Soluble and conductive polypyrrole copolymers containing silicone tegomers

Soluble and processable conductive copolymers of silicone tegomers and pyrrole were developed. This was easily accomplished by the oxidative polymerization of pyrrole monomer by Ce(IV) salt in the presence of silicone tegomers with hydroxyl chain ends. The resulting copolymers were soluble in dimethylformamide. The products were characterized by Fourier transform infrared, ¹H‐NMR, and four‐point probe conductivity, and their surface properties were investigated with contact‐angle measurements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2896–2901, 2003     

Bioresorbable and bioactive polymer/Bioglass® composites with tailored pore structure for tissue engineering applications

An overview about the development of porous bioresorbable composite materials for applications as scaffolds in tissue engineering is presented. A thermally induced phase separation method was developed to fabricate porous foam-like structures of poly(lactide-co-glycolide) (PLGA) containing bioactive glass particle additions (up to 50 wt.%) and exhibiting well-defined, oriented and interconnected porosity. The in vitro bioactivity and the degradability of the composite foams were investigated in contact with phosphate buffer saline (PBS). Weight loss, water absorption and molecular weight measurements were used to monitor the polymer degradation after incubation periods of up to 7 weeks in PBS. It was found that the presence of bioactive glass retards the polymer degradation rate for the time period investigated. The present results show a way of controlling the in vitro degradation behaviour of PLGA porous composite scaffolds by tailoring the concentration of bioactive glass.     

High‐Performance,Monolithic Polyaniline Electrochemical Actuators

New polyaniline (PANI) asymmetric membranes were fabricated using a phase‐inversion technique with hexane as the coagulation bath. These membranes exhibit a dense structure with macrovoids distributed asymmetrically throughout the cross‐section. A stress–strain study demonstrated that the Young's modulus (1.421 GPa) and strain at break (7.6 %) of the new PANI asymmetric membranes prepared from hexane are approximately 12 and 4 times higher, respectively, than the values reported previously for the PANI integrally skinned asymmetric membranes (ISAMs) (123 MPa Young's modulus and 1.8 % strain at break). Furthermore, monolithic electrochemical actuators based on a single PANI asymmetric membrane were constructed, and a bending movement of up to 20 Hz was experimentally recorded in a hydrochloric acid aqueous solution. A lifetime of over 329 500 cycles was determined for these actuators at a ± 2° angular displacement (5 Hz). The lifetime is limited by a bending fatigue that creates a transversal crack on the PANI membrane at the air–water interface. Control over the actuator movement is also manifested by the linear dependences of the bending angle on the charge and of the angular velocity on the current. These relationships are independent of both the kind of applied electric signal and the frequency used.     

Measuring and modeling the rheological data of diglycidylether of bisphenol‐A during polymerization for finite element analyses

Finite element analyses (FEA) of thermosets are often performed on the basis of rheological data for fully cured resin. For the FEA of thermosets during curing, a material model is established and a technique is demonstrated, which allows the rheological data of the linear viscoelastic material to be derived. As the moduli are sensitive to conversion, all measured properties are related to temperature and conversion. Therefore the basis for the rheological data has to be a suitable reaction kinetic. Based on the kinetics shear and compression properties are measured independently and modeled mathematically with the focus to gain a formulation, which is suitable for FEA. The considered time constants are in the range between one second and one month as these times are relevant for the investigated relaxation times. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1868–1872, 2003     

Repair of Cracked Aluminum Overhead Sign Structures with Glass Fiber Reinforced Polymer Composites

Transportation departments have been using aluminum overhead sign structures since the 1950s. It is well documented that cracks develop in the welds between diagonal and chord members due to fatigue stresses from wind-induced vibration of the slender members. The cracks propagate to complete failure of the members, which can cause collapse of the truss and inflict injuries. The original design of overhead sign structures did not consider fatigue as a limit state. In addition, field welding of aluminum structures for any possible repairs is prohibited. A repair method for the cracked aluminum welded connections between diagonals and chord members using glass fiber reinforced polymer composites (GFRPs) is proposed. The static load carrying capacity of the welded connection, and the cracked connection repaired with GFRP composites are established. The paper describes the surface preparation of the aluminum tubular members, and the architecture and application sequence of the GFRP composite to retrofit the connection. Experimental results are presented from static tests of welded aluminum connections, welded aluminum connections retrofitted with GFRP composites, and new aluminum connections that depend only on GFRP composite elements for their strength. The results from monotonic static tests carried out on cracked welded specimens from actual sign structures show that the retrofitted connection with GFRP reinforcement achieved 1.17 to 1.25 times the capacity of the welded aluminum connection without any visible cracks. This result, and the minimal traffic disruption anticipated in the actual field application, makes this retrofit method a good candidate for implementation.     

