Compatibilisation of heterogeneous polymer blends by reactive processing

Functionalisation of polystyrene, PS, and ethylene-co-propylene-co-cyclopentadiene terpolymer, EPDM, with acrylic acid, AA, in a melt reactive processing procedure, in the presence of peroxide, trigonox 101, and coagents, Divinyl benzene, DVB (for PS), and trimethylolpropane triacrylate, TRIS (for EPDM), were successfully carried out. The level of grafting of the AA, as determined by infrared analysis, was significantly enhanced by the coagents. The grafting reaction of AA takes place simultaneously with homopolymerisation of the monomers, melt degradation and crosslinking reactions of the polymers. The extent of these competing reactions were inferred from measurements of melt flow index and insoluble gel content. Through a judicious use of both the peroxide and the coagent, particularly TRIS, unwanted side reactions were minimized. Five different processing methods were investigated for both functionalisation experiments; the direct addition of the pre-mixed polymer with peroxide and reactive modifiers was found to give optimum condition for grafting. The functionalised PS, F-PS, and EPDM, F-EPD, and maleinised polypropylene carrying a potential antioxidant, N-(4-anilinophenyl maleimide), F-PP were melt blended in binary mixtures of F-PS/F-EPD and F-PP/F-EPD in the presence (or absence) of organic diamines which act as an interlinking agent, e.g, Ethylene Diamine, EDA, and Hexamethylene Diamine, HEMDA. The presence of an interlinking agent, particularly HEMDA shows significant enhancement in the mechanical properties of the blend, suggesting that the copolymer formed has acted as compatibiliser to the otherwise incompatible polymer pairs. The functionalised and amidised blends, F and A-PSIEPDM (SPOI) and F and A-PPIEPDM (SPD2) were subsequently used as compatibiliser concentrates in the corresponding PSIEPDM and PPIEPDM blends containing various weight propotion of the homopolymers. The SPD1 caused general decreased in tensile strength, albeit increased in drop impact strength particularly in blend containing high PS content (80%). The SPD2 was particularly effective in enhancing impact strength in blends containing low weight ratio of PP (<70%). The SPD2 was also a good thermal antioxidant albeit less effective than commercial antioxidant. In all blends the evidence of compatibility was examined by scanning electron microscopy.

Reactive processing of polymers:effect of bifunctional and tri-functional comonomers on melt grafting of glycidyl methacrylate onto polypropylene

Two reactive comonomers, divinyl benzene (DVB) and trimethylolpropane triacrylate (TRIS), were evaluated for their role in effecting the melt free radical grafting reaction of the monomer glycidyl methacrylate (GMA) onto polypropylene (PP). The characteristics of the GMA-grafting systems in the presence and absence of DVB or TRIS were examined and compared in terms of the yield of the grafting reaction and the extent of the main side reactions, namely homopolymerisation of GMA (poly-GMA) and polymer degradation, using different chemical compositions of the reactive systems and processing conditions. In the absence of the comonomers, i.e. in a conventional system, high initiator concentrations of peroxides were typically required to achieve the highest possible GMA grafting levels which were found to be generally low. Concomitantly, both poly-GMA and degradation of the polymer by chain scission takes place with increasing initiator amounts. On the other hand, the presence of a small amount of the comonomers, DVB or Tris, in the GMA-grafting system, was shown to bring about a significant increase in the grafting level paralleled by a large reduction in poly-GMA and PP degradation. In the presence of these highly reactive comonomers, the optimum grafting system requires a much lower concentration of the peroxide initiator and, consequently, would lead to the much lower degree of polymer degradation observed in these systems. The differences in the effects of the presence of DVB and that of TRIS in the grafting systems on the rate of the GMA-grafting and homopolymerisation reactions, and the extent of PP degradation (through melt flow changes), were compared and contrasted with a conventional GMA-grafting system.

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.

A comparison of in situ constant and falling head permeameter tests to assess the distribution of clogging within horizontal subsurface flow constructed wetlands

Clogging is the main operational problem associated with horizontal subsurface flow constructed wetlands (HSSF CWs). The measurement of saturated hydraulic conductivity has proven to be a suitable technique to assess clogging within HSSF CWs. The vertical and horizontal distribution of hydraulic conductivity was assessed in two full-scale HSSF CWs by using two different in situ permeameter methods (falling head (FH) and constant head (CH) methods). Horizontal hydraulic conductivity profiles showed that both methods are correlated by a power function (FH= CH 0.7821, r 2=0.76) within the recorded range of hydraulic conductivities (0-70 m/day). However, the FH method provided lower values of hydraulic conductivity than the CH method (one to three times lower). Despite discrepancies between the magnitudes of reported readings, the relative distribution of clogging obtained via both methods was similar. Therefore, both methods are useful when exploring the general distribution of clogging and, specially, the assessment of clogged areas originated from preferential flow paths within full-scale HSSF CWs. Discrepancy between methods (either in magnitude and pattern) aroused from the vertical hydraulic conductivity profiles under highly clogged conditions. It is believed this can be attributed to procedural differences between the methods, such as the method of permeameter insertion (twisting versus hammering). Results from both methods suggest that clogging develops along the shortest distance between water input and output. Results also evidence that the design and maintenance of inlet distributors and outlet collectors appear to have a great influence on the pattern of clogging, and hence the asset lifetime of HSSF CWs. © Springer Science+Business Media B.V. 2011.

