Molecular organization and viscosity of a thin film of molten polymer between two surfaces as probed by force measurements

Measurements are presented of the force between two molecularly smooth mica surfaces immersed in liquid poly(dimethylsiloxane) (Dow Corning 200 of nominal viscosity 50 cS) over a range of film thicknesses from 3 to 200 nm. There is a repulsion, attributed to conformational restrictions, when the polymer molecules are confined to a gap less than about 15 nm thick. In extremely thin films (<5 nm) the force is an oscillatory function of thickness with a repeat spacing corresponding to the width of the polymer molecule, which suggests that the polymer segments are arranged in layers near the solid surfaces. Dynamic force measurements show that the polymer has a viscosity equal to its bulk value even in very thin films, but a region next to each surface, only about one radius of gyration thick, does not flow. Saturation of the polymer with water destabilizes the film when it is very thin.

Efficient design of polarization insensitive polymer optical waveguide devices considering stress-induced effects

We present an approach for the efficient design of polarization insensitive polymeric optical waveguide devices considering stress-induced effects. In this approach, the stresses induced in the waveguide during the fabrication process are estimated first using a more realistic model in the finite element analysis. Then we determine the perturbations in the material refractive indices caused by the stress-optic effect. It is observed that the stresses cause non-uniform optical anisotropy in the waveguide materials, which is then incorporated in the modal analysis considering a multilayer structure of waveguide. The approach is exploited in the design of a Bragg grating on strip waveguide. Excellent agreement between calculated and published experimental results confirms the feasibility of our approach in the accurate design of polarization insensitive polymer waveguide devices.

RAFT controlled synthesis of graphene/polymer hydrogel with enhanced mechanical property for pH-controlled drug release

A pH-sensitive, mechanically strong and thermally stable graphene/poly (acrylic acid) (graphene/PAA) hydrogel was prepared via reversible addition fragmentation transfer (RAFT) polymerizations in the presence of a cross-linking agent. The RAFT agent was covalently coupled onto graphene basal planes via an esterification reaction, with benzoic acid functionalities pre-attached on graphene with its aryl diazonium salt precursor. AFM and SEM analysis revealed the successful preparation of single layered graphene sheets and graphene/polymer hydrogels with pH controlled porous structures. Attenuated total reflection infrared (ATR-IR) and thermogravimetric analyzer (TGA) verified the successful stepwise preparation of graphene/PAA hydrogel. This graphene/PAA hydrogel was pH-sensitive and more mechanically elastic than the PAA hydrogel prepared without graphene. The pH sensitivity of the hydrogel was further utilized for controlled drug release. Doxorubicin was chosen as a model drug and loaded into the hydrogels. The drug loading and release experiment indicated that this hydrogel can be used to efficiently control drug release in the intestine environment (pH = 7.4), better than release in a more acidic environment.© 2013 Elsevier Ltd. All rights reserved.

Nonlinear large deformation dynamic analysis of electroactive polymer actuators

Electroactive polymers have attracted considerable attention in recent years due to their sensing and actuating properties which make them a material of choice for a wide range of applications including sensors, biomimetic robots, and biomedical micro devices. This paper presents an effective modeling strategy for nonlinear large deformation (small strains and moderate rotations) dynamic analysis of polymer actuators. Considering that the complicated electro-chemo-mechanical dynamics of these actuators is a drawback for their application in functional devices, establishing a mathematical model which can effectively predict the actuator's dynamic behavior can be of paramount importance. To effectively predict the actuator's dynamic behavior, a comprehensive mathematical model is proposed correlating the input voltage and the output bending displacement of polymer actuators. The proposed model, which is based on the rigid finite element (RFE) method, consists of two parts, namely electrical and mechanical models. The former is comprised of a ladder network of discrete resistive-capacitive components similar to the network used to model transmission lines, while the latter describes the actuator as a system of rigid links connected by spring-damping elements (sdes). Both electrical and mechanical components are validated through experimental results.

Graphene and graphitic derivative filled polymer composites as potential sensors

Graphite and numerous graphitic-derived micro- and nano-particles have gained importance in current materials science research. These two-dimensional sheets of sp(2)-hybridized carbon atoms remarkably influence the properties of polymers. Graphene mono-layers, graphene oxides, graphite oxides, exfoliated graphite, and other related materials are derived from a parental graphite structure. In this review, we focus primarily on the role of these fillers in regulating the electrical and sensing properties of polymer composites. It has been demonstrated that the addition of an optimized mixture of graphene and or its derivatives to various polymers produces a record-high enhancement of the electrical conductivity and achieved semiconducting characteristics at small filler loading, making it suitable for sensor manufacture. Promising sensing characteristics are observed in graphite-derived composite films compared with those of micro-sized composites and the properties are explained mainly based on the filler volume fraction, nature and rate of dispersion and the filler polymer interactions at the interface. In short, this critical review aims to provide a thorough understanding of the recent advances in the area of graphitic-based polymer composites in advanced electronics. Future perspectives in this rapidly developing field are also discussed.

