Semicrystalline network

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

The volume inside the semicrystalline polymers can be divided between the crystallized and amorphous parts of the polymer. The crystalline part usually forms a complicated network in the matrix of the amorphous polymer. A visualization of a single-polymer crystallite done [111] by the Atomic Force Microscopy (AFM) is shown in Fig. 9. The most common morphology observable in the semicrystalline polymer is that of a spherulitic microstructure [112], where the crystalline lamellae grows more or less radially from the central nucleus in all directions. The different crystal lamellae can nucleate separately... 

Thus the factor (Mc — M )/(Mn — M ) may be thought of as the sieving term mentioned in the theory of Yasuda et al. [150], In the Peppas-Reinhart theory, the sieving mechanism takes an understandable form which is a function of the structure of the network. It must be noted that the presence of semicrystalline regions in the polymer membrane leads to deviations from the predicted dependencies in this theory. These researchers found that as the crosslinking density in the polymer membrane increased, the solute diffusion coefficient decreased, further illustrating the importance of structural parameters of the polymer network in predicting the solute diffusion coefficient [156],... 

Semicrystalline polyamide fine powders have been used as toughening agents for epoxy networks. The powders can be obtained by grinding granules, or directly by anionic polymerization of lactams, 6 or 12, in an organic solvent from which the formed semicrystalline polymer precipitates. Microporous powders with an average particle size in the range of 10 pm and a narrow particle-size distribution, are obtained. 

Cavitation is often a precursor to craze formation [20], an example of which is shown in Fig. 5 for bulk HDPE deformed at room temperature. It may be inferred from the micrograph that interlamellar cavitation occurs ahead of the craze tip, followed by simultaneous breakdown of the interlamellar material and separation and stretching of fibrils emanating from the dominant lamellae visible in the undeformed regions. The result is an interconnected network of cavities and craze fibrils with diameters of the order of 10 nm. This is at odds with the notion that craze fibrils in semicrystalline polymers deformed above Tg are coarser than in glassy polymers [20, 28], as well as with models for craze formation in which lamellar fragmentation constitutes an intermediate step [20, 29] but, as will be seen, it is difficult to generalise and a variety of mechanisms and structures is possible. 

In man-made fibres, any stretching will irreversibly alter the crystallinity and there is no control of the lateral size of polymer crystals. Semicrystalline polymer networks typically consist of platelet type crystals whose width exceeds their thickness by several order of magnitudes because only the thickness is controlled by the chain folding [61]. In contrast to synthetic fibres, spider silk does not need any mechanical treatment by external forces the constituents self-assemble directly during the spinning-process. These examples clearly demonstrate the need for more detailed control of the mesoscopic structures for further development of man-made materials. 

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