This research is the first systematic investigation of solid-state orientation as a novel method for controlling drug release from biodegradable polymers. The effect of various degrees of polymer orientation was studied in oriented Poly (L-lactic acid) (PLA) films containing curcumin and theophylline as model drugs. Additionally, direction specific drug release was studied from oriented PLA rods containing paracetamol. The films oriented to 2X uniaxial constant width (UCW) or 2X2Y biaxial draw ratio showed retardation of drug release, when their nematic structure was stabilised by the presence of crystalline theophylline. Contrarily, the same films when contained solid solution of curcumin, shrunk in the release medium and exhibited a release profile similar to the un-oriented films. All films oriented to the UCW draw ratio ≥ 3X contained α crystalline form of PLA and showed acceleration of drug release proportionate to the draw ratio. According to the proposed mechanism augmented formation of water filled channels in these films was responsible for faster drug release. Similarly, the paracetamol loaded PLA rods die-drawn to uniaxial draw ratios ≥ 3X exhibited enhancement of drug release. Importantly, the amount of drug released along the oriented chain axis was significantly larger than that in the perpendicular direction. Drug release from the die-drawn rods was accelerated by a greater degree than that observed from the oriented films. This can be correlated to the differences in their size, geometry and the crystalline form of PLA. In conclusion, the current study provided substantial evidence that solid-state orientation can offer a control over drug release from PLA.

Yes / The shape memory effect of highly oriented long‐chain‐branched poly(lactic acid) (LCB‐PLA) prepared through solid‐phase die drawing technology was studied by comparison with PLA. When the recovery temperature increased from 60°C to 120°C, for PLA, only one‐step recovery at about 80°C can be observed and the recovery ratio was below 21.5%, while, for LCB‐PLA, multiple recovery behavior with high recovery ratio of 78.8% can be achieved. For oriented PLA, the recovery curve of the final sample showed the same trend with that of sample suffering just free drawing; while for oriented LCB‐PLA, the recovery curve of the final sample showed the same trend with that of sample suffering just die drawing. After shape recovery, the mechanical properties of LCB‐PLA showed a linear downward trend with the recovery temperature. Together with amorphous phase, the oriented mesomorphic phase, which formed during solid die drawing, can act as switching domains. And thus, upon heating, the chain segment of amorphous phase relaxed at first and triggered the first macroscopical shape recovery, leading to the decrease of long period (Lac) and the thickness of the amorphous layer (La). Then, with further increasing temperature, the oriented mesomorphic phase gradually relaxed resulting subsequently multi‐shape recovery, and the Lac and the La further decreased. Therefore, by regulating the recovery temperature of oriented LCB‐PLA, the shape recovery ratio and mechanical strength can be controlled effectively, and thus the self‐reinforced and self‐fastening effect can be achieved simultaneously for PLA as bone fixation material.

This research is the first systematic investigation of solid-state orientation as a novel method for controlling drug release from biodegradable polymers. The effect of various degrees of polymer orientation was studied in oriented Poly (L-lactic acid) (PLA) films containing curcumin and theophylline as model drugs. Additionally, direction specific drug release was studied from oriented PLA rods containing paracetamol. The films oriented to 2X uniaxial constant width (UCW) or 2X2Y biaxial draw ratio showed retardation of drug release, when their nematic structure was stabilised by the presence of crystalline theophylline. Contrarily, the same films when contained solid solution of curcumin, shrunk in the release medium and exhibited a release profile similar to the un-oriented films. All films oriented to the UCW draw ratio ≥ 3X contained α crystalline form of PLA and showed acceleration of drug release proportionate to the draw ratio. According to the proposed mechanism augmented formation of water filled channels in these films was responsible for faster drug release. Similarly, the paracetamol loaded PLA rods die-drawn to uniaxial draw ratios ≥ 3X exhibited enhancement of drug release. Importantly, the amount of drug released along the oriented chain axis was significantly larger than that in the perpendicular direction. Drug release from the die-drawn rods was accelerated by a greater degree than that observed from the oriented films. This can be correlated to the differences in their size, geometry and the crystalline form of PLA. In conclusion, the current study provided substantial evidence that solid-state orientation can offer a control over drug release from PLA.

The goal of this research is to investigate the combined effects of glass fibre reinforcement and molecular orientation in polypropylene-short glass fibre composites. Specimens have been fabricated using the injection moulding process and drawn using a small die drawing rig. The effects of die drawing on the fibre composites are complex, with the drawing process orienting both the polymer molecules and the glass fibres. This may be accompanied by the creation of voids in the polymer matrix and their destruction in the compressive stress field thus restoring the interfacial contact area between fibre and matrix. Unfilled and short glass fibre filled polypropylene specimens, with fibre content 7% wt, 13%wt, 27%wt, and 55%wt, were injection moulded prior to the die drawing process. An experimental program of die drawing within an oven at elevated temperature was conducted for polypropylene filled to various levels and at different strain rates. The specimens drew to draw ratios in the range γ=1.41 to γ=5.6. Mechanical characterization of the test materials has been conducted by examining the tensile stress strain and fracture behaviour under uniaxial conditions. The influence of glass fibre content and drawing conditions (draw ratio) on the fracture toughness and crack propagation was investigated using the double edge notched fracture test. The notch lengths ranged from 1.5 to 2.5 mm for 10 mm wide specimens. The critical stress intensity factor increased as the fibre content increased up to a limiting filler level. The fracture toughness of both unfilled and fibre filled polypropylene were found to be highly dependent on draw ratio. The results were analysed to find out the optimal draw ratio and fibre content that yielded the maximum modulus, strength and fracture toughness. Data showed that, at a given draw ratio, modulus, strength and fracture toughness increased with increasing fibre content to a maximum and then decreased. The optimum material was obtained at a draw ratio of 2.5 and filler loading 13wt%.

The goal of this research is to investigate the combined effects of glass fibre reinforcement and molecular orientation in polypropylene-short glass fibre composites. Specimens have been fabricated using the injection moulding process and drawn using a small die drawing rig. The effects of die drawing on the fibre composites are complex, with the drawing process orienting both the polymer molecules and the glass fibres. This may be accompanied by the creation of voids in the polymer matrix and their destruction in the compressive stress field thus restoring the interfacial contact area between fibre and matrix. Unfilled and short glass fibre filled polypropylene specimens, with fibre content 7% wt, 13%wt, 27%wt, and 55%wt, were injection moulded prior to the die drawing process. An experimental program of die drawing within an oven at elevated temperature was conducted for polypropylene filled to various levels and at different strain rates. The specimens drew to draw ratios in the range ¿=1.41 to ¿=5.6. Mechanical characterization of the test materials has been conducted by examining the tensile stress strain and fracture behaviour under uniaxial conditions. The influence of glass fibre content and drawing conditions (draw ratio) on the fracture toughness and crack propagation was investigated using the double edge notched fracture test. The notch lengths ranged from 1.5 to 2.5 mm for 10 mm wide specimens. The critical stress intensity factor increased as the fibre content increased up to a limiting filler level. The fracture toughness of both unfilled and fibre filled polypropylene were found to be highly dependent on draw ratio. The results were analysed to find out the optimal draw ratio and fibre content that yielded the maximum modulus, strength and fracture toughness. Data showed that, at a given draw ratio, modulus, strength and fracture toughness increased with increasing fibre content to a maximum and then decreased. The optimum material was obtained at a draw ratio of 2.5 and filler loading 13wt%.