Eco-efficiency measurement and material balance principle:an application in power plants Malmquist Luenberger Index

Incorporating Material Balance Principle (MBP) in industrial and agricultural performance measurement systems with pollutant factors has been on the rise in recent years. Many conventional methods of performance measurement have proven incompatible with the material flow conditions. This study will address the issue of eco-efficiency measurement adjusted for pollution, taking into account materials flow conditions and the MBP requirements, in order to provide ‘real’ measures of performance that can serve as guides when making policies. We develop a new approach by integrating slacks-based measure to enhance the Malmquist Luenberger Index by a material balance condition that reflects the conservation of matter. This model is compared with a similar model, which incorporates MBP using the trade-off approach to measure productivity and eco-efficiency trends of power plants. Results reveal similar findings for both models substantiating robustness and applicability of the proposed model in this paper.

Effect of oscillatory flow on nucleation kinetics of butyl paraben

More than 165 induction times of butyl paraben-ethanol solution in a batch moving fluid oscillation baffled crystallizer with various amplitudes (1-9 mm) and frequencies (1.0-9.0 Hz) have been determined to study the effect of COBR operating conditions on nucleation. The induction time decreases with increasing amplitude and frequency at power density below about 500 W/m3; however, a further increase of the frequency and amplitude leads to an increase of the induction time. The interfacial energies and pre-exponential factors in both homogeneous and heterogeneous nucleation are determined by classical nucleation theory at oscillatory frequency 2.0 Hz and amplitudes of 3 or 5 mm both with and without net flow. To capture the shear rate conditions in oscillatory flow crystallizers, a large eddy simulation approach in a computational fluid dynamics framework is applied. Under ideal conditions the shear rate distribution shows spatial and temporal periodicity and radial symmetry. The spatial distributions of the shear rate indicate an increase of average and maximum values of the shear rate with increasing amplitude and frequency. In continuous operation, net flow enhances the shear rate at most time points, promoting nucleation. The mechanism of the shear rate influence on nucleation is discussed.

Exploration of a simple, low cost, micro gas turbine recuperator solution for a domestic combined heat and power unit

For micro gas turbines (MGT) of around 1 kW or less, a commercially suitable recuperator must be used to produce a thermal efficiency suitable for use in UK Domestic Combined Heat and Power (DCHP). This paper uses computational fluid dynamics (CFD) to investigate a recuperator design based on a helically coiled pipe-in-pipe heat exchanger which utilises industry standard stock materials and manufacturing techniques. A suitable mesh strategy was established by geometrically modelling separate boundary layer volumes to satisfy y + near wall conditions. A higher mesh density was then used to resolve the core flow. A coiled pipe-in-pipe recuperator solution for a 1 kW MGT DCHP unit was established within the volume envelope suitable for a domestic wall-hung boiler. Using a low MGT pressure ratio (necessitated by using a turbocharger oil cooled journal bearing platform) meant unit size was larger than anticipated. Raising MGT pressure ratio from 2.15 to 2.5 could significantly reduce recuperator volume. Dimensional reasoning confirmed the existence of optimum pipe diameter combinations for minimum pressure drop. Maximum heat exchanger effectiveness was achieved using an optimum or minimum pressure drop pipe combination with large pipe length as opposed to a large pressure drop pipe combination with shorter pipe length. © 2011 Elsevier Ltd. All rights reserved.

Design of a low power - high temperature heated ceramic sensor to detect halogen gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO 3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li 2SiO3 shows the best results, including a stable current and response to the gas. ^

Design of a Low Power – High Temperature Heated Ceramic Sensor to Detect Halogen Gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li2SiO3 shows the best results, including a stable current and response to the gas.

Surface Mean Flow and Turbulence Structure in Tropical Cyclone Winds

Hurricanes are one of the deadliest and costliest natural hazards affecting the Gulf coast and Atlantic coast areas of the United States. An effective way to minimize hurricane damage is to strengthen structures and buildings. The investigation of surface level hurricane wind behavior and the resultant wind loads on structures is aimed at providing structural engineers with information on hurricane wind characteristics required for the design of safe structures. Information on mean wind profiles, gust factors, turbulence intensity, integral scale, and turbulence spectra and co-spectra is essential for developing realistic models of wind pressure and wind loads on structures. The research performed for this study was motivated by the fact that considerably fewer data and validated models are available for tropical than for extratropical storms. Using the surface wind measurements collected by the Florida Coastal Monitoring Program (FCMP) during hurricane passages over coastal areas, this study presents comparisons of surface roughness length estimates obtained by using several estimation methods, and estimates of the mean wind and turbulence structure of hurricane winds over coastal areas under neutral stratification conditions. In addition, a program has been developed and tested to systematically analyze Wall of Wind (WoW) data, that will make it possible to perform analyses of baseline characteristics of flow obtained in the WoW. This program can be used in future research to compare WoW data with FCMP data, as gust and turbulence generator systems and other flow management devices will be used to create WoW flows that match as closely as possible real hurricane wind conditions. Hurricanes are defined as tropical cyclones for which the maximum 1-minute sustained surface wind speeds exceed 74 mph. FCMP data include data for tropical cyclones with lower sustained speeds. However, for the winds analyzed in this study the speeds were sufficiently high to assure that neutral stratification prevailed. This assures that the characteristics of those winds are similar to those prevailing in hurricanes. For this reason in this study the terms tropical cyclones and hurricanes are used interchangeably.

