Fibrillar

The resulting porous, fibrillar polyacetylene film is highly crystalline, so is therefore insoluble, infusible, and otherwise nonprocessible. It is also unstable in air in both the conducting and insulating form. 

Since PAN-based carbon fibers tend to be fibrillar in texture, they are unable to develop any extended graphitic structure. Hence, the modulus of a PAN-based fiber is considerably less than the theoretical value (a limit which is nearly achieved by mesophase fibers), as shown in Fig. 9. On the other hand, most commercial PAN-based fibers exhibit higher tensile strengths than mesophase-based fibers. This can be attributed to the fact that the tensile strength of a brittle material is eontrolled by struetural flaws [58]. Their extended graphitic structure makes mesophase fibers more prone to this type of flaw. The impure nature of the pitch preciusor also contributes to their lower strengths. 

Prior, J., Wallace, D., Hamer, A. and Powers, N., A sprayable hemostat containing fibrillar collagen, bovine thrombin, and autologous plasma. Ann. Thome. Surg., 68, 479-485 (1999). 

In the work reported here, we produced highly fibrillar polypropylene (PP)-LCP blends that were subsequently processed by injection molding without melting the LCP fibers again in order to create tough PP-LCP... 

In an earlier study (44) on the effect of viscosity ratio on the morphology of PP-LCP blends we found that the viscosity ratio is a critical factor in determining the blend morphology. The most fibrillar structure was achieved when the viscosity ratio (i7lcp i7pp) ranged from about 0.5-1. At even lower viscosity ratios the fiber structure was coarser, while at viscosity ratios above unity, the LCP domains tended to be spherical or clusterlike (Fig. 1)=... 

In addition, it was found that the blends with highly fibrillar structure exhibited a significantly lowered viscosity. Increased shear rate caused slight changes in the blend morphology but did not enhance the fiber formation. Thus, in addition to shear, elongational forces are needed to achieve a well-fibrillated blend structure and significant mechanical reinforcement. 

The tensile properties of the extruded blends and composites are presented in Table 2. Compared to the neat PP, a clear reinforcement was achieved after twin-screw blending. The reinforcing effect was even more pronounced with the higher take-up speed (H), evidently due to the extremely fibrillar morphology, as seen in Fig. 3. 

In both the blends and composites, the addition of LCP reinforced the PP matrix considerably. On the basis of the fibrillar morphology throughout the specimens, even better mechanical properties were expected for the composites than for the blends. The poorer than expected reinforcement was primarily due to the lack of adhesion between fiber and matrix. 

During a steady-state capillary flow, several shear-induced effects emerge on blend morphology [4-6]. It is, for instance, frequently observed that TLCP domains form a fibrillar structure. The higher the shear rate, the higher the aspect ratio of the TLCP fibrils [7]. It is even possible that fibers coalesce to form platelet or interlayers. 

The formation of a fibrillar structure in TLCP blends makes the mechanical properties of this kind of composites similar to those of conventional fiber reinforced thermoplastics [11,26]. However, because the molecular orientation and fibrillation of TLCPs are generally flow-induced, the formation, distribution, and alignment of these droplets and fibers are considerably more processing-dependent. We do not know ... 

PET fibers and filaments are characterized by a fibrillar superstructure that corresponds to the general concept of the fibrillar structure of synthetic fibers. The fibrillar... 

Activation of matrix metalloproteinases (MMP) is also involved in vascular and cardiac remodelling. For example, the fibrillar collagen matrix of the heart... 

Menashi et al.153) could confirm the results of Privalov and Tiktopulo152 and inter-prete the described effects as follows In the case of native tropocollagen, the pyrrolidine residues are probably directed away from the fibrillar axis and are mostly coated by water which is structured in the immediate neighbourhood to the pyrrolidine residues. During the denaturation these pyrrolidine residues form hydrophobic bonds with each other or with other apolar residues within the same chain (endothermic interaction) while the structure of water breaks down (increase of entropy). 

Model peptides that could build up quarternary fibrillar structures are not yet known. Though complete explanation of the interdependence between the primary structure and the stability of the quarternary structure has not yet been possible, i.e. the role of the different amino acids in collagen could be understood completely only in correlation with the fibril formation (formation of polar and hydrophobic clusters ). 

Hence, the main aim of the technological process in obtaining fibres from flexible-chain polymers is to extend flexible-chain molecules and to fix their oriented state by subsequent crystallization. The filaments obtained by this method exhibit a fibrillar structure and high tenacity, because the structure of the filament is similar to that of fibres prepared from rigid-chain polymers (for a detailed thermodynamic treatment of orientation processes in polymer solutions and the thermokinetic analysis of jet-fibre transition in longitudinal solution flow see monograph3. ... 

Hence, the extension of an isotropic unoriented partially crystalline polymer leads to the formation of a highly organized material with a characteristic fibrillar structure. The anisotropy of the sample as a whole is expressed by a higher modulus, tenacity and optical anisotropy. It would seem that the increase in strength in the drawing direction suggests that the oriented samples consist of completely extended chains. However, while the strength of such perfect structure for polyethylene has been evaluated as 13000 MPas), the observed values for an oriented sample are 50 to 30 MPa. 

The formation of fibrillar structures during the crystallization of deformed solutions and melts under various conditions of mechanical treatment was observed by many authors22,24,25 who studied the crystallization in stirred or flowing solutions. In all cases... 

The most important feature of polymers obtained by these methods is their high mechanical strength, primarily their elastic moduli and tenacities that, in some cases, approach the theoretical values. It has been recognized that these mechanical properties are uniquely related to the existence of ECC with very perfect chain packing in fibrillar crystals. 

Many authors studying the formation of ECC from melts and solutions suggested that preliminary unfolding and extension of macromolecules occurs. Keller and Maehin25 have shown that in all known cases (including such extreme variants as the crystallization of natural rubber under extension and a polyethylene melt under flow) the same initial process of linear nucleation occurs and fibrillar structures is formed by the macromolecu-lar chains oriented parallel to the fibrillar axes27. ... 

We will compare the change in the free energy per macromolecule in the formation of folded-chain (curve 1) and fibrillar (curve 2) crystals as a function of /J. Figure 8 b shows these curves calculated for the corresponding equilibrium values [a]. The increase... 

Fig. 8a-c. Dependence of the degree of crystallinity (a), free energy (b) and melting temperature (c) on fi. 1 folded-chain crystals, 2 fibrillar crystals the broken line corresponds tofi=fia... 

To avoid misunderstanding, it should be emphasized that if the transition from one type of crystallization to the other one is considered, this does not imply a transformation of crystals of one type into the other one during stretching. In contrast, if the molecule enters a folded-chain crystal, it is virtually impossible to extend it. In this case, we raise the question, which of the two crystallization mechanisms controls the process at each given value of molecular orientation in the melt (this value being kept constant in the crystallization process during subsequent cooling of the system). At /J < /3cr, only folded-chain crystals are formed whereas at / > only fibrillar crystals result at /8 /3cr, crystals of both types can be formed. 

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