Modelling the Mechanical and Strain Recovery Behaviour of Partially Crystalline PLA

YesThis is a study of the modelling and prediction of strain recovery in a polylactide. Strain recovery near the glass transition temperature is the underlying mechanism for the shape memory in an amorphous polymer. The investigation is aimed at modelling such shape memory behaviour. A PLA-based copolymer is subjected to stress-strain, stress relaxation and strain recovery experiments at large strain at 60 °C just below its glass transition temperature. The material is 13% crystalline. Using published data on the mechanical properties of the crystals, finite element modelling was used to determine the effect of the crystal phase on the overall mechanical behaviour of the material, which was found to be significant. The finite element models were also used to relate the stress-strain results to the yield stress of the amorphous phase. This yield stress was found to possess strain rate dependence consistent with an Eyring process. Stress relaxation experiments were also interpreted in terms of the Eyring process, and a two-process Eyring-based model was defined that was capable of modelling strain recovery behaviour. This was essentially a model of the amorphous phase. It was shown to be capable of useful predictions of strain recovery.Engineering and Physical Sciences Research Council, grant number EP/L020572/1.. Not submitted within 3 months from acceptance or publication but is a Gold paper

Visualisation and analysis of polyethylene coextrusion melt flow

Polymer melts experience complex, time variant, stress and deformation fields on their passage through fixed geometries in many conversion operations. Flow complexity is further increased in operations involving the co-joining of two or more melt streams where one confining boundary is moving and viscoelastic. Such a complex situation arises in coextrusion processes. This work covers experimental studies on polyethylene melt flows in complex coextrusion geometries with a view to understanding the stress fields involved and their effects on flow stability. A 30°1coextrusion geometry is studied using two extrusion arrangements. In one arrangement a single extruder is used to feed a 'bifurcated' die design wherein the melt stream is split prior to, and rejoined after, a divider plate in the die. In the other design melt streams are delivered to, and converged at 30°, using two independent extruders. In a second die melt streams are brought together at 90°. In each die arrangement melt flow in the confluent region and die land to the die exit was observed through side windows of a visualisation cell. Velocity ratios of the two melt streams were varied and layer thickness ratios producing instability are determined for each melt for a variety of flow conditions. Stress and velocity fields in the coextrusion arrangements were quantified using stress birefringence and particle image velocimetry techniques. The study demonstrates conclusively that wave type interfacial instability occurred in the coextrusion geometries when the same low density polyethylene melt is used in each stream. This observation occurred at specific, repeatable, stream layer ratios in each die arrangement. The complex flows were numerical modelled using a modified Leonov model and Flow 2000P software. There was reasonable agreement between modelled at experimentally determined stress fields. Modelling however provided far more detailed stress gradient information than could be resolved from the optical techniques. A total normal stress difference (TNSD) sign criterion was used to predict the critical layer ratio for the onset of the interfacial instability in one die arrangement and good agreement between theory and experiment has been obtained. The study conclusively demonstrates wave type interfacial instability in the coextrusion process is not caused by process perturbations potentially introduced by extruder screw rotation but is associated with process-history dependant differences in melt elasticity. © 2009 American Institute of Physics

Mechanism of Hydrogen-Bonded Complex Formation between Ibuprofen and Nanocrystalline Hydroxyapatite.

Nanocrystalline hydroxyapatite (nanoHA) is the main hard component of bone and has the potential to be used to promote osseointegration of implants and to treat bone defects. Here, using active pharmaceutical ingredients (APIs) such as ibuprofen, we report on the prospects of combining nanoHA with biologically active compounds to improve the clinical performance of these treatments. In this study, we designed and investigated the possibility of API attachment to the surface of nanoHA crystals via the formation of a hydrogen-bonded complex. The mechanistic studies of an ibuprofen/nanoHA complex formation have been performed using a holistic approach encompassing spectroscopic (Fourier transform infrared (FTIR) and Raman) and X-ray diffraction techniques, as well as quantum chemistry calculations, while comparing the behavior of the ibuprofen/nanoHA complex with that of a physical mixture of the two components. Whereas ibuprofen exists in dimeric form both in solid and liquid state, our study showed that the formation of the ibuprofen/nanoHA complex most likely occurs via the dissociation of the ibuprofen dimer into monomeric species promoted by ethanol, with subsequent attachment of a monomer to the HA surface. An adsorption mode for this process is proposed; this includes hydrogen bonding of the hydroxyl group of ibuprofen to the hydroxyl group of the apatite, together with the interaction of the ibuprofen carbonyl group to an HA Ca center. Overall, this mechanistic study provides new insights into the molecular interactions between APIs and the surfaces of bioactive inorganic solids and sheds light on the relationship between the noncovalent bonding and drug release properties

The effect of materials, process settings and screw geometry on energy consumption and melt temperature in single screw extrusion

