Polymers in drug delivery and molecular recognition

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Biodegradable polymers as drug delivery systems.

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Biodegradable polymers as drug delivery systems

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The synthesis and avaluation of Friedel-Crafts polymers

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Optical wave turbulence

We review recent progress in optical wave turbulence with a specific focus on the fast growing field of fibre lasers. Weak irregular nonlinear interactions between a large number of resonator modes are responsible for practically important characteristics of fibre lasers such as spectral broadening of radiation. Wave turbulence is a fundamental nonlinear phenomenon which occurs in a variety of nonlinear wave-bearing physical systems. The experimental impediments and the computationally intensive nature of simulating of hydrodynamic or plasma wave turbulence often make it rather challenging to collect a significant number of statistical data The study of turbulent wave behaviour in optical devices offers quite a unique opportunity to collect an enormous amount of data on statistical properties of wave turbulence using high-speed, high precision optical measurements during a relatively short period of time. We present recent theoretical, numerical and experimental results on optical wave turbulence in fibre lasers ranging from weak to strong developed turbulence for different signs of fibre dispersion. Furthermore, we report on our studies of spectral wave condensate in fibre lasers that make interdisciplinary links with a number of other research fields.

Dynamics of anchored polymers under an oscillating force

We study the dynamics of a polymer of varying stiffness, pinned or grafted at both ends and subjected to an oscillatory forcing at an intermediate point. Via stochastic simulations, we find a crossover from a periodic limit cycle to an aperiodic dynamics as the polymer gets "stiffer." An analytical argument valid in the 2D grafted case shows that in such a case this aperiodic dynamics has some chaotic signatures. © 2007 The American Physical Society.

Two-dimensional viscoelastic discrete triangular system with negative-stiffness components

Potential applications of high-damping and high-stiffness composites have motivated extensive research on the effects of negative-stiffness inclusions on the overall properties of composites. Recent theoretical advances have been based on the Hashin-Shtrikman composite models, one-dimensional discrete viscoelastic systems and a two-dimensional nested triangular viscoelastic network. In this paper, we further analyze the two-dimensional triangular structure containing pre-selected negative-stiffness components to study its underlying deformation mechanisms and stability. Major new findings are structure-deformation evolution with respect to the magnitude of negative stiffness under shear loading and the phenomena related to dissipation-induced destabilization and inertia-induced stabilization, according to Lyapunov stability analysis. The evolution shows strong correlations between stiffness anomalies and deformation modes. Our stability results reveal that stable damping peaks, i.e. stably extreme effective damping properties, are achievable under hydrostatic loading when the inertia is greater than a critical value. Moreover, destabilization induced by elemental damping is observed with the critical inertia. Regardless of elemental damping, when the inertia is less than the critical value, a weaker system instability is identified.

Oxidative degradation and stabilisation of polymers

The aim of this review is to present a coherent treatment of the fundamental aspects of the science that underpins current technological practices, and future advances, in the stabilisation of synthetic organic polymers. Aspects of polymer oxidation are introduced first before discussing the role of antioxidants, with numerous examples, to illustrate their basic mechanisms of action. The state of the art is discussed with particular emphasis on recent development and progress.

Dynamics of linear polymers in random media

We study phenomenological scaling theories of the polymer dynamics in random media, employing the existing scaling theories of polymer chains and the percolation statistics. We investigate both the Rouse and the Zimm model for Brownian dynamics and estimate the diffusion constant of the center-of-mass of the chain in such disordered media. For internal dynamics of the chain, we estimate the dynamic exponents. We propose similar scaling theory for the reptation dynamics of the chain in the framework of Flory theory for the disordered medium. The modifications in the case of correlated disorders are also discussed. .

