Effects of storage on thermomechanical properties of poly(epsilon-caprolactone) blends containing poly(vinyl pyrrolidone/iodine)

This study reports the effects of: the molecular weight ratio of poly(epsilon -caprolactone) (PCL) in blends containing polymer of high (50 000 g mol(-1)) and low (4000 g mol(-1)) molecular weight; the concentration (0, 1, and 5 wt-%) of poly(vinyl pyrrolidone/iodine) (PVP/I); and storage at 30 degreesC and 75% relative humidity; on the thermomechanical properties of films prepared by solvent evaporation from solutions containing both PCL and PVP/I. The tensile properties were found to be statistically dependent on the molecular weight ratio of PCL but not on the concentration of PVP/I. The reductions in tensile strength and elongation at break associated with increasing amounts of low molecular weight PCL were attributed to a reduction in the concentration of chain entanglements. No changes were observed in viscoelastic properties or the glass transition temperature. Following storage there were no changes in the tensile strength, glass transition temperature, or viscoelastic properties of the films; however, significant reductions in elongation at break were observed. It is suggested that this is due to hydrolytic chain scission of amorphous PCL. Inclusion of 5 wt-% PVP/I increased this process in films containing 100:0 and 80:20 high/low molecular weight PCL (but not 60.40), but the extent of this was small. This study highlighted significant aging properties of PCL in a moist atmosphere. Consequently, it is recommended that suitable packaging materials should be employed to control the exposure of PCL films to water during storage.

Dynamic grey-box modeling for online monitoring of extrusion viscosity

Melt viscosity is a key indicator of product quality in polymer extrusion processes. However, real time monitoring and control of viscosity is difficult to achieve. In this article, a novel “soft sensor” approach based on dynamic gray-box modeling is proposed. The soft sensor involves a nonlinear finite impulse response model with adaptable linear parameters for real-time prediction of the melt viscosity based on the process inputs; the model output is then used as an input of a model with a simple-fixed structure to predict the barrel pressure which can be measured online. Finally, the predicted pressure is compared to the measured value and the corresponding error is used as a feedback signal to correct the viscosity estimate. This novel feedback structure enables the online adaptability of the viscosity model in response to modeling errors and disturbances, hence producing a reliable viscosity estimate. The experimental results on different material/die/extruder confirm the effectiveness of the proposed “soft sensor” method based on dynamic gray-box modeling for real-time monitoring and control of polymer extrusion processes. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers

Anther Extrusion and Fusarium Head Blight Resistance in European Wheat

Anther extrusion has been widely discussed as a factor influencing fusarium head blight (FHB) resistance in wheat. This is despite a paucity of quantitative information on its importance, between cultivars, in contrast to that for heading date and plant height. We describe a method applicable to a plant breeding
situation at 10 days postanthesis, for assessing the distinct characteristics of anther retention (anthers held within the spikelet) and trapped anthers (partially
extruded and trapped between the lemma and palea of the wheat spikelet). FHB resistance was tested in field experiments in 2004 and 2005. In these experiments designed to resemble applications to a plant breeding selection scheme anther retention was significantly correlated with FHB in 2004 (r = 0.26; P < 0.05) and 2005 (r = 0.26; P < 0.05). A higher proportion of anthers retained relating, albeit weakly, with increased FHB susceptibility in European wheat.

Spin-Based Diagnostic of Nanostructure in Copper Phthalocyanine-C-60 Solar Cell Blends

Nanostructure and molecular orientation play a crucial role in determining the functionality of organic thin films. In practical devices, such as organic solar cells consisting of donor-acceptor mixtures, crystallinity is poor and these qualities cannot be readily determined by conventional diffraction techniques, while common microscopy only reveals surface morphology. Using a simple nondestructive technique, namely, continuous-wave electron paramagnetic resonance spectroscopy, which exploits the well-understood angular dependence of the g-factor and hyperfine tensors, we show that in the solar cell blend of C-60 and copper phthalocyanine (CuPc)-for which X-ray diffraction gives no information-the CuPc, and by implication the C-60, molecules form nanoclusters, with the planes of the CuPc molecules oriented perpendicular to the film surface. This information demonstrates that the current nanostructure in CuPc:C-60 solar cells is far from optimal and suggests that their efficiency could be considerably increased by alternative film growth algorithms.

Development of novel oral formulations prepared via hot melt extrusion for targeted delivery of photosensitizer to the colon

Colon-residing bacteria, such as vancomycin-resistant Enterococcus faecalis and Bacteroides fragilis, can cause a range of serious clinical infections. Photodynamic antimicrobial chemotherapy (PACT) may be a novel treatment option for these multidrug resistant organisms. The aim of this study was to formulate a Eudragit®-based drug delivery system, via hot melt extrusion (HME), for targeting colonic release of photosensitizer. The susceptibility of E. faecalis and B. fragilis to PACT mediated by methylene blue (MB), meso-tetra(N-methyl-4-pyridyl)porphine tetra-tosylate (TMP), or 5-aminolevulinic acid hexyl-ester (h-ALA) was determined, with tetrachlorodecaoxide (TCDO), an oxygen-releasing compound, added in some studies. Results show that, for MB, an average of 30% of the total drug load was released over a 6-h period. For TMP and h-ALA, these values were 50% and 16% respectively. No drug was released in the acidic media. Levels of E. faecalis and B. fragilis were reduced by up to 4.67 and 7.73 logs, respectively, on PACT exposure under anaerobic conditions, with increased kill associated with TCDO. With these formulations, photosensitizer release could potentially be targeted to the colon, and colon-residing pathogens killed by PACT. TCDO could be used in vivo to generate oxygen, which could significantly impact on the success of PACT in the clinic.

