Studies of the cationic polymerisation of vinylic and energetic cyclic ether monomers

The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied. In concurrent work the carbocationic polymerisations of isobutylene or substituted styrenes have been studied. Materials with narrow molecular weight distributions have been prepared using the diphenyl phosphate/BCl3 initiator. These systems and monomers are expected to be used in the synthesis of thermoplastic elastomers.

The effect of bioglass addition on mechanical and physical properties of photoactive UDMA-TEGDMA resin composites

Light curable dimethacrylate resin composites undergo free radical photopolymerisation in response to blue light (wavelength 450-500 nm) and may offer superior handling and setting characteristics for novel hard tissue repair materials. The current investigation aims to determine the optimum formulation of bisphenol-A glycidyl methacrylate and triethyleneglycoldimethacrylate (bisGMA/TEGDMA) or urethane dimethacrylate (UDMA)/TEGDMA resin mixtures and the effect of Bioglass incorporation on the rate of polymerisation (RP), degree of conversion (DC) and flexural strength (FS) of light-curable filled resin composites (FRCs). Experimental photoactive resins containing a range of bisGMA, UDMA and TEGDMA ratios and/or filled with non-silanised irregular or spherical 45S5-Bioglass (50 μm; 5-40 wt%) and/or silanised silicate glass filler particulates (0.7 μm; 50-70 wt%) were tested. RP and DC were analysed in real-time using nearinfrared spectroscopy. FS of resins and FRCs were determined using three-point flexural strength tests. UDMA/TEGDMA resins exhibited increased DC compared with bisGMA/TEGDMA resins (p<0.05). The addition of spherical particles of Bioglass had a detrimental effect on the FS (p>0.05), whereas they increased DC of UDMA/TEGDMA resins (p<0.05). Addition of irregular shaped Bioglass particles increased the FS of UDMA/TEGDMA resins up to 20 wt% Bioglass (p<0.05). The flexibility and strength conferred by the urethane group in UDMA may result in enhanced physical and mechanical properties compared with conventional resins containing bulky (bisGMA) molecules. Addition of 45S5-Bioglass with specific filler content, size and morphology resulted in enhanced mechanical and physical properties of UDMA/TEGDMA composites. © (2014) Trans Tech Publications, Switzerland.

Shear induced toughening in bonded joints:experiments and analysis

Bonded joint specimens were fabricated from composite adherends and either an epoxy or a urethane adhesive. In mixed-mode fracture experiments, the epoxy bonded specimens generally failed by subinterfacial fracture in the composite, while specimens bonded with urethane failed very close to the adhesive/substrate interface. For the epoxy bonded specimens, fracture toughness did not change significantly with mode-mix, but for urethane bonded joints, fracture toughness increased with increasing shear load. Finite element analysis, which modeled specimens bonded with the two adhesives, showed similar trends. The different toughening behaviors for the two bonded joints can be attributed to dissipation of energy through inelastic deformation, which was insignificant in the epoxy-bonded joints but substantial when the urethane was used as the bonding agent.