Phase separation, porous structure, and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester

Thermosetting blends of an aliphatic epoxy resin and a hydroxyl-functionalized hyperbranched polymer (HBP), aliphatic hyperbranched polyester Boltorn H40, were prepared using 4,4'-diaminodiphenylmethane (DDM) as the curing agent. The phase behavior and morphology of the DDM-cured epoxy/HBP blends with HBP content up to 40 wt% were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The cured epoxy/HBP blends are immiscible and exhibit two separate glass transitions, as revealed by DMA. The SEM observation showed that there exist two phases in the cured blends, which is an epoxy-rich phase and an HBP-rich phase, which is responsible for the two separate glass transitions. The phase morphology was observed to be dependent on the blend composition. For the blends with HBP content up to 10 wt%, discrete HBP domains are dispersed in the continuous cured epoxy matrix, whereas the cured blend with 40 wt% HBP exhibits a combined morphology of connected globules and bicominuous phase structure. Porous epoxy thermosets with continuous open structures on the order of 100-300 nm were formed after the HBP-rich phase was extracted with solvent from the cured blend with 40 wt% HBP. The DSC study showed that the curing rate is not obviously affected in the epoxy/HBP blends with HBP content up to 40 wt %. The activation energy values obtained are not remarkably changed in the blends; the addition of HBP to epoxy resin thus does not change the mechanism of cure reaction of epoxy resin with DDM. (c) 2006 Wiley Periodicals, Inc.

RAFT-mediated emulsion polymerization of styrene using a non-ionic surfactant

We report the successful RAFT-mediated emulsion polymerization of styrene using a non-ionic surfactant (Brij98), the highly reactive 1-phenylethyl phenyldithioacetate (PEPDTA) RAFT agent, and water-soluble initiator ammonium persulfate (APS). The molar ratio of RAFT agent to APS was identical in all experiments. Most of the monomer was contained within the micelles, analogous to microemulsion or miniemulsion systems but without the need of shear, sonication, cosurfactant, or a hydrophobe. The number-average molecular weight increased with conversion and the polydispersity index was below 1.2. This ideal 'living' behavior was only found when molecular weights of 9000 and below were targeted. It was postulated that the rapid transportation of RAFT agent from the monomer swollen micelles to the growing particles was fast on the polymerization timescale, and most if not all the RAFT agent is consumed within the first 10% conversion. In addition, it was postulated that the high nucleation rate from the high rate of exit ( of the R radical from the RAFT agent) and high entry rate from water-phase radicals ( high APS concentration) reduced the effects of 'superswelling' and therefore a similar molar ratio of RAFT agent to monomer was maintained in all growing particles. The high polydispersity indexes found when targeting molecular weights greater than 9000 were postulated to be due to the lower nucleation rate from the lower weight fractions of both APS and RAFT agent. In these cases, 'superswelling' played a dominant role leading to a heterogeneous distribution of RAFT to monomer ratios among the particles nucleated at different times.

Transition from time-continuous systems to discrete mappings

Detailed transport studies in plasmas require the solution of the time evolution of many different initial positions of test particles in the phase space of the systems to be investigated. To reduce this amount of numerical work, one would like to replace the integration of the time-continues system with a mapping.

Polymer fractionation by continuous chromatography

A review is given of general chromatographic theory, the factors affecting the performance of chromatographi c columns, and aspects of scale-up of the chromatographic process. The theory of gel permeation chromatography (g. p. c.) is received, and the results of an experimental study to optimize the performance of an analytical g.p.c. system are reported. The design and construction of a novel sequential continuous chromatographic refining unit (SCCR3), for continuous liquid-liquid chromatography applications, is described. Counter-current operation is simulated by sequencing a system of inlet and outlet port functions around a connected series of fixed, 5.1 cm internal diameter x 70 cm long, glass columns. The number of columns may be varied, and, during this research, a series of either twenty or ten columns was used. Operation of the unit for continuous fractionation of a dextran polymer (M. W. - 30,000) by g.p.c. is reported using 200-400 µm diameter porous silica beads (Spherosil XOB07S) as packing, and distilled water for the mobile phase. The effects of feed concentration, feed flow rate, and mobile and stationary phase flow rates have been investigated, by means of both product, and on-column, concentrations and molecular weight distributions. The ability to operate the unit successfully at on-column concentrations as high as 20% w/v dextran has been demonstrated, and removal of both high and low molecular weight ends of a polymer feed distribution, to produce products meeting commercial specifications, has been achieved. Equivalent throughputs have been as high as 2.8 tonnes per annum for ten columns, based on continuous operation for 8000 hours per annum. A concentration dependence of the equilibrium distribution coefficient, KD observed during continuous fractionation studies, is related to evidence in the literature and experimental results obtained on a small-scale batch column. Theoretical treatments of the counter-current chromatographic process are outlined, and a preliminary computer simulation of the SCCR3 unit t is presented.

