Associative properties of perfluorooctyl end‐functionalized polystyrene–poly(ethylene oxide) diblock copolymers

The synthesis of 2,2,3,3‐tetrahydro‐perfluoroundecanoyl end‐functionalized polystyrene–poly(ethylene oxide) block (PS‐block‐PEO‐R_F) copolymers and their matching PS‐block‐PEO diblock copolymers was carried out by sequential anionic polymerization. Viscometry and ¹⁹F NMR studies show that the PS‐block‐PEO copolymers, in contrast to their matching PS‐block‐PEO‐R_F copolymers, exhibit a micellar rather than the associative behavior seen for the latter. However, the presence of an excess of fluorinated acid, used for end‐functionalization, produces a reduction of the associative behavior above the overlap concentration, with the fluorinated acid acting like a surfactant. A competition may also occur between PS—and R_F—mediated micellization. Copyright © 2004 Society of Chemical Industry     

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.     

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.     

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.     

Thermally stimulated shrinkage forces in oriented polymers: 1. Temperature dependence

Temperature dependences of shrinkage forces appearing in oriented polymer samples when heated at constant length were recorded for polycarbonate, polyethylene terephthalate, polyethylene and polypropylene. The influence of various processing conditions on thermally stimulated shrinkage forces is demonstrated. A four-state model is proposed which qualitatively describes the temperature dependences of shrinkage forces in amorphous polymers.     

A force modulation study on crystallization process in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films

This paper introduces the Force Modulation technique to the study of crystallization process in ferroelectric vinylidene fluoride and trifluoroethylene copolymer films. Using this technique we have successfully visualized ferroelectric crystalline domains and observed that these ferroelectric domains grow out from amorphous phase, unite into strip-like structures, and finally congregate into a union. Force Modulation can weaken the influence of topography on imaging of ferroelectric domains, and reveal more details, which are difficult to be observed in topographical image.     

聚合物冷拉过程的流函数分析

用流函数法分析了聚合物拉伸成形时，颈缩的发生和扩展过程，文中论证了采用流函数法的优越性和适用性，并将流函数法计算结果和有限元法计算结果作了对比。