Coronary Heart Disease (CHD) is one of the leading causes of death worldwide, claiming over seven million lives each year. Permanent metal stents, the current standard of care for CHD, inhibit arterial vasomotion and induce serious complications such as late stent thrombosis. Bioresorbable vascular scaffolds (BVSs) made from poly L-lactide (PLLA) overcome these complications by supporting the occluded artery for 3-6 months and then being completely resorbed in 2-3 years, leaving behind a healthy artery. The BVS that recently received clinical approval is, however, relatively thick (~150 µm, approximately twice as thick as metal stents~80 µm). Thinner scaffolds would facilitate implantation and enable treatment of smaller arteries. The key to a thinner scaffold is careful control of the PLLA microstructure during processing to confer greater strength in a thinner profile. However, the rapid time scales of processing (~1 s) defy prediction due to a lack of structural information. Here, we present a custom-designed instrument that connects the strain-field imposed on PLLA during processing to in situ development of microstructure observed using synchrotron X-ray scattering. The connection between deformation, structure and strength enables processing-structure-property relationships to guide the design of thinner yet stronger BVSs.
In situ synchrotron X-ray scattering was used to reveal the transient microstructure of poly(L-lactide) (PLLA)/tungsten disulfide inorganic nanotubes (WS2NTs) nanocomposites. This microstructure is formed during the blow molding process (“tube expansion”) of an extruded polymer tube, an important step in the manufacturing of PLLA-based bioresorbable vascular scaffolds (BVS). A fundamental understanding of how such a microstructure develops during processing is relevant to two unmet needs in PLLA-based BVS: increasing strength to enable thinner devices and improving radiopacity to enable imaging during implantation. Here, we focus on how the flow generated during tube expansion affects the orientation of the WS2NTs and the formation of polymer crystals by comparing neat PLLA and nanocomposite tubes under different expansion conditions. Surprisingly, the WS2NTs remain oriented along the extrusion direction despite significant strain in the transverse direction while the PLLA crystals (c-axis) form along the circumferential direction of the tube. Although WS2NTs promote the nucleation of PLLA crystals in nanocomposite tubes, crystallization proceeds with largely the same orientation as in neat PLLA tubes. We suggest that the reason for the unusual independence of the orientations of the nanotubes and polymer crystals stems from the favorable interaction between PLLA and WS2NTs. This favorable interaction leads WS2NTs to disperse well in PLLA and strongly orient along the axis of the PLLA tube during extrusion. As a consequence, the nanotubes are aligned orthogonally to the circumferential stretching direction, which appears to decouple the orientations of PLLA crystals and WS2NTs.
Transfer of excitation from cadmium to sodium atoms was investigated in anheat pipe oven illuminated by a pulsed laser tuned on the intercombinationtransition of cadmium. A rich emission spectrum with cadmium as well assodium lines was observed. Intramultiplet mixing distributes the initialexcited level population 5p3P1 to the nearby fine structurelevels 5p3P0,2 of the same multiplet. We have experimentalevidence that the energy transfer pathway is from Cd (5p3PJ) to Na(4p2PJ) which is collisionally rapidly converted toNa(3d2DJ), from which the strongest emission was observed.PACS No.: 34.90+q
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