Nanoscale detection of metal-labeled copolymers in patchy polymersomes

We report the synthesis of polymersome-forming block copolymers using two different synthetic routes based on Atom Transfer Radical Polymerization (ATRP) and Reversible Addition Fragmentation chain Transfer (RAFT) polymerization, respectively. Functionalization with 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) allowed the block copolymer chains to be labelled with electron-dense metal ions (e.g. indium). The resulting metal-conjugated copolymers can be visualized by transmission electron microscopy with single chain resolution, hence enabling the study of polymer/polymer immiscibility and phase separation on the nano-scale.

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.

Label-free Detection of Microcystin-LR in Waters Using Real-Time Potentiometric Biosensors Based on Single-Walled Carbon Nanotubes Imprinted Polymers

Microcystin-LR (MC-LR) is a dangerous toxin found in environmental waters, quantified by high performance liquid chromatography and/or enzyme-linked immunosorbent assays. Quick, low cost and on-site analysis is thus required to ensure human safety and wide screening programs. This work proposes label-free potentiometric sensors made of solid-contact electrodes coated with a surface imprinted polymer on the surface of Multi-Walled Carbon NanoTubes (CNTs) incorporated in a polyvinyl chloride membrane. The imprinting effect was checked by using non-imprinted materials. The MC-LR sensitive sensors were evaluated, characterized and applied successfully in spiked environmental waters. The presented method offered the advantages of low cost, portability, easy operation and suitability for adaptation to flow methods.

Time Reversibility of Stationary Regular Finite State Markov Chains

We propose an alternate parameterization of stationary regular finite-state Markov chains, and a decomposition of the parameter into time reversible and time irreversible parts. We demonstrate some useful properties of the decomposition, and propose an index for a certain type of time irreversibility. Two empirical examples illustrate the use of the proposed parameter, decomposition and index. One involves observed states; the other, latent states.

Effect of Polymer Architecture on the Structural and Biophysical Properties of PEG-PLA Nanoparticles

Polymers made of poly(ethylene glycol) chains grafted to poly(lactic acid) chains (PEG-g-PLA) were used to produce stealth drug nanocarriers. A library of comb-like PEG-g-PLA polymers with different PEG grafting densities was prepared in order to obtain nanocarriers with dense PEG brushes at their surface, stability in suspension, and resistance to protein adsorption. The structural properties of nanoparticles (NPs) produced from these polymers by a surfactant-free method were assessed by DLS, zeta potential, and TEM and were found to be controlled by the amount of PEG present in the polymers. A critical transition from a solid NP structure to a soft particle with either a “micelle-like” or “polymer nano-aggregate” structure was observed when the PEG content was between 15 to 25% w/w. This structural transition was found to have a profound impact on the size of the NPs, their surface charge, their stability in suspension in presence of salts as well as on the binding of proteins to the surface of the NPs. The arrangement of the PEG-g-PLA chains at the surface of the NPs was investigated by 1H NMR and X-ray photoelectron spectroscopy (XPS). NMR results confirmed that the PEG chains were mostly segregated at the NP surface. Moreover, XPS and quantitative NMR allowed quantifying the PEG chain coverage density at the surface of the solid NPs. Concordance of the results between the two methods was found to be remarkable. Physical-chemical properties of the NPs such as resistance to aggregation in saline environment as well as anti-fouling efficacy were related to the PEG surface density and ultimately to polymer architecture. Resistance to protein adsorption was assessed by isothermal titration calorimetry (ITC) using lysozyme. The results indicate a correlation between PEG surface coverage and level of protein interactions. The results obtained lead us to propose such PEG-g-PLA polymers for nanomedecine development as an alternative to the predominant polyester-PEG diblock polymers.