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

On thermodynamics in the primary power conversion of oscillating water column wave energy converters

The paper presents an investigation to the thermodynamics of the air flow in the air chamber for the oscillating water column wave energy converters, in which the oscillating water surface in the water column pressurizes or de-pressurises the air in the chamber. To study the thermodynamics and the compressibility of the air in the chamber, a method is developed in this research: the power take-off is replaced with an accepted semi-empirical relationship between the air flow rate and the oscillating water column chamber pressure, and the thermodynamic process is simplified as an isentropic process. This facilitates the use of a direct expression for the work done on the power take-off by the flowing air and the generation of a single differential equation that defines the thermodynamic process occurring inside the air chamber. Solving the differential equation, the chamber pressure can be obtained if the interior water surface motion is known or the chamber volume (thus the interior water surface motion) if the chamber pressure is known. As a result, the effects of the air compressibility can be studied. Examples given in the paper have shown the compressibility, and its effects on the power losses for large oscillating water column devices.

Piezoelectric energy harvesting using blood-flow-like excitation for implantable devices

The goal of this research is to produce a system for powering medical implants to increase the lifetime of the implanted devices and reduce the battery size. The system consists of a number of elements – the piezoelectric material for generating power, the device design, the circuit for rectification and energy storage. The piezoelectric material is analysed and a process for producing a repeatable high quality piezoelectric material is described. A full width half maximum (FWHM) of the rocking curve X-Ray diffraction (XRD) scan of between ~1.5° to ~1.7° for test wafers was achieved. This is state of the art for AlN on silicon and means devices with good piezoelectric constants can be fabricated. Finite element modelling FEM) was used to design the structures for energy harvesting. The models developed in this work were established to have an accuracy better than 5% in terms of the difference between measured and modelled results. Devices made from this material were analysed for power harvesting ability as well as the effect that they have on the flow of liquid which is an important consideration for implantable devices. The FEM results are compared to experimental results from laser Doppler vibrometry (LDV), magnetic shaker and perfusion machine tests. The rectifying circuitry for the energy harvester was also investigated. The final solution uses multiple devices to provide the power to augment the battery and so this was a key feature to be considered. Many circuits were examined and a solution based on a fully autonomous circuit was advanced. This circuit was analysed for use with multiple low power inputs similar to the results from previous investigations into the energy harvesting devices. Polymer materials were also studied for use as a substitute for the piezoelectric material as well as the substrate because silicon is more brittle.

Results of Closed-Flow Column Experiments (zip-archive 2.3 MB)

The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to observations of the solute breakthrough in column outflow experiments. This parameters uncertainty can be approached by the application of multiple experimental designs such as column experiments in open-flow mode and the recently proposed closed-flow mode. Latter are characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow. Depending on the experimental conditions, the solute concentration in the solution supply vessel and the effluent follows a damped sinusoidal oscillation. As a result, the closed-flow experiment provides additional observables in the breakthrough curve. The evaluation of these emergent features allows intrinsic control over boundary conditions and impacts the uncertainty of parameters in inverse modeling. We present a comprehensive sensitivity analysis to illustrate the potential application of closed-flow experiments. We show that the sensitivity with respect to the apparent dispersion can be controlled by the experimenter leading to a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude for optimal settings. With these finding we are also able to reduce the equifinality found for situations, where rate-limited interactions impede a proper determination of the apparent dispersion and rate coefficients. Furthermore, we show the expected breakthrough curve for equilibrium and kinetic sorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. This renders the closed-flow mode a useful complementary approach to classical column experiments.

Coagent Modified Polypropylene Prepared by Reactive Extrusion: A New Look Into the Structure-Property Relations of Injection Molded Parts

Peroxide-mediated reactive extrusion of linear isotactic polypropylene (L-PP) was conducted in the presence of trimethylolpropane trimethacrylate (TMPTMA) and triallyl trimesate (TAM) coagents, using a twin screw extruder. The resulting coagent-modified polypropylenes (CM-PP) had higher viscosities and elasticities, as well as increased crystallization temperature compared to PP reacted only with peroxide (DCP-PP). Additionally, deviations from terminal flow, and strain hardening were observed in PP modified with TAM, signifying the presence of long chain branching (LCB). The CM-PP formulations retained the modulus and tensile strength of the parent L-PP, in spite of their lower molar mass and viscosities, whereas their elongation at break and the impact strength were better. This was attributed to the finer spherulitic structure of these materials, and to the disappearance of the skin-core layer in the injection molded specimens.