Anomalies in stiffness and damping of a 2D discrete viscoelastic system due to negative stiffness components

The recent development of using negative stiffness inclusions to achieve extreme overall stiffness and mechanical damping of composite materials reveals a new avenue for constructing high performance materials. One of the negative stiffness sources can be obtained from phase transforming materials in the vicinity of their phase transition, as suggested by the Landau theory. To understand the underlying mechanism from a microscopic viewpoint, we theoretically analyze a 2D, nested triangular lattice cell with pre-chosen elements containing negative stiffness to demonstrate anomalies in overall stiffness and damping. Combining with current knowledge from continuum models, based on the composite theory, such as the Voigt, Reuss, and Hashin-Shtrikman model, we further explore the stability of the system with Lyapunov's indirect stability theorem. The evolution of the microstructure in terms of the discrete system is discussed. A potential application of the results presented here is to develop special thin films with unusual in-plane mechanical properties. © 2006 Elsevier B.V. All rights reserved.

Metallocene ethylene-1-octene copolymers:effect of extrusion conditions on thermal oxidation of polymers with different comonomer content

Metallocene ethylene-1-octene copolymers having different densities and comonomer content ranging from 11 to 36 wt% (m-LLDPE), and a Ziegler copolymer (z-LLDPE) containing the same level of short-chain branching (SCB) corresponding to one of the m-LLDPE polymers, were subjected to extrusion. The effects of temperature (210-285 °C) and multi-pass extrusions (up to five passes) on the rheological and structural characteristics of these polymers were investigated using melt index and capillary rheometry, along with spectroscopic characterisation of the evolution of various products by FTIR, C-NMR and colour measurements. The aim is to develop a better understanding of the effects of processing variables on the structure and thermal degradation of these polymers. Results from rheology show that both extrusion temperature and the amount of comonomer have a significant influence on the polymer melt thermo-oxidative behaviour. At low to intermediate processing temperatures, all m-LLDPE polymers exhibited similar behaviour with crosslinking reactions dominating their thermal oxidation. By contrast, at higher processing temperatures, the behaviour of the metallocene polymers changed depending on the level of comonomer content: higher SCB gave rise to predominantly chain scission reactions whereas polymers with lower level of SCB continued to be dominated by crosslinking. This temperature dependence was attributed to changes in the different evolution of carbonyl and unsaturated compounds including vinyl, vinylidene and trans-vinylene. © 2007 Elsevier Ltd. All rights reserved.

Reactive processing of polymers:functionalisation of ethylene-propylene diene terpolymer (EPDM) in the presence and absence of a co-agent and effect of functionalised EPDM on compatibilisation of poly(ethylene terephthalate)/EPDM blends

Ethylene-propylene diene terpolymer (EPDM) was functionalized with glycidyl methacrylate (GMA) during melt processing by free radical grafting with peroxide initiation in the presence and absence of a reactive comonomer trimethylolpropane triacrylate (Tris). Increasing the peroxide concentration resulted in an increase in the GMA grafting yield, albeit the overall grafting level was low and was accompanied by higher degree of crosslinking of EPDM which was found to be the major competing reaction. The presence of Tris in the grafting system gave rise to higher grafting yield produced at a much lower peroxide concentration though the crosslinking reactions remained high but without the formation of GMA-homopolymer in either of the two systems. The use of these functionalized EPDM (f-EPDM) samples with PET as compatibilisers in binary and ternary blends of PET/EPDM/f-EPDM was evaluated. The influence of the different functionalisation routes of the rubber phase (in presence and absence of Tris) and the effect of the level of functionality and microstructure of the resultant f-EPDM on the extent of the interfacial reaction, morphology and mechanical properties was also investigated. It is suggested that the mechanical properties of the blends are strongly influenced by the performance of the graft copolymer, which is in turn, determined by the level of functionality, molecular structure of the functionalized rubber and the interfacial concentration of the graft copolymer across the interface. The cumulative evidence obtained from torque rheometry, scanning electron microscopy, SEM, dynamic mechanical analysis (DMA), tensile mechanical tests and Fourier transform infrared (FTIR) supports this. It was shown that binary and ternary blends prepared with f-EPDM in the absence of Tris and containing lower levels of g-GMA effected a significant improvement in mechanical properties. This increase, particularly in elongation to break, could be accounted for by the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET that would result in a graft copolymer which could, most probably, preferentially locate at the interface, thereby acting as an 'emulsifier' responsible for decreasing the interfacial tension between the otherwise two immiscible phases. This is supported by results from FTIR analysis of the fractionated PET phase of these blends which confirm the formation of an interfacial reaction, DMA results which show a clear shift in the T s of the blend components and SEM results which reveal very fine morphology, suggesting effective compatibilisation that is concomitant with the improvement observed in their tensile properties. Although Tris has given rise to highest amount of g-GMA, it resulted in lower mechanical properties than the optimized blends produced in the absence of Tris. This was attributed to the difference in the microstructure of the graft and the level of functionality in these samples resulting in less favourable structure responsible for the coarser dispersion of the rubber phase observed by SEM, the lower extent of T shift of the PET phase (DMA), the lower height of the torque curve during reactive blending and FTIR analysis of the separated PET phase that has indicated a lower extent of the interfacial chemical reaction between the phases in this Tris-containing blend sample. © 2005 Elsevier Ltd. All rights reserved.

