A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. II. Coulomb interaction effects in single conjugated polymer chains

Conjugated polymers have attracted considerable attention in the last few decades due to their potential for optoelectronic applications. A key step that needs optimisation is charge carrier separation following photoexcitation. To understand better the dynamics of the exciton prior to charge separation, we have performed simulations of the formation and dynamics of localised excitations in single conjugated polymer strands. We use a nonadiabatic molecular dynamics method which allows for the coupled evolution of the nuclear degrees of freedom and of multiconfigurational electronic wavefunctions. We show the relaxation of electron-hole pairs to form excitons and oppositely charged polaron pairs and discuss the modifications to the relaxation process predicted by the inclusion of the Coulomb interaction between the carriers. The issue of charge photogeneration in conjugated polymers in dilute solution is also addressed. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600404]

Perturbed frequency-selective surfaces fabricated on large thin polymer membranes for multiband infrared applications

The design, fabrication, and characterization of single-screen perturbed frequency-selective surfaces (FSS) at infrared frequencies for single and multiband applications are reported. Single-band FSS based on parallel strips have been perturbed by decreasing the length of every second strip within the array in order to achieve dual band-stop responses. The same principle has been extended to design FSS exhibiting tri- and quadreflection bands. In addition, strip FSSs have been perturbed by replacing every second strip for a metallic ring, resulting in dual-band filters with different polarization responses of the bands. These designs have been fabricated on large thin polyimide membranes using sacrificial silicon wafers. An oxide interlayer between the sacrificial silicon wafer and the polyimide membrane is employed to stop the silicon etching and is wet etched subsequently by a solution of ammonium fluoride and acetic acid that does not attack either the polyimide membrane or the aluminium FSS elements. Fourier transform infrared spectroscopy measurements are presented to validate the predicted responses of the fabricated prototypes.

A new model based approach for the prediction and optimisation of thermal homogeneity in single screw extrusion

In polymer extrusion, delivery of a melt which is homogenous in composition and temperature is important for good product quality. However, the process is inherently prone to temperature fluctuations which are difficult to monitor and control via single point based conventional thermo- couples. In this work, the die melt temperature profile was monitored by a thermocouple mesh and the data obtained was used to generate a model to predict the die melt temperature profile. A novel nonlinear model was then proposed which was demonstrated to be in good agreement with training and unseen data. Furthermore, the proposed model was used to select optimum process settings to achieve the desired average melt temperature across the die while improving the temperature homogeneity. The simulation results indicate a reduction in melt temperature variations of up to 60%.

Polymer electrolyte membrane water electrolyser with Aquivion short side chain perfluorosulfonic acid ionomer binder in catalyst layers

The Aquivion short-side-chain (SSC) perfluorosulfonic acid (PFSA) ionomer was adopted in catalyst layers (CL) of polymer electrolyte membrane water electrolysers (PEMWE) instead of long-side-chain (LSC) Nafion ionomer. The effects of SSC ionomer content in CL for oxygen evolution reaction were studied in half cell with cyclic voltammetry and steady state linear sweep. In a single cell test the MEA with SSC-PFSA Aquivion ionomer exhibited better thermal stability than the one with LSC-PFSA Nafion ionomer at 90 °C. The cell voltage at a current density of 1 A cm was 1.63 V at 90 °C using the SSC-PFSA Aquivion ionomer binder, Nafion 117 membrane, and without back pressurizing. In a continuous operation the cell voltage degradation rate of the MEA using Aquivion ionomer binder was only about 0.82 mV h.

Energy monitoring and quality control of a single screw extruder

Polymer extrusion, in which a polymer is melted and conveyed to a mould or die, forms the basis of most polymer processing techniques. Extruders frequently run at non-optimised conditions and can account for 15–20% of overall process energy losses. In times of increasing energy efficiency such losses are a major concern for the industry. Product quality, which depends on the homogeneity and stability of the melt flow which in turn depends on melt temperature and screw speed, is also an issue of concern of processors. Gear pumps can be used to improve the stability of the production line, but the cost is usually high. Likewise it is possible to introduce energy meters but they also add to the capital cost of the machine. Advanced control incorporating soft sensing capabilities offers opportunities to this industry to improve both quality and energy efficiency. Due to strong correlations between the critical variables, such as the melt temperature and melt pressure, traditional decentralized PID (Proportional–Integral–Derivative) control is incapable of handling such processes if stricter product specifications are imposed or the material is changed from one batch to another. In this paper, new real-time energy monitoring methods have been introduced without the need to install power meters or develop data-driven models. The effects of process settings on energy efficiency and melt quality are then studied based on developed monitoring methods. Process variables include barrel heating temperature, water cooling temperature, and screw speed. Finally, a fuzzy logic controller is developed for a single screw extruder to achieve high melt quality. The resultant performance of the developed controller has shown it to be a satisfactory alternative to the expensive gear pump. Energy efficiency of the extruder can further be achieved by optimising the temperature settings. Experimental results from open-loop control and fuzzy control on a Killion 25 mm single screw extruder are presented to confirm the efficacy of the proposed approach.

