Shaofeng Ran

Structure and process relationship of electrospun bioabsorbable nanofiber membranes

Abstract An electrospinning method was used to fabricate bioabsorbable amorphous poly( d , l -lactic acid) (PDLA) and semi-crystalline poly( l -lactic acid) (PLLA) nanofiber non-woven membranes for biomedical applications. The structure and morphology of electrospun membranes were investigated by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and synchrotron wide-angle X-ray diffraction/small angle X-ray scattering. SEM images showed that the fiber diameter and the nanostructured morphology depended on processing parameters such as solution viscosity (e.g. concentration and polymer molecular weight), applied electric field strength, solution feeding rate and ionic salt addition. The combination of different materials and processing parameters could be used to fabricate bead-free nanofiber non-woven membranes. Concentration and salt addition were found to have relatively larger effects on the fiber diameter than the other parameters. DSC and X-ray results indicated that the electrospun PLLA nanofibers were completely non-crystalline but had highly oriented chains and a lower glass transition temperature than the cast film.

Control of structure, morphology and property in electrospun poly(glycolide-co-lactide) non-woven membranes via post-draw treatments

Non-woven biodegradable membranes fabricated by electrospinning have recently attracted a great deal of attention for biomedical applications. In this study, microstructure, morphology and texture of electrospun poly(glycolide-co-lactide) (GA/LA: 90:10, PLA10GA90) non-woven membranes were investigated after post-draw and thermal treatments to tailor the degradation and mechanical properties. As-prepared electrospun PLA10GA90 membranes exhibited a low degree of crystallinity. When annealed at elevated temperatures without drawing, the membrane showed a higher degree of crystallinity with distinct lamellar structure but no overall orientation. The crystal orientation improved significantly when the membrane was drawn and annealed. As the elongation ratio increased, the degree of orientation and the tensile strength were increased. The corresponding tensile retention time was also increased from 2 to 12 days during in vitro degradation. Post-drawn and annealed membranes exhibited a slower degradation rate in the beginning of incubation, but a faster rate after two weeks of degradation when compared to as-spun membranes.

Structural changes during deformation of Kevlar fibers via on-line synchrotron SAXS/WAXD techniques

Abstract On-line studies of structure and morphology changes in Kevlar 49 fibers during stretching were carried out using synchrotron simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. A unique two-dimensional (2D) image analysis method was used to extract quantitative information of crystal, amorphous and mesomorphic fractions from 2D WAXD patterns. Results showed that about 20% of the fraction (mass) in the Kevlar 49 fiber was mesophase, 50% was crystalline and 30% was amorphous. There were transitions between crystal, amorphous and mesomorphic fractions during deformation. The crystal orientation was obtained in terms of the Hermans orientation function f2 from the azimuthal scan of the (200) crystal reflection. The crystal orientation was found to be quite high in the Kevlar 49 fiber and increased with the stretch ratio. The fibril length and misorientation were also obtained from 2D SAXS patterns by using the Ruland method. Results showed that the fibril length decreased with the stretch ratio until 2.0% and then increased. The misorientation decreased with increasing stretch ratio.

Molecular orientation and structural development in vulcanized polyisoprene rubbers during uniaxial deformation by in situ synchrotron X-ray diffraction

Abstract Molecular orientation and strain-induced crystallization of vulcanized natural rubbers (by sulfur and peroxide) and synthetic polyisoprene rubber (by sulfur) during uniaxial deformation at 0 °C were studied by in situ synchrotron wide-angle X-ray diffraction. The high intensity of synchrotron X-rays and new image analysis methods made it possible to estimate the mass fractions of strain-induced crystals and amorphous chains in both oriented and unoriented states. Most of the polymer chains (∼75%) were found to be in the random coil state even at large strains (>5.0). Only about 5% the amorphous chains were oriented, whereas the rest of the chains (∼20%) were in the crystalline phase. Sulfur vulcanized and peroxide vulcanized natural rubbers did not exhibit notable differences in structure and property relationships. In contrast, synthetic polyisoprene rubber showed a different behavior of deformation-induced structural changes, which can be attributed to the difference in cross-link topology. Our results indicated that strain induces a network of microfibrillar crystals in both natural and synthetic polyisoprene rubbers due to the inhomogeneity of cross-link distribution that is responsible for their elastic properties.