Micellar polymerisation of ionic surfactants studied by conductimetry

The micellar polymerisation of ionic surfactants such as allyldodecyl-dimethylammonium bromide and 3-dodecyl-1-vinyl imidazolium iodide has been studied by conductimetry in aqueous solution. The polymerisation was carried out using two different sources of γ rays directed into solutions of surfactant above the critical micellar concentration. Conductimetry is shown to be a very good physicochemical method for analysis of these solutions. The results showed different behaviour for the two surfactants, which has highlighted a change in the structure of their aggregates which led to the assumption of an interaction between the polymers of high mass and different products of the polymerisation (oligomers, products of degradation, monomers etc.). Ultrafiltration experiments coupled with ¹H-NMR and conductivity analysis confirm these assumptions.     

Fractional composition of partly hydrolysed polyvinyl acetate and its compatibility with hydroxypropyl methylcellulose in aqueous solutions

Fractionation of partly hydrolysed polyvinyl acetate (PVA) was performed by warming of its aqueous solutions. The following properties of the obtained fractions were determined: viscosity, molecular weight and molecular weight distribution, surface tension, and absorbance in the IR range. The blockiness of the polymer molecules, characterized by their behaviour towards iodine-containing systems such as I₂,-H₃BO₃ and I₂,-KI, was estimated. Fractionation of the aqueous solutions of PVA by warming is based mainly on the different internal molecular structure of the separated products, i.e. on the length of the vinyl acetate blocks in the PVA molecules and, to a lesser extent, on the degree of hydrolysis and the degree of polymerization. The more blocklike are the PVA molecules, the less compatible are the polymers in the PVA-hydroxypropyl methylcellulose (HPMC)-water system. At phase separation in this sytem the PVA molecules which are not compatible with HPMC are, in the first place, those of the highest blockiness.     

Bulk modification of styrene–butadiene–styrene triblock copolymer with maleic anhydride

The bulk modification of SBS rubber with maleic anhydride in a mixing chamber of a Haake rheomixer was studied. The effect of temperature, maleic anhydride, and benzoyl peroxide concentrations on the grafting efficiency was evaluated. High grafting efficiency was achieved when the ratio of peroxide and maleic anhydride concentration was high. On the other hand, on this condition high insoluble fraction was generated. The addition of a diamine, 4,4′‐diaminediphenylmethane to the reaction mixture minimizes the amount of insoluble polymer. However, the grafted MAH content also decreases. The graft copolymer was characterized by infrared spectroscopy and the grafting extension was determined by titration. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2953–2960, 2002; DOI 10.1002/app.10355     

N.m.r. study of the ferroelectric phase transition in a 7030mol% copolymer of vinylidene fluoride (VF2) and trifluoroethylene (TrFE)

Nuclear magnetic resonance (n.m.r.) studies of ¹⁹F nuclei in a $\text{70}\text{30}\text{mol}\text{\%}$ random copolymer of vinylidene fluoride and trifluoroethylene were performed at 9.14 MHz and 20.0 MHz. The free induction decays (FIDs) were analysed in terms of two T₂ components attributed to the amorphous and crystalline portions of the polymer. The changes in crystallinity as well as the effects of the ferroelectric transition were observed during cycles of heating and cooling between 20°C and 140°C. The crystalline component of the FID lengthens by a factor of 2 at 100°C on heating and decreases by this factor at 60°C on cooling, thus exhibiting the thermal hysteresis of this ferroelectric transition. The spin-lattice relaxation was also investigated. From measurements at 9.14 MHz the observed longitudinal relaxation time T₁ appears to be dominated by the dynamics of the amorphous phase and exhibits no anomaly through the phase transition. However, from measurements at 20 MHz, well defined minima of T₁ were observed, which are associated with the ferroelectric transition (especially after repeated annealing of the samples). Results are discussed in terms of the crystalline phase structure, which appears dynamically disordered above the ferroelectric phase transition. An analogy is considered with the plastic phase transitions encountered in molecular crystals.     

Head-to-head polymers: 33. Bromination of cis-1,4-polybutadiene to head-to-head poly(vinyl bromide)

Cis-1,4-polybutadiene (PB) in a 0.5% solution of a solvent mixture of dichloromethane and 1,2-dibromoethane or tetrahydrofuran was quantitatively brominated with elemental bromine at 0°C under careful exclusion of oxygen to head-to-head poly(vinyl bromide). Partially brominated PB has a structure of random or block sequences of butadiene units in the polymer depending on the bromination solvent but shows no stereospecificity in the CHBrCHBr-dyads. Partially brominated PB with block structure showed a microphase-separated morphology over a wide range of composition. Microphase separation is less pronounced for the more random structure of butadiene units. I.r and ¹³C n.m.r. spectroscopy of the partially brominated PB was used to follow the progress of the bromination.