Micro fibril orientation

These are covered with a sheath of para-crystaUine polyglucosan material surrounded by hemicellulose [29]. In most natural fibers, these micro-fibrils orient themselves at an angle to the fiber axis called the micro-fibril angle. The ultimate mechanical properties of natural fibers are found to be dependent on the microfibrillar angle. Gassan et al. have performed calculations on the elastic properties of natural fibers [30]. 

The dominating S2-layer contains the cellulose micro fibrils orientated under an acute angle toward the fiber axis. Such orientation of the microfibrils imparts to natural cellulose fibers increased mechanical properties. The microfibrils of the cell wall consist of elementary nanofibrils, and each such fibril is built of ordered nanocrystallites and low ordered non-crystalline (amorphous] domains statistically alternated along the fibril. The early investigations supposed the presence in various cellulose samples of elementary nanofibrils having a constant lateral size of 3.5 nm (Manley, 1964 Muhlenthaler, 1969]. However, recent... 

In order to supplement micro-mechanical investigations and advance knowledge of the fracture process, micro-mechanical measurements in the deformation zone are required to determine local stresses and strains. In TPs, craze zones can develop that are important microscopic features around a crack tip governing strength behavior. For certain plastics fracture is preceded by the formation of a craze zone that is a wedge shaped region spanned by oriented micro-fibrils. Methods of craze zone measurements include optical emission spectroscopy, diffraction... 

In some respects semi-crystalline polymers are similar to filled reinforced systems (crystallites, embedded in amorphous matrix) in the same way highly oriented semicrystalline polymers are similar to fibber-reinforced systems (micro-fibrils embedded in... 

Extended chain crystals can be obtained by crystallization under high pressures or under uniaxial extension. So-called shish-kebob structures are frequently observed when crystallizing polymers under orientation, e.g. in stirred solutions and polymer processing from the melt. Similar to lamellae and (micro) fibrils treated in previous chapters, these structures can be routinely visualized and analyzed by AFM. 

As will be discussed later (see p. 332), these data provide strong support for the argument that the microfibrils are produced by on-the-site synthesis and orientation (apposition) of the cellulosic microfibrils under the guiding influence of the living cell, rather than by a mechanism that proposes synthesis of the micro fibrils within the cell and subsequent translocation and crystallization (deposition) of microfibrils on the cell wall by exocellular factors. Further factors relevant to these opposing theories emerge from study of the fine structure of the cellulosic microfibrils, as discussed in the following Section. 

Orientation. The orientation of the cellulose chain axis in a number of different fibers has been studied in detail (21-22). Much less is known about the cellulose orientation in the plane perpendicular to the chain axis. The orientation in this plane is determined by the lateral arrangement of the microfibrils relative to each other. In algal celluloses, the evidence from x-ray and electron diffraction indicates that the microfibrils are arranged nonrandomly in the plane perpendicular to the chain axis (21-29). Preston (22) proposed the model shown in Figure 1 to explain his x-ray data. There are two different orientations of the microfibrils. The 002 planes in one set of microfibrils are approximately perpendicular to the 002 planes in the second set. In both sets of micro-fibrils, the 101 planes are oriented parallel to the cell wall surface (refer to Figure 1). Preston s model has been confirmed in more recent studies (29). In the remainder of this report, the type of orientation shown in Figure 1 will be referred to as alternating orientation. 

As previously mentioned, natural fibres present a multi-level organization and consist of several cells formed out of semi-crystalline oriented cellulose micro fibrils. Each microfibril can be considered as a string of cellulose crystallites, linked along the chain axis by amorphous domains (Fig. 19.10) and having a modulus close to the theoretical limit for cellulose. They are biosynthesized by enzymes and deposited in a continuous fashion. A similar structure is reported for chitin, as discussed in Chapter 25. Nanoscale dimensions and impressive mechanical properties make polysaccharide nanocrystals, particularly when occurring as high aspect ratio rod-like nanoparticles, ideal candidates to improve the mechanical properties of the host material. These properties are profitably exploited by Mother Nature. 

Hierarchical fibrillar model [80] This model was proposed for drawn TLCP fibers. They are composed of bundles of macro fibrils (5 p,m), fibrils (0.5 (Jim), and micro fibrils (0.05 p.m) in a hierarchical order (see Figure 8.17). This type of highly oriented fibrillar morphology is also found in the inner skin region of the injection-molded parts, as illustrated in Figure 8.18. 

Emons A.M.C., Derksen X, and Sassen M.M.A. 1992. Do microtubules orient plant cell wall micro-fibrils Physiol Plant 84 486-493. 

The template-assisted synthetic strategies outlined above produce micro- or mesoporous stmetures in which amorphous or crystalline polymers can form around the organic template ligands (174). Another approach is the use of restricted spaces (eg, pores of membranes, cavities in zeolites, etc.) which direct the formation of functional nanomaterials within thek cavities, resulting in the production of ultrasmaU particles (or dots) and one-dimensional stmetures (or wkes) (178). For example, in the case of polypyrrole and poly(3-methylthiophene), a solution of monomer is separated from a ferric salt polymerization agent by a Nucleopore membrane (linear cylindrical pores with diameter as small as 30 nm) (179—181). Nascent polymer chains adsorb on the pore walls, yielding a thin polymer film which thickens with time to eventually yield a completely filled pore. De-encapsulation by dissolving the membrane in yields wkes wherein the polymer chains in the narrowest fibrils are preferentially oriented parallel to the cjlinder axes of the fibrils. 

Figure 5.15. MFC can be obtained from incompatible polymer blends by extrusion and orientation (the fibrillization step) followed by thermal treatment at a temperature between the melting points of the two components at constant strain (the isotropization step). The block copolymers formed during the isotropization (in the case of condensation polymers) play the role of a self-compatibilizer. Prolonged annealing transforms the matrix into a block and thereafter into a random copolymer (a) an MFC on the macro level, (b) an MFC on the micro (molecular) level (Fakirov Evstatiev, 1994).

Another aspect of the multiphase rheometry is related to the interrelations between the flow field and system morphology. In this text the term morphology will refer to the overall physical form or shape of the physical structure of a material, usually described as either a dispersed phase (particles or domains), co-continuous lamellae, fibrils or spherulites. Furthermore, morphology considers distribution and orientation of the phases, the interfacial area, the volume of the interphase, etc. However, the term must be distinguished from micro-morphology, which describes structures of the crystalline phase. Flow may induce two modifications of morphology that may complicate interpretation of data the concentra-... 

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