Polymer Nanocomposites: Crystallization, Reinforcement and Conductivity through SWNTs

The current research investigates the possibility of using single walled carbon nanotubes (SWNTs) as filler in polymers to impart several properties to the matrix polymer. SWNTs in a polymer matrix like poly(ethylene terephthalate) induce nucleation in its melt crystallization, provide effective reinforcement and impart electrical conductivity. We adopt a simple melt compounding technique for incorporating the nanotubes into the polymer matrix. For attaining a better dispersion of the filler, an ultrasound assisted dissolution-evaporation method has also been tried. The resulting enhancement in the materials properties indicates an improved disentanglement of the nanotube ropes, which in turn provides effective matrix-filler interaction. PET-SWNT nanocomposite fibers prepared through melt spinning followed by subsequent drawing are also found to have significantly higher mechanical propertiesas compared to pristine PET fiber.SWNTs also find applications in composites based on elastomers such as natural rubber as they can impart electrical conductivity with simultaneous improvement in the mechanical properties.

Modification of Polyethylenes by Reactive Extrusion

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

A comparative study of energy transfer in dye mixtures in monomer and polymer matrices under pulsed laser excitation

This study was conducted to identify the concentration dependence of the operating wavelengths and the relative intensities in which a dye mixture doped polymer optical fibre can operate. A comparative study of the radiative and Forster type energy transfer processes in Coumarin 540:Rhodamine 6G, Coumarin 540:Rhodamine B and Rhodamine 6G:Rhodamine B in methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) was done by fabricating a series of dye mixture doped polymer rods which have two emission peaks with varying relative intensities. These rods can be used as preforms for the fabrication of polymer optical fibre amplifiers operating in the multi-wavelength regime. The 445 nm line from an Nd:YAG pumped optical parametric oscillator (OPO) was used as the excitation source for the first two dye pairs and a frequency doubled Nd:YAG laser emitting at 532 nm was used to excite the Rh 6G:Rh B pair. The fluorescence lifetimes of the donor molecule in pure form as well as in the mixtures were experimentally measured in both monomer and polymer matrices by time-correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed. It was found that radiative energy transfer mechanisms are more efficient in all the three dye pairs in liquid and solid matrices.

Excitation wavelength dependence of energy transfer in dye mixture doped polymer optical fibre preforms

Dependence of energy transfer parameters on excitation wavelength has been investigated in poly (methyl methacrylate) (PMMA) optical fibre preforms doped with C 540:Rh B dye mixture by studying the fluorescence intensity and the lifetime variations. A fluorescence spectrophotometer was used to record the excitation spectra of the samples for the emission wavelengths 495 and 580 nm. The fluorescence emission from the polymer rods was studied at four specific excitation wavelengths viz; 445, 465, 488 and 532 nm. The fluorescence lifetime of the donor molecule was experimentally measured in polymer matrix by time correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed for three excitation wavelengths. It was found that any change in the excitation wavelength leads to significant variations in the quenching characteristics, which in turn affect the calculated energy transfer parameters.

Fluorescence characterization and gain studies on a dye-doped graded index polymer optical-fiber preform

Preparation of an appropriate optical-fiber preform is vital for the fabrication of graded-index polymer optical fibers (GIPOF), which are considered to be a good choice for providing inexpensive high bandwidth data links, for local area networks and telecommunication applications. Recent development of the interfacial gel polymerization technique has caused a dramatic reduction in the total attenuation in GIPOF, and this is one of the potential methods to prepare fiber preforms for the fabrication of dye-doped polymer-fiber amplifiers. In this paper, the preparation of a dye-doped graded-index poly(methyl methacrylate) (PMMA) rod by the interfacial gel polymerization method using a PMMA tube is reported. An organic compound of high-refractive index, viz., diphenyl phthalate (DPP), was used to obtain a graded-index distribution, and Rhodamine B (Rh B), was used to dope the PMMA rod. The refractive index profile of the rod was measured using an interferometric technique and the index exponent was estimated. The single pass gain of the rod was measured at a pump wavelength of 532 nm. The extent of doping of the Rh B in the preform was studied by axially exciting a thin slice of the rod with white light and measuring the spatial variation of the fluorescence intensity across the sample.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.