Polymeric membranes electron microscopy

In addition to enzymatic hydrolysis of natural lipids in polymeric membranes as discussed in chapter 4.2.2., other methods have been applied to trigger the release of vesicle-entrapped compounds as depicted in Fig. 37. Based on the investigations of phase-separated and only partially polymerized mixed liposomes 101, methods to uncork polymeric vesicles have been developed. One specific approach makes use of cleavable lipids such as the cystine derivative (63). From this fluorocarbon lipid mixed liposomes with the polymerizable dienoic acid-containing sulfolipid (58) were prepared in a molar ratio of 1 9 101115>. After polymerization of the matrix forming sulfolipids, stable spherically shaped vesicles are obtained as demonstrated in Fig. 54 by scanning electron microscopy 114>. 

The hole formation in the liposomal membrane after treating the vesicles with reducing agents can be demonstrated by the fast and complete release of eosin, a fluorescent marker. Final proof that the polymeric backbone of the uncorked vesicles does not collapse comes from scanning electron microscopy. Fig. 56 shows the spherical structure of the liposomes with holes. 

The first three methods involve the measurement of structural-related parameters while the last one is a typical permeation-related teclmique. Both electron microscopy and AFM can provide qualitative measurement of membrane materials. Figure 7 shows the top surface of porous polymeric membrane observed by scaiming electron microscopy (SEM). The bubble point method and permeation measurement, on the other hand, provide quantitative information of membrane materials. 

Fig. 7. Visualization of top surface of a porous polymeric membrane by scanning electron microscopy (10,000x).

Fujii et al. [13] studied morphological structures of the cross section of various hollow fibers and fiat sheet membranes by high-resolution field emission scanning electron microscopy. Figure 6.8 shows a cross-sectional structure of a flat sheet cellulose acetate RO membrane. The layer near the top surface is composed of a densely packed monolayer of polymeric spheres, which is supported by a layer formed with completely packed spheres. The contours of the spheres in the top layer can be observed. The middle layer is also composed of loosely packed and partly fused spheres, which are larger than the spheres in the surface layer. In the middle layer, there are many microvoids, the sizes of which are the same as the spheres. The layer near the bottom is denser than the middle layer, and the spheres are deformed and fused. Interstitial void spaces between the spheres, which may be called microvoids, are clearly observed. This structure seems common for the flat sheet as well as the hollow fiber membranes. For example. Fig. 6.9 shows a cross section of a hollow fiber made of PMMA B-2 (a copolymer containing methyl methacrylate and a small amount of sulfonate groups). The inside surface layer is composed of the dense structure of compactly packed fine polymeric particles. The particle structure of the middle layer... 

Many experimental techniques have been used to examine the detailed structure of perfluorinated polymeric membranes. These include transmission electron microscopy [23], small angle X-ray scattering [24], Infra Red spectroscopy [25,26], neutron diffraction [27], Nuclear Magnetic Resonance [26,28], mechanical and dielectric relaxation [25,29], X-ray diffraction, and transport measurements. All these methods show convincing evidence for the existence of two phases in the perfluorosulfonate and perfluorocarboxylate polymers. One phase has crystallinity and a structure close to that of polytetrafluoroethylene (PTFE), and the other is an aqueous phase containing ionic groups. 

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