The performance of poly(styrene)-block-poly(2-vinyl pyridine)-block- poly(styrene) triblock copolymers as pH-driven actuators

Poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) (PS-b-P2VP-b-PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification. Well-ordered structures not only provide an isotropic network, which reduces localised stress within the material, but are also essential for fundamental studies of soft matter because their activity on the molecular scale must be analysed and understood prior to their use in technological applications. Well-characterised PS-b-P2VP-b-PS materials have been coupled to a pH-oscillating reaction and their potential application as responsive actuators is discussed. This journal is © The Royal Society of Chemistry.

Metallocene ethylene-1-octene copolymers:influence of comonomer content on thermo-mechanical, rheological, and thermo-oxidative behaviours before and after melt processing in an internal mixer

The influence of the comonomer content in a series of metallocene-based ethylene-1-octene copolymers (m-LLDPE) on thermo-mechanical, rheological, and thermo-oxidative behaviours during melt processing were examined using a range of characterisation techniques. The amount of branching was calculated from 13C NMR and studies using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were employed to determine the effect of short chain branching (SCB, comonomer content) on thermal and mechanical characteristics of the polymer. The effect of melt processing at different temperatures on the thermo-oxidative behaviour of the polymers was investigated by examining the changes in rheological properties, using both melt flow and capillary rheometry, and the evolution of oxidation products during processing using infrared spectroscopy. The results show that the comonomer content and catalyst type greatly affect thermal, mechanical and oxidative behaviour of the polymers. For the metallocene polymer series, it was shown from both DSC and DMA that (i) crystallinity and melting temperatures decreased linearly with comonomer content, (ii) the intensity of the ß-transition increased, and (iii) the position of the tan δmax peak corresponding to the a-transition shifted to lower temperatures, with higher comonomer content. In contrast, a corresponding Ziegler polymer containing the same level of SCB as in one of the m-LLDPE polymers, showed different characteristics due to its more heterogeneous nature: higher elongational viscosity, and a double melting peak with broader intensity that occurred at higher temperature (from DSC endotherm) indicating a much broader short chain branch distribution. The thermo-oxidative behaviour of the polymers after melt processing was similarly influenced by the comonomer content. Rheological characteristics and changes in concentrations of carbonyl and the different unsaturated groups, particularly vinyl, vinylidene and trans-vinylene, during processing of m-LLDPE polymers, showed that polymers with lower levels of SCB gave rise to predominantly crosslinking reactions at all processing temperatures. By contrast, chain scission reactions at higher processing temperatures became more favoured in the higher comonomer-containing polymers. Compared to its metallocene analogue, the Ziegler polymer showed a much higher degree of crosslinking at all temperatures because of the high levels of vinyl unsaturation initially present.

Phase-conjugated pilots for fibre nonlinearity compensation in CO-OFDM transmission

We experimentally demonstrate a novel fibre nonlinearity compensation technique for CO-OFDM based on phase-conjugated pilots (PCPs), showing that, by varying the PCP overhead a performance improvement up to 4 dB can be achieved allowing highly flexible adaptation to link characteristics.

Phase-conjugated subcarrier coding for fibre nonlinearity mitigation in CO-OFDM transmission

We demonstrate a novel subcarrier coding scheme combined with pre-EDC for fibre nonlinearity mitigation in CO-OFDM, showing that a performance improvement of 1.5 dB can be achieved in a 150 Gb/s BPSK PDM CO-OFDM transmission.

Demonstration of phase-conjugated subcarrier coding for fiber nonlinearity compensation in CO-OFDM transmission

In this paper, we demonstrate through computer simulation and experiment a novel subcarrier coding scheme combined with pre-electrical dispersion compensation (pre-EDC) for fiber nonlinearity mitigation in coherent optical orthogonal frequency division multiplexing (CO-OFDM) systems. As the frequency spacing in CO-OFDM systems is usually small (tens of MHz), neighbouring subcarriers tend to experience correlated nonlinear distortions after propagation over a fiber link. As a consequence, nonlinearity mitigation can be achieved by encoding and processing neighbouring OFDM subcarriers simultaneously. Herein, we propose to adopt the concept of dual phase conjugated twin wave for CO-OFDM transmission. Simulation and experimental results show that this simple technique combined with 50% pre-EDC can effectively offer up to 1.5 and 0.8 dB performance gains in CO-OFDM systems with BPSK and QPSK modulation formats, respectively.

Phase-conjugated pilots for fibre nonlinearity compensation in CO-OFDM transmission

In this paper, we demonstrate a novel fiber nonlinearity compensation technique for coherent optical orthogonal frequency-division multiplexing (CO-OFDM) systems based on the transmission of phase-conjugated pilots (PCPs). In this scheme, a portion of OFDM subcarriers (up to 50%) is transmitted with its phase conjugates, which is used at the receiver to estimate the nonlinear distortions in the respective subcarriers and other subcarriers, which are not accompanied by PCPs. Simulation and experimental results show that by varying the PCP overhead, a performance improvement up to 4 dB can be achieved. In addition, the proposed technique can be effectively applied in both single polarization and polarization-division multiplexed systems, in both single channel and wavelength-division multiplexing systems, thus, offering highest flexibility in implementations.

Fullerene-capped copolymers for bulk heterojunctions: device stability and efficiency improvements

A fullerene end-capped polymer-compatibilizer based on poly(3-hexylthiophene) (P3HT) was synthesized and demonstrated to have a remarkable effect on both the stability and efficiency of devices made from exemplar P3HT and [6,6]-phenyl C61-butyric acid methyl ester (PCBM). P3HT with ethynyl chain-ends and α-azido-ω-bromo-PS were prepared via Grignard metathesis (GRIM) and atom transfer radical polymerisation, respectively. “Click” chemistry resulted in the preparation of poly(3-hexylthiophene)-block-ω-bromo-polystyrene (P3HT-b-PS-Br), and subsequent atom transfer radical addition chemistry with fullerene (C60) yielded the donor–acceptor block copolymer P3HT-b-PS-C60. Both P3HT-b-PS-Br and P3HT-b-PS-C60 were considered as compatibilizers with P3HT/PCBM blends, with the study detailing effects on active-layer morphology, device efficiency and stability. When used at low concentrations, both P3HT-b-PS-Br (1%) and P3HT-b-PS-C60 (0.5%) resulted in considerable 28% and 35% increases in efficiencies with respect to devices made from P3HT/PCBM alone. Furthermore, P3HT-b-PS-C60 (0.5%) resulted in an important improvement in device stability.