Mass transfer characteristics of two-aqueous-phase liquid-liquid mixtures

Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.

Batch and continuous fermentation methods for the production of dextransucrase

The available literature concerning dextransucrase and dextran production and purification has been reviewed along with the reaction mechanisms of the enzyme. A discussion of basic fermentation theory is included, together with a brief description of bioreactor hydrodynamics and general biotechnology. The various fermenters used in this research work are described in detail, along with the various experimental techniques employed. The micro-organism Leuconostoc mesenteroides NRRL B512 (F) secretes dextransucrase in the presence of an inducer, sucrose, this being the only known inducer of the enzyme. Dextransucrase is a growth related product and a series of fed-batch fermentations have been carried out to extend the exponential growth phase of the organism. These experiments were carried out in a number of different sized vessels, ranging in size from 2.5 to 1,000 litres. Using a 16 litre vessel, dextransucrase activities in excess of 450 DSU/cm3 (21.67 U/cm3) have been obtained under non-aerated conditions. It has also been possible to achieve 442 DSU/cm3 (21.28 U/cm3) using the 1,000 litre vessel, although this has not been done consistently. A 1 litre and a 2.5 litre vessel were used for the continuous fermentations of dextransucrase. The 2.5 litre vessel was a very sophisticated MBR MiniBioreactor and was used for the majority of continuous fermentations carried out. An enzyme activity of approximately 108 DSU/cm3 (5.20 U/cm3) was achieved at a dilution rate of 0.50 h-1, which corresponds to the maximum growth rate of the cells under the process conditions. A number of continuous fermentations were operated for prolonged periods of time, with experimental run-times of up to 389 h being recorded without any incidence of contamination. The phenomenon of enzyme enhancement on hold-up of up to 100% was also noted during these fermentations, with dextransucrase of activity 89.7 DSU/cm3 (4.32 U/cm3) being boosted to 155.7 DSU/cm3 (7.50 U/cm3) following 24 hours of hold-up. These findings support the recommendation of a second reactor being placed in series with the existing vessel.

Simultaneous biochemical reaction and separation in a continuous rotating annular chromatograph

The aim of this work has been to investigate the behaviour of a continuous rotating annular chromatograph (CRAC) under a combined biochemical reaction and separation duty. Two biochemical reactions have been employed, namely the inversion of sucrose to glucose and fructose in the presence of the enzyme invertase and the saccharification of liquefied starch to maltose and dextrin using the enzyme maltogenase. Simultaneous biochemical reaction and separation has been successfully carried out for the first time in a CRAC by inverting sucrose to fructose and glucose using the enzyme invertase and collecting continuously pure fractions of glucose and fructose from the base of the column. The CRAC was made of two concentric cylinders which form an annulus 140 cm long by 1.2 cm wide, giving an annular space of 14.5 dm3. The ion exchange resin used was an industrial grade calcium form Dowex 50W-X4 with a mean diameter of 150 microns. The mobile phase used was deionised and dearated water and contained the appropriate enzyme. The annular column was slowly rotated at speeds of up to 240°h-1 while the sucrose substrate was fed continuously through a stationary feed pipe to the top of the resin bed. A systematic investigation of the factors affecting the performance of the CRAC under simultaneous biochemical reaction and separation conditions was carried out by employing a factorial experimental procedure. The main factors affecting the performance of the system were found to be the feed rate, feed concentrations and eluent rate. Results from the experiments indicated that complete conversion could be achieved for feed concentrations of up to 50% w/v sucrose and at feed throughputs of up to 17.2 kg sucrose per m3 resin/h. The second enzymic reaction, namely the saccharification of liquefied starch to maltose employing the enzyme maltogenase has also been successfully carried out on a CRAC. Results from the experiments using soluble potato starch showed that conversions of up to 79% were obtained for a feed concentration of 15.5% w/v at a feed flowrate of 400 cm3/h. The product maltose obtained was over 95% pure. Mathematical modelling and computer simulation of the sucrose inversion system has been carried out. A finite difference method was used to solve the partial differential equations and the simulation results showed good agreement with the experimental results obtained.

