Structure-Property Relationships in Biaxially Deformed Polypropylene Nanocomposites

Semi-solid forming processes such as thermoforming and injection blow moulding are used to make much of today’s packaging. As for most packaging there is a drive to reduce product weight and improve properties such as barrier performance. Polymer nanocomposites offer the possibility of increased modulus
(and hence potential product light weighting) as well as improved barrier properties and are the subject of much research attention. In this particular study, polypropylene–clay nanocomposite sheets produced via biaxial deformation are investigated and the structure of the nanocomposites is quantitatively determined in order to gain a better understanding of the influence of the composite structure on mechanical properties. Compression moulded sheets of polypropylene and polypropylene/Cloisite 15A nanocomposite (5 wt.%) were biaxially stretched to different stretching ratios, and then the structure of
the nanocomposite was examined using XRD and TEM techniques. Different stretching ratios produced different degrees of exfoliation and orientation of the clay tactoids. The sheet properties were then investigated using DSC, DMTA, and tensile tests .It was found that regardless of the degree of exfoliation or
orientation, the addition of clay has no effect on percentage crystallinity or melting temperature, but it has an effect on the crystallization temperature and on the crystal size distribution. DMTA and tensile tests show that both the degree of exfoliation and the degree of orientation positively correlate with the dynamic mechanical properties and the tensile properties of the sheet.

Investigation of swelling and network parameters of poly (ethylene glycol)-crosslinked poly (methyl vinyl ether-co-maleic acid) hydrogels

he influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the CO peak from 1708 to 1731 cm-1, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer–water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the Mw of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices.

Viscoelastic Material Models of Polypropylene for Thermoforming Applications

Polypropylene (PP), a semi-crystalline material, is typically solid phase thermoformed at temperatures associated with crystalline melting, generally in the 150° to 160°Celsius range. In this very narrow thermoforming window the mechanical properties of the material rapidly decline with increasing temperature and these large changes in properties make Polypropylene one of the more difficult materials to process by thermoforming. Measurement of the deformation behaviour of a material under processing conditions is particularly important for accurate numerical modelling of thermoforming processes. This paper presents the findings of a study into the physical behaviour of industrial thermoforming grades of Polypropylene. Practical tests were performed using custom built materials testing machines and thermoforming equipment at Queen′s University Belfast. Numerical simulations of these processes were constructed to replicate thermoforming conditions using industry standard Finite Element Analysis software, namely ABAQUS and custom built user material model subroutines. Several variant constitutive models were used to represent the behaviour of the Polypropylene materials during processing. This included a range of phenomenological, rheological and blended constitutive models. The paper discusses approaches to modelling industrial plug-assisted thermoforming operations using Finite Element Analysis techniques and the range of material models constructed and investigated. It directly compares practical results to numerical predictions. The paper culminates discussing the learning points from using Finite Element Methods to simulate the plug-assisted thermoforming of Polypropylene, which presents complex contact, thermal, friction and material modelling challenges. The paper makes recommendations as to the relative importance of these inputs in general terms with regard to correlating to experimentally gathered data. The paper also presents recommendations as to the approaches to be taken to secure simulation predictions of improved accuracy.

Influence of molten-state annealing on the phase structure and crystallization behaviour of high impact polypropylene copolymer

The phase structure evolution of high impact polypropylene copolymer (IPC) during molten-state annealing and its influence on crystallization behaviour were studied. An entirely different architecture of the IPC melt was observed after being annealed, and this architecture resulted in variations of the crystallization behaviour. In addition, it was found that the core-shell structure of the dispersed phase was completely destroyed and the sizes of the dispersed domains increased sharply after being annealed at 200 degrees C for 200 min. Through examination of the coarseness of the phase morphology using phase contrast microscopy (PCM), it was found that a co-continuous structure and an abnormal 'sea-island' structure generally appeared with an increase in annealing time. The original matrix PP component appeared as a dispersed phase, whereas the copolymer components formed a continuous 'sea-island' structure. This change is ascribed to the large tension induced by solidification at the phase interface and the great content difference between the components. When the temperature was reduced the structure reverted to its original form. With increasing annealing time, the spherulite profiles became more defined and the spherulite birefringence changed from vague to clear. Overall crystallization rates and nucleation densities decreased, but the spherulite radial growth rates remained almost constant, indicating that molten-state annealing mainly affects the nucleation ability of IPC, due to a coarsened microstructure and decreased interface area. (C) 2011 Elsevier Ltd. All rights reserved.

Physicochemical and drug diffusion analysis of rifampicin containing polyethylene glycol-poly(epsilon-caprolactone) networks designed for medical device applications

This study reports the physicochemical and drug diffusion properties of rifampicin containing poly(epsilon-caprolactone) (PCL)/polyethylene glycol (PEG) networks, designed as bioactive biomaterials. Uniquely, the effects of the states of both rifampicin and PEG and the interplay between these components on these properties are described. PCL matrices containing rifampicin (1-5%, w/w) and PEG 200 (0-15%, w/w) were prepared by casting from an organic solvent (dichloromethane). The films were subsequently characterized in terms of their thermal/thermorheological, surface and tensile properties, biodegradation and drug diffusion/release properties. Incorporation of PEG and/or rifampicin significantly affected the tensile and surface properties of PCL, lowering the ultimate tensile strength, % elongation at break, Young modulus and storage and loss moduli. Both in the absence and presence of PEG, solubilisation of rifampicin within the crystalline domains of PCL was observed. PEG was present as a dispersed liquid phase. The release of rifampicin (3% loading) was unaffected by the presence of PEG. Similarly the release of rifampicin (5%) was unaffected by low concentrations of PEG (5-10%) however, at higher loadings, the release rate of rifampicin was enhanced by the presence of PEG. Rifampicin release (10% loading) was enhanced by the presence of PEG in a concentration dependent fashion. These observations were accredited to enhanced porosity of the matrix. In all cases, diffusion-controlled release of rifampicin occurred which was unaffected by polymer degradation. This study has uniquely illustrated the effect of hydrophilic pore formers on the physicochemical properties of PCL. Interestingly, enhanced diffusion controlled release was only observed from biomaterials containing high loadings of PEG and rifampicin (5, 10%), concentrations that were shown to affect the mechanical properties of the biomaterials. Care should therefore be shown when adopting this strategy to enhance release of bioactive agents from biomaterials. (C) 2011 Elsevier B.V. All rights reserved.