Addition of biological functionality to poly(epsilon-caprolactone) films

Biodegradable polyesters such as poly(epsilon-caprolactone) (PCL) have a number of biomedical applications; however, their usage is often limited by a lack of biological functionality. In this paper, a PCL-based polymer containing pendent groups activated by 4-nitrophenyl chloroformate (NPC) and reactive toward primary amines has been cast into thin films. The reactivity of the films toward poly(l-lysine) and the cell adhesion peptide, GRGDS, was assessed, and their cell adhesive capabilities were characterized. ATR-FTIR analysis found that NPC functional groups were present on the surface of the cast film, and the synthesis, conjugation, and visualization of a fluorescent molecule on these films further demonstrated the success of this functionalization methodology. The immersion of these films into a solution of either poly(l-lysine) (PLL) or GRGDS in PBS (pH 7.4) and subsequent 3T3 fibroblast adhesion studies demonstrated significant improvement in cell adhesion and spreading over films cast from unmodified PCL. This investigation has shown that this novel NPC-containing polymer can be utilized in many applications where increased cellular adhesion is required, or the coupling of specific molecules to polymer surfaces is of interest.

Conjugation of bioactive groups to poly(lactic acid) and poly[(lactic acid)-co-(glycolic acid)] films

A novel PLA-based polymer containing reactive pendent ketone or hydroxyl groups was synthesized by the copolymerization of L-lactide with epsilon-caprolactone-based monomers. The polymer was activated with NPC, resulting in an amine-reactive polymer which was then cast into thin polymeric films, either alone or as part of a blend with PLGA, before immersion into a solution of the cell adhesion peptide GRGDS in PBS buffer allowed for conjugation of GRGDS to the film surfaces. Subsequent 3T3 fibroblast cell adhesion studies demonstrated an increase in cellular adhesion and spreading over films cast from unmodified PLGA. Hence the new polymer can be used to obtain covalent linkage of amine-containing molecules to polymer surfaces.

Conductive polymer coatings

Conducting polymer-coated textiles possess a wide range of electrical properties. The surface resistivity is influenced by concentrations of the reactants, the thickness of the coating, the nature of the substrate surface, the extent of penetration of the polymer into the textile structure, and the strength of the binding of the coating to the textile surface. Low resistivity in fabric results from highly doped thicker coatings that penetrate well into the textile structure, thus enabling good electrical contact between fibers. Microwave studies showed that conductive textiles are not highly effective as electromagnetic shielding materials owing to their medium-level conductivity and therefore large skin depth. Combined with the fact that coatings are around 1. ?m thick, they cannot act as effective reflective barriers to electromagnetic radiation. However, because they are highly absorptive in the microwave region, absorbing materials can be designed in conjunction with conductive textiles. Study of Fourier transform-infrared spectra of aged polypyrrole films has shown an increase in intensity of an ?,?-unsaturated conjugated carbonyl peak that may be linked to the increase in resistance but cannot be the only factor, because the rate of electrical decay was influenced by several factors such as temperature, the type and concentration of the dopant, and the aging time, all of which signify a complex mechanism of degradation of conductivity. Degradation is a major concern for conductive textile systems that needs to be characterized before considering these materials for potential applications.

Molecular mechanism of stabilization of thin films for improved water evaporation protection

All-atom molecular dynamics simulations and experimental characterization have been used to examine the structure and dynamics of novel evaporation-suppressing films where the addition of a water-soluble polymer to an ethylene glycol monooctadecyl ether monolayer leads to improved water evaporation resistance. Simulations and Langmuir trough experiments demonstrate the surface activity of poly(vinyl pyrrolidone) (PVP). Subsequent MD simulations performed on the thin films supported by the PVP sublayer show that, at low surface pressures, the polymer tends to concentrate at the film/water interface. The simulated atomic concentration profiles, hydrogen bonding patterns, and mobility analyses of the water-polymer-monolayer interfaces reveal that the presence of PVP increases the atomic density near the monolayer film, improves the film stability, and reduces the mobility of interfacial waters. These observations explain the molecular basis of the improved efficacy of these monolayer/polymer systems for evaporation protection of water and can be used to guide future development of organic thin films for other applications.