The role of organoclay in promoting co-continuous morphology in high-density poly(ethylene)/poly(amide) 6 blends

The effect of organically modified clay on the morphology, rheology and mechanical properties of high-density polyethylene (HDPE) and polyamide 6 (PA6) blends (HDPE/PA6 = 75/25 parts) is studied. Virgin and filled blends were prepared by melt compounding the constituents using a twin-screw extruder. The influence of the organoclay on the morphology of the hybrid was deeply investigated by means of wide-angle X-ray diffractometry, transmission and scanning electron microscopies and quantitative extraction experiments. It has been found that the organoclay exclusively places inside the more hydrophilic polyamide phase during the melt compounding. The extrusion process promotes the formation of highly elongated and separated organoclay-rich PA6 domains. Despite its low volume fraction, the filled minor phase eventually merges once the extruded pellets are melted again, giving rise to a co-continuous microstructure. Remarkably, such a morphology persists for long time in the melt state. A possible compatibilizing action related to the organoclay has been investigated by comparing the morphology of the hybrid blend with that of a blend compatibilized using an ethylene–acrylic acid (EAA) copolymer as a compatibilizer precursor. The former remains phase separated, indicating that the filler does not promote the enhancement of the interfacial adhesion. The macroscopic properties of the hybrid blend were interpreted in the light of its morphology. The melt state dynamics of the materials were probed by means of linear viscoelastic measurements. Many peculiar rheological features of polymer-layered silicate nanocomposites based on single polymer matrix were detected for the hybrid blend. The results have been interpreted proposing the existence of two distinct populations of dynamical species: HDPE not interacting with the filler, and a slower species, constituted by the organoclay-rich polyamide phase, which slackened dynamics stabilize the morphology in the melt state. In the solid state, both the reinforcement effect of the filler and the co-continuous microstructure promote the enhancement of the tensile modulus. Our results demonstrate that adding nanoparticles to polymer blends allows tailoring the final properties of the hybrid, potentially leading to high-performance materials which combine the advantages of polymer blends and the merits of polymer nanocomposites.

Selective localization of organoclay and effects on the morphology and mechanical properties of LDPE/PA11 blends with distributed and co-continuous morphology

A study was made on the effect of small amounts of organically modified clay on the morphology and mechanical properties of blends of low-density polyethylene and polyamide 11 at different compositions. The influence of the filler on the blend morphology was investigated using wide angle X-ray diffractometry, scanning and transmission electron microscopy and selective extraction experiments. The filler was found to locate predominantly in the more hydrophilic polyamide phase. Although such uneven distribution does not have a significant effect on the onset of phase co-continuity of the polymer components, it brings about a drastic refinement of the microstructure for the blends both with droplets/matrix and co-continuous morphologies. In addition to the expected reinforcing action of the filler, the resulting fine microstructure plays an important role in enhancing the mechanical properties of the blends. This is essentially because of a good quality of stress transfer across the interface between the constituents, which also seems to benefit for a good interfacial adhesion promoted by the filler. Our results provide the experimental evidence for the capabilities of nanoparticles added to multiphase polymer systems to act selectively as a reinforcing agent for specific domains of the material and as a medium able to assist the refinement of the polymer phases during mixing.