Reactive processing of polymers:effect of in situ compatibilisation on characteristics of blends of polyethylene terephthalate and ethylene-propylene rubber

Ethylene-propylene rubber (EPR) functionalised with glycidyl methacrylate (GMA) (f-EPR) during melt processing in the presence of a co-monomer, such as trimethylolpropane triacrylate (Tris), was used to promote compatibilisation in blends of polyethylene terephthalate (PET) and f-EPR, and their characteristics were compared with those of PET/f-EPR reactive blends in which the f-EPR was functionalised with GMA via a conventional free radical melt reaction (in the absence of a co-monomer). Binary blends of PETand f-EPR (with two types of f-EPR prepared either in presence or absence of the co-monomer) with various compositions (80/20, 60/40 and 50/50 w/w%) were prepared in an internal mixer. The blends were evaluated by their rheology (from changes in torque during melt processing and blending reflecting melt viscosity, and their melt flow rate), morphology scanning electron microscopy (SEM), dynamic mechanical properties (DMA), Fourier transform infrared (FTIR) analysis, and solubility (Molau) test. The reactive blends (PET/f-EPR) showed a marked increase in their melt viscosities in comparison with the corresponding physical (PET/EPR) blends (higher torque during melt blending), the extent of which depended on the amount of homopolymerised GMA (poly-GMA) present and the level of GMA grafting in the f-EPR. This increase was accounted for by, most probably, the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET. Morphological examination by SEM showed a large improvement of phase dispersion, indicating reduced interfacial tension and compatibilisation, in both reactive blends, but with the Tris-GMA-based blends showing an even finer morphology (these blends are characterised by absence of poly-GMA and presence of higher level of grafted GMA in its f-EPR component by comparison to the conventional GMA-based blends). Examination of the DMA for the reactive blends at different compositions showed that in both cases there was a smaller separation between the glass transition temperatures compared to their position in the corresponding physical blends, which pointed to some interaction or chemical reaction between f-EPR and PET. The DMA results also showed that the shifts in the Tgs of the Tris-GMA-based blends were slightly higher than for the conventional GMA-blends. However, the overall tendency of the Tgs to approach each other in each case was found not to be significantly different (e.g. in a 60/40 ratio the former blend shifted by up to 4.5 °C in each direction whereas in the latter blend the shifts were about 3 °C). These results would suggest that in these blends the SEM and DMA analyses are probing uncorrelatable morphological details. The evidence for the formation of in situ graft copolymer between the f-EPR and PET during reactive blending was clearly illustrated from analysis by FTIR of the separated phases from the Tris-GMA-based reactive blends, and the positive Molau test pointed out to graft copolymerisation in the interface. A mechanism for the formation of the interfacial reaction during the reactive blending process is proposed.