Novel image analysis of two-dimensional X-ray fiber diffraction patterns : example of a polypropylene fiber drawing study

On-line studies of the structural development during continuous drawing of a polypropylene fiber were carried out using synchrotron wide-angle X-ray diffraction. A unique image analysis method was introduced to extract quantitative information on the crystal, amorphous and mesomorphic fractions. In addition, the unit-cell parameters and the crystal orientation were obtained under various draw conditions. It was found that the mesophase remained about constant during drawing. At draw ratios less than 6.0, the crystallinity increased and the crystal density decreased as a result of the stress-induced crystallization of crystals with a large degree of disordering. At draw ratios above 6.0, the crystallinity increased slowly and the decrease in crystal density was also retarded because of the draw-induced melting. The crystal orientation increased with increasing draw ratio up to a ratio of 6.0 and then decreased, probably because of chain breakage.

Strain-induced molecular orientation and crystallization in natural and synthetic rubbers under uniaxial deformation by in-situ synchrotron X-ray study

Abstract In-situ synchrotron wide-angle X-ray diffraction (WAXD) studies and simultaneous measurements of stress and strain during uniaxial stretching of various vulcanized rubbers were carried out (at room temperature and 0°C) to reveal the strain-induced molecular orientation and crystallization relationships. Rubbers evaluated included natural rubber (NR), synthetic poly-isoprene rubber (IR), poly-cis-1,4-butadiene rubber (BR) and butyl rubber (IIR). Some universal features were observed in these systems: (i) At high strains (> 5.0), the majority of the chains (up to 50 ≈ 75%) in natural and synthetic rubbers remained in the un-oriented amorphous state with only a small amount of crystalline fraction formed (10–20%). The rest of the chains were in the oriented amorphous state. (ii) During deformation, the oriented amorphous chains acted as precursors to strain-induced crystallization. A network of micro-fibrillar crystallites is formed within the closely populated vulcanization points, leading to the e...

Studies of the mesophase development in polymeric fibers during deformation by synchrotron SAXS/WAXD

On-line structural and morphological studies on Kevlar 49 and isotactic polypropylene (iPP) fibers during deformation were carried out using synchrotron small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). A novel image analysis method was used to extract quantitative fractions of the crystal phase, the amorphous phase and a “mesomorphic” (intermediate) phase from two-dimensional (2D) WAXD patterns. Results showed that about 20 wt% in the Kevlar 49 fiber had an intermediate mesophase morphology. The transitions between crystal phase, amorphous phase and mesophase were not obvious during deformation of Kevlar 49 fiber at room temperatures. 2D SAXS patterns indicated that the superstructure of the Kevlar 49 fiber was fibril in nature. 2D WAXD results of iPP fibers showed that the α-form crystals were quite defective in the initial state and were converted to the well-known mesomorphic form by drawing at room temperatures. The mesophase in Kevlar 49 fibers was then compared with that in iPP fibers. The shape of one-dimensional equatorial peak of the mesophase in the iPP fiber was similar to that in the Kevlar fiber, indicating that the mesophase in both iPP and Kevlar fibers could be similar in some aspects of molecular arrangement. Corresponding 2D SAXS patterns showed that there was no obvious long period in the mesophase of the drawn iPP fiber. We speculate that the constituents of the mesomorphic fraction extracted in the drawn iPP fibers may consist of partially oriented bundles of helical chains with random helical hands as well as oriented chains with no helical structures (consisting of stereo/tacticity defects). The latter is similar to the mesophase of rigid chains in Kevlar fibers, consisting of only oriented chains with no helical structures.

Combined techniques of Raman spectroscopy and synchrotron two-dimensional x-ray diffraction for in situ study of anisotropic system: Example of polymer fibers under deformation

Simultaneous measurements of Raman spectroscopy and synchrotron two-dimensional (2D) wide-angle x-ray diffraction (WAXD) have been successfully demonstrated for in situ study of an anisotropic system: isotactic polypropylene (iPP) fiber under tensile deformation. A fiber-optic probe was used to remotely deliver the incident laser beam on the sample as well as to collect the Raman signal based on the confocal arrangement, whereas high resolution 2D WAXD patterns were obtained simultaneously at the same position during deformation of polymers. The combined techniques yielded complementary information on the molecular structural evolution in both crystalline and amorphous phases. 2D WAXD results showed that the α-form iPP crystals were converted into the mesophase upon stretching at room temperature. Corresponding Raman spectra showed that characteristic bands from the crystal phase became weaker or disappeared during the transition from the crystal phase to the mesophase. However, the bands associated with ...