Preparation of Aqueous Core/Polymer Shell Microcapsules by Internal Phase Separation

Aqueous core/polymer shell microcapsules with mommuclear and polynuclear core morphologies have been formed by internal phase separation from water-in-oil emulsions. The water-in-oil emulsions were prepared with the shell polymer dissolved in the aqueous phase by adding a low boiling point cosolvent. Subsequent removal of this cosolvent (by evaporation) leads to phase separation of the polymer and, if the spreading conditions are correct, formation of a polymer shell encapsulating the aqueous core. Poly(tetrahydrofuran) (PTHF) shell/aqueous core microcapsules, with a single (mononuclear) core, have been prepared, but the low T-g (-84 degreesC) of PTHF makes characterization of the particles more difficult. Poly(methyl methacrylate) and poly(isobutyl methacrylate) have higher T-g values (105 and 55 degreesC, respectively) and can be dissolved in water at sufficiently high acetone concentrations, but evaporation of the acetone from the emulsion droplets in these cases mostly resulted in polynuclear capsules, that is, having cores with many very small water droplets contained within the polymer matrix. Microcapsules with fewer, larger aqueous droplets in the core could be produced by reducing the rate of evaporation of the acetone. A possible mechanism for the formation of these polynuclear cores is suggested. These microcapsules were prepared dispersed in an oil-continuous phase. They could, however, be successfully transferred to a water-continuous phase, using a simple centrifugation technique. In this way, microcapsules with aqueous cores, dispersed in an aqueous medium, could be made. It would appear that a real challenge with the water-core systems, compared to the previous oil-core systems, is to obtain the correct order of magnitude of the three interfacial tensions, between the polymer, the aqueous phase, and the continuous oil phase; these control the spreading conditions necessary to produce shells rather than "acorns".

Process efficiency in polymer extrusion: Correlation between the energy demand and melt thermal stability

Thermal stability is of major importance in polymer extrusion, where product quality is dependent upon the level of melt homogeneity achieved by the extruder screw. Extrusion is an energy intensive process and optimisation of process energy usage while maintaining melt stability is necessary in order to produce good quality product at low unit cost. Optimisation of process energy usage is timely as world energy prices have increased rapidly over the last few years. In the first part of this study, a general discussion was made on the efficiency of an extruder. Then, an attempt was made to explore correlations between melt thermal stability and energy demand in polymer extrusion under different process settings and screw geometries. A commodity grade of polystyrene was extruded using a highly instrumented single screw extruder, equipped with energy consumption and melt temperature field measurement. Moreover, the melt viscosity of the experimental material was observed by using an off-line rheometer. Results showed that specific energy demand of the extruder (i.e. energy for processing of unit mass of polymer) decreased with increasing throughput whilst fluctuation in energy demand also reduced. However, the relationship between melt temperature and extruder throughput was found to be complex, with temperature varying with radial position across the melt flow. Moreover, the melt thermal stability deteriorated as throughput was increased, meaning that a greater efficiency was achieved at the detriment of melt consistency. Extruder screw design also had a significant effect on the relationship between energy consumption and melt consistency. Overall, the relationship between the process energy demand and thermal stability seemed to be negatively correlated and also it was shown to be highly complex in nature. Moreover, the level of process understanding achieved here can help to inform selection of equipment and setting of operating conditions to optimise both energy and thermal efficiencies in parallel. 

Efficient and selective hydrogen peroxide-mediated oxidation of sulfides in batch and segmented and continuous flow using a peroxometalate-based polymer immobilised ionic liquid phase catalyst

The peroxometalate-based polymer immobilized ionic liquid phase catalyst [PO4{WO(O-2)(2)}(4)]@PIILP has been prepared by anion exchange of ring opening metathesis-derived pyrrolidinium-decorated norbornene/ cyclooctene copolymer and shown to be a remarkably efficient system for the selective oxidation of sulfides under mild conditions. A cartridge packed with a mixture of [PO4{WO(O-2)(2)}(4)]@PIILP and silica operated as a segmented or continuous flow process and gave good conversions and high selectivity for either sulfoxide (92% in methanol at 96% conversion for a residence time of 4 min) or sulfone (96% in acetonitrile at 96% conversion for a residence time of 15 min). The immobilized catalyst remained active for 8 h under continuous flow operation with a stable activity/selectivity profile that allowed 6.5 g of reactant to be processed (TON = 46 428) while a single catalyst cartridge could be used for the consecutive oxidation of multiple substrates giving activity-selectivity profiles that matched those obtained with fresh catalyst.