YesPolymer extrusion is an energy intensive production process and process energy e ciency has become a key concern in the current industry with the pressure of reducing the global carbon footprint. Here, knowledge of the pattern of energy usage and losses of each component in the plant is highly useful in the process energy optimization. Moreover, it is essential to maintain the melt quality while improving the energy e ciency in polymer processing. In this work, an investigation was made on the total energy consumption, drive motor energy consumption, power factor and the melt temperature profile across the die melt flow (as an indication of the melt thermal quality) of an industrial scale extruder with three di erent screw geometries, three polymer types and wide range of processing conditions (altogether 135 di erent processing situations were observed). This aims to widen the knowledge on process energy and thermal behaviors while exploring possible correlation/s between energy demand and melt quality (in terms of melt temperature fluctuations across the melt flow). The results showed that the level and fluctuations of the extruder’s power factor is particularly dependent upon the material being processed. Moreover, it seems that there is a relation between the level of energy demand of the heaters and the level of melt temperature fluctuations. While the extruder specific energy consumption decreases with increasing screw speed, specific energy consumption of the drive motor may have either increasing or decreasing behavior. Overall, this study provides new insights in a wide range on process energy demand and melt thermal quality in polymer extrusion. Moreover, further research is recommended to establish strong correlation/s between process energy consumption and melt thermal quality which should help to enhance process control and hence the product quality in single screw polymer extrusion

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

YesThermal 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.This work was funded through an inter-disciplinary research programme (Grant No. EP/G059330/1) by the EPSRC-UK. The technical assistance provided by Ken Howell, Roy Dixon and John Wyborn is greatly appreciated

Effect of Ultrasound on Molecular Structure Development of Polylactide

YesIn this work, effect of ultrasound on molecular structure development of Polylactide (PLA) was studied. It was found that the intrinsic viscosity of PLA decreased with increasing treating time, temperature and ultrasound time. Different from traditional thermal degradation of PLA, the degradation of PLA under ultrasound treatment showed that chain scission and chain combination of PLA competed with each other in the degradation process, which could be divided into two steps. The mechanism of ultrasound degradation of PLA was proposed. Furthermore, Thermal properties were characterized by DSC to show heat and ultrasound effects on molecular structure development of PLA

Continuous Manufacturing of Cocrystals Using Solid State Shear Milling Technology

yesSolid state shear milling (S3M) is reported as a scalable, continuous, polymer-assisted cocrystallization technique. A specially designed milling pan was employed to provide high levels of applied shear, and the addition of a polymeric processing aid enabled generation of high stress fields. Carbamazepine–salicylic acid cocrystals were produced with 5–25 wt % of poly(ethylene oxide) (PEO). A systematic study was carried out to understand the effect of process variables on properties and performance of the cocrystals. S3M offers an important new route for continuous manufacturing of pharmaceutical cocrystals

Fibrillation of chain branched poly (lactic acid) with improved blood compatibility and bionic structure

YesHighly-oriented poly (lactic acid) (PLA) with bionic fibrillar structure and micro-grooves was fabricated through solid hot drawing technology for further improving the mechanical properties and blood biocompatibility of PLA as blood-contacting medical devices. In order to enhance the melt strength and thus obtain high orientation degree, PLA was first chain branched with pentaerythritol polyglycidyl ether (PGE). The branching degree as high as 12.69 mol% can be obtained at 0.5 wt% PGE content. The complex viscosity, elastic and viscous modulus for chain branched PLA were improved resulting from the enhancement of molecular entanglement, and consequently higher draw ratio can be achieved during the subsequent hot stretching. The stress-induced crystallization of PLA occurred during stretching, and the crystal structure of the oriented PLA can be attributed to the α′ crystalline form. The tensile strength and modulus of PLA were improved dramatically by drawing. Chain branching and orientation could significantly enhance the blood compatibility of PLA by prolonging clotting time and decreasing hemolysis ratio, protein adsorption and platelet activation. Fibrous structure as well as micro-grooves can be observed for the oriented PLA which were similar to intimal layer of blood vessel, and this bionic structure was considered to be beneficial to decrease the activation and/or adhesion of platelets

Highly toughened polylactide with novel sliding graft copolymer by in situ reactive compatibilization, crosslinking and chain extension

YesThe “sliding graft copolymer” (SGC), in which many linear poly-ε-caprolactone (PCL) side chains are bound to cyclodextrin rings of a polyrotaxane (PR), was prepared and employed to toughen brittle polylactide (PLA) with methylene diphenyl diisocyanate (MDI) by reactive blending. The SGC was in situ crosslinked and therefore transformed from a crystallized plastic into a totally amorphous elastomer during reactive blending. Meanwhile, PLA-co-SGC copolymer was formed at interface to greatly improve the compatibility between PLA and SGC, and the chain extension of PLA also occurred, were confirmed by FTIR, GPC, SEM, and TEM. The resulting PLA/SGC/MDI blends displayed super impact toughness, elongation at break and nice biocompatibility. It was inferred from these results the crosslinked SGC (c-SGC) elastomeric particles with sliding crosslinking points performed as stress concentrators and absorbed considerable energy under impact and tension process.This work was supported by the National Natural Science Foundation of China (50933001, 51221002 and 51320105012)

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

YesExtrusion 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