of the polymer fibers. This twisted structure was transferred onto a polymer network during the polymerization process within a short-pitch SmC* phase. The increase of the apparent elasticity can then be interpreted by a strong interaction between polymer network and the liquid-crystal molecules. From our experimental data, the coupling coefficient, W(p), characterizing this interaction was evaluated for all studied polymer concentrations.