Dynamic modelling of die melt temperature profile in polymer extrusion: Effects of process settings, screw geometry and material

Extrusion is one of the major methods for processing polymeric materials and the thermal homogeneity of the process output is a major concern for manufacture of high quality extruded products. Therefore, accurate process thermal monitoring and control are important for product quality control. However, most industrial extruders use single point thermocouples for the temperature monitoring/control although their measurements are highly affected by the barrel metal wall temperature. Currently, no industrially established thermal profile measurement technique is available. Furthermore, it has been shown that the melt temperature changes considerably with the die radial position and hence point/bulk measurements are not sufficient for monitoring and control of the temperature across the melt flow. The majority of process thermal control methods are based on linear models which are not capable of dealing with process nonlinearities. In this work, the die melt temperature profile of a single screw extruder was monitored by a thermocouple mesh technique. The data obtained was used to develop a novel approach of modelling the extruder die melt temperature profile under dynamic conditions (i.e. for predicting the die melt temperature profile in real-time). These newly proposed models were in good agreement with the measured unseen data. They were then used to explore the effects of process settings, material and screw geometry on the die melt temperature profile. The results showed that the process thermal homogeneity was affected in a complex manner by changing the process settings, screw geometry and material.

Investigation of the temperature homogeneity of die melt flows in polymer extrusion

Polymer extrusion is fundamental to the processing of polymeric materials and melt flow temperature homogeneity is a major factor which influences product quality. Undesirable thermal conditions can cause problems such as melt degradation, dimensional instability, weaknesses in mechanical/optical/geometrical properties, and so forth. It has been revealed that melt temperature varies with time and with radial position across the die. However, the majority of polymer processes use only single-point techniques whose thermal measurements are limited to the single point at which they are fixed. Therefore, it is impossible for such techniques to determine thermal homogeneity across the melt flow. In this work, an extensive investigation was carried out into melt flow thermal behavior of the output of a single extruder with different polymers and screw geometries over a wide range of processing conditions. Melt temperature profiles of the process output were observed using a thermocouple mesh placed in the flow and results confirmed that the melt flow thermal behavior is different at different radial positions. The uniformity of temperature across the melt flow deteriorated considerably with increase in screw rotational speed while it was also shown to be dependent on process settings, screw geometry, and material properties. Moreover, it appears that the effects of the material, machine, and process settings on the quantity and quality of the process output are heavily coupled with each other and this may cause the process to be difficult to predict and variable in nature

The effect of melt viscosity on thermal efficiency for single screw extrusion of HDPE

In this work, a highly instrumented single screw extruder has been used to study the effect of polymer rheology on the thermal efficiency of the extrusion process. Three different molecular weight grades of high density polyethylene (HDPE) were extruded at a range of conditions. Three geometries of extruder screws were used at several set temperatures and screw rotation speeds. The extruder was equipped with real-time quantification of energy consumption; thermal dynamics of the process were examined using thermocouple grid sensors at the entrance to the die. Results showed that polymer rheology had a significant effect on process energy consumption and thermal homogeneity of the melt. Highest specific energy consumption and poorest homogeneity was observed for the highest viscosity grade of HDPE. Extruder screw geometry, set extrusion temperature and screw rotation speed were also found to have a direct effect on energy consumption and melt consistency. In particular, specific energy consumption was lower using a barrier flighted screw compared to single flighted screws at the same set conditions. These results highlight the complex nature of extrusion thermal dynamics and provide evidence that rheological properties of the polymer can significantly influence the thermal efficiency of the process.

Microplasma Processed Ultrathin Boron Nitride Nanosheets for Polymer Nanocomposites with Enhanced Thermal Transport Performance

This paper reports on the enhancement of the thermal transport properties of nanocomposite materials containing hexagonal boron nitride in poly (vinyl alcohol)through room-temperature atmospheric pressure direct-current microplasma processing. Results show that the microplasma treatment leads to exfoliation of the hexagonal boron nitride in isopropyl alcohol, reducing the number of stacks from >30to a few or single layers. The thermal diffusivity of the resulting nanocomposites reaches 8.5 mm2 s-1, 50 times greater than blank poly (vinyl alcohol) and twice that ofnanocomposites containing non-plasma treated boron nitride nanosheets. From TEM analysis, we observe much less aggregation of the nanosheets after plasma processing along with indications of an amorphous carbon interfacial layer which may contribute to stable dispersion of boron nitride nanosheets in the resulting plasma treated colloids.