Low-cost Process monitoring for polymer extrusion

Polymer extrusion is regarded as an energy-intensive production process, and the real-time monitoring of both energy consumption and melt quality has become necessary to meet new carbon regulations and survive in the highly competitive plastics market. The use of a power meter is a simple and easy way to monitor energy, but the cost can sometimes be high. On the other hand, viscosity is regarded as one of the key indicators of melt quality in the polymer extrusion process. Unfortunately, viscosity cannot be measured directly using current sensory technology. The employment of on-line, in-line or off-line rheometers is sometimes useful, but these instruments either involve signal delay or cause flow restrictions to the extrusion process, which is obviously not suitable for real-time monitoring and control in practice. In this paper, simple and accurate real-time energy monitoring methods are developed. This is achieved by looking inside the controller, and using control variables to calculate the power consumption. For viscosity monitoring, a ‘soft-sensor’ approach based on an RBF neural network model is developed. The model is obtained through a two-stage selection and differential evolution, enabling compact and accurate solutions for viscosity monitoring. The proposed monitoring methods were tested and validated on a Killion KTS-100 extruder, and the experimental results show high accuracy compared with traditional monitoring approaches.

Real time measurement and control of viscosity for extrusion processes using recycled materials

The aim of this paper is to develop a new generation of extruder control system for recycled materials which has ability to automatically maintain constant a polymer melt viscosity of mixed recycled polymers during extrusion, regardless of variations in the Melt Flow Index (MFI) of recycled mixed grade high density polyethylene (HDPE) feedstock. The variations in MFI are due to differences in the source of the recycled material used. The work describes how melt viscosity for specific extruder/die system is calculated in real time using the rheological properties of the materials, the pressure drop through the extruder die and the actual throughput measurements using a gravimetric loss-in-weight hopper feeder. A closed-loop controller is also developed to automatically regulate screw speed and barrel temperature profile to achieve constant viscosity and enable consistent processing of variable grade recycled HDPE materials. Such a system will improve processability of mixed MFI polymers may also reduce the risk of polymer melt degradation, reduce producing large volumes of scrap/waste and lead to improvement in product quality. The experimental results of real time viscosity measurement and control using a 38 mm single screw extruder with different recycled HDPEs with widely different MFIs are reported in this work.

Automatic extruder for processing recycled polymers with ultrasound and temperature control system

Melt viscosity is one of the main factors affecting product quality in extrusion processes particularly with regard to recycled polymers. However, due to wide variability in the physical properties of recycled feedstock, it is difficult to maintain the melt viscosity during extrusion of polymer blends and obtain good quality product without generating scrap. This research investigates the application of ultrasound and temperature control in an automatic extruder controller, which has ability to maintain constant melt viscosity from variable recycled polymer feedstock during extrusion processing. An ultrasonic modulation system has been developed and fitted to the extruder prior to the die to convey ultrasonic energy from a high power ultrasonic generator to the polymer melt. Two separate control loops have been developed to run simultaneously in one controller: the first loop controls the ultrasonic energy or temperature to maintain constant die pressure, the second loop is used to control extruder screw speed to maintain constant throughput at the extruder die. Time response and energy consumption of the control methods in real-time experiments are also investigated and reported this paper.

Identification of vegetable oil botanical speciation in refined vegetable oil blends using an innovative combination of chromatographic and spectroscopic techniques

European Regulation 1169/2011 requires producers of foods that contain refined vegetable oils to label the oil types. A novel rapid and staged methodology has been developed for the first time to identify common oil species in oil blends. The qualitative method consists of a combination of a Fourier Transform Infrared (FTIR) spectroscopy to profile the oils and fatty acid chromatographic analysis to confirm the composition of the oils when required. Calibration models and specific classification criteria were developed and all data were fused into a simple decision-making system. The single lab validation of the method demonstrated the very good performance (96% correct classification, 100% specificity, 4% false positive rate). Only a small fraction of the samples needed to be confirmed with the majority of oils identified rapidly using only the spectroscopic procedure. The results demonstrate the huge potential of the methodology for a wide range of oil authenticity work.

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. 

Investigation of the process energy demand in polymer extrusion: a brief review and an experimental study

Extrusion is one of the fundamental production methods in the polymer processing industry and is used in the production of a large number of commodities in a diverse industrial sector. Being an energy intensive production method, process energy efficiency is one of the major concerns and the selection of the most energy efficient processing conditions is a key to reducing operating costs. Usually, extruders consume energy through the drive motor, barrel heaters, cooling fans, cooling water pumps, gear pumps, etc. Typically the drive motor is the largest energy consuming device in an extruder while barrel/die heaters are responsible for the second largest energy demand. This study is focused on investigating the total energy demand of an extrusion plant under various processing conditions while identifying ways to optimise the energy efficiency. Initially, a review was carried out on the monitoring and modelling of the energy consumption in polymer extrusion. Also, the power factor, energy demand and losses of a typical extrusion plant were discussed in detail. The mass throughput, total energy consumption and power factor of an extruder were experimentally observed over different processing conditions and the total extruder energy demand was modelled empirically and also using a commercially available extrusion simulation software. The experimental results show that extruder energy demand is heavily coupled between the machine, material and process parameters. The total power predicted by the simulation software exhibits a lagging offset compared with the experimental measurements. Empirical models are in good agreement with the experimental measurements and hence these can be used in studying process energy behaviour in detail and to identify ways to optimise the process energy efficiency.