Phase shift keyed systems based on a gain switched laser transmitter

Return-to-Zero (RZ) and Non-Return-to-Zero (NRZ) Differential Phase Shift Keyed (DPSK) systems require cheap and optimal transmitters for widespread implementation. The authors report on a gain switched Discrete Mode (DM) laser that can be employed as a cost efficient transmitter in a 10.7 Gb/s RZ DPSK system and compare its performance to that of a gain switched Distributed Feed-Back (DFB) laser. Experimental results show that the gain switched DM laser readily provides error free performance and a receiver sensitivity of -33.1 dBm in the 10.7 Gbit/s RZ DPSK system. The standard DFB laser on the other hand displays an error floor at 10(-1) in the same RZ DPSK system. The difference in performance, between the two types of gain switched transmitters, is analysed by investigating their linewidths. We also demonstrate, for the first time, the generation of a highly coherent gain switched pulse train which displays a spectral comb of approximately 13 sidebands spaced by the 10.7 GHz modulation frequency. The filtered side-bands are then employed as narrow linewidth Continuous Wave (CW) sources in a 10.7 Gb/s NRZ DPSK system.

Design optimization of short-stroke single-phase tubular permanent-magnet motor for refrigeration applications

This paper describes a design methodology to achieve optimal performance for a short-stroke single-phase tubular permanent-magnet motor which drives a reciprocating vapor compressor. The steady-state characteristic of the direct-drive linear-motor compressor system is analyzed, an analytical formula for predicting iron loss is presented, and a motor-design procedure which takes into account the effect of compressor loads under nominal operating condition is formulated. It is shown that the motor efficiency can be optimized with respect to two leading dimensional ratios. Experimental results validate the proposed design methodology. Copyright © 2010 IEEE.

Power-controlled phase-matching and instability of CW propagation in multicore optical fibers with a central core

We present modulation instability analysis including azimuthal perturbations of steady-state continuous wave (CW) propagation in multicore-fiber configurations with a central core. In systems with a central core, a steady CW evolution regime requires power-controlled phase matching, which offers interesting spatial-division applications. Our results have general applicability and are relevant to a range of physical and engineering systems, including high-power fiber lasers, optical transmission in multicore fiber, and systems of coupled nonlinear waveguides. © 2013 Optical Society of America.

A high-power-factor, three-phase isolated AC-DC converter using high-frequency current injection

A single-stage, three-phase AC-to-DC converter topology is proposed for high-frequency power supply applications. The principal features of the circuit include continuous current operation of the three AC input inductors, inherent shaping of the input currents, resulting in high power factor, a transformer isolated output, and only two active devices are required, both soft-switched. Resonant conversion techniques are used, and a high power factor is achieved by injecting high-frequency currents into the three-phase rectifier, producing a high frequency modulation of the rectifier input voltages. The current injection principle is explained and the system operation is confirmed by a combination of simulation and experimental results.

Slow-phase onset influence on waveform identification and foveation time measure in congenital nystagmus

Congenital nystagmus (CN) is an ocular-motor disorder characterised by involuntary, conjugated ocular oscillations and its pathogenesis is still under investigation. This kind of nystagmus is termed congenital (or infantile) since it could be present at birth or it can arise in the first months of life. Most of CN patients show a considerable decrease of their visual acuity: image fixation on the retina is disturbed by nystagmus continuous oscillations, mainly horizontal. However, the image of a given target can still be stable during short periods in which eye velocity slows down while the target image is placed onto the fovea (called foveation intervals). To quantify the extent of nystagmus, eye movement recording are routinely employed, allowing physicians to extract and analyse nystagmus main features such as waveform shape, amplitude and frequency. Using eye movement recording, it is also possible to compute estimated visual acuity predictors: analytical functions which estimates expected visual acuity using signal features such as foveation time and foveation position variability. Use of those functions extend the information from typical visual acuity measurement (e.g. Landolt C test) and could be a support for therapy planning or monitoring. This study focuses on detection of CN patients' waveform type and on foveation time measure. Specifically, it proposes a robust method to recognize cycles corresponding to the specific CN waveform in the eye movement pattern and, for those cycles, evaluate the exact signal tracts in which a subject foveates. About 40 eyemovement recordings, either infrared-oculographic or electrooculographic, were acquired from 16 CN subjects. Results suggest that the use of an adaptive threshold applied to the eye velocity signal could improve the estimation of slow phase start point. This can enhance foveation time computing and reduce influence of repositioning saccades and data noise on the waveform type identification.