Kink-bands

Resistance to axial compressive deformation is another interesting property of the silk fibers. Based on microscopic evaluations of knotted single fibers, no evidence of kink-band failure on the compressive side of a knot curve has been observed (33,35). Synthetic high performance fibers fail by this mode even at relatively low strain levels. This is a principal limitation of synthetic fibers in some stmctural appHcations. 

Compression along the grain causes the kinking of cell walls, in much the same way that composites fail in compression (Chapter 25, Fig. 25.5). The kink usually initiates at points where the cells bend to make room for a ray, and the kink band forms at an angle of 45° to 60°. Because of this kinking, the compressive strength is less (by a factor of about 2 - see Table 26.1) than the tensile strength, a characteristic of composites. 

Figure 2.46 Model of packing of conformationally disordered chains of sPP in disordered modifications of form II presenting kink bands.189,190 Chains drawn with thick and thin fines are at 0 and 0.5 along b. In the ordered portion of crystal chains are in ordered twofold (T2G2)B helical conformation, whereas in the defective portion (delimited by dashed lines) chains are in T2G2T6 conformation.

Figure 2.47 Models of packing in limit-ordered forms (a) II and (c) IV of sPP and (b) model of conformationally disordered modification, presenting kink bands, intermediate between limit-ordered models of form II and form IV. In defective region of model (b), delimited by dashed lines, chains are packed as in form IV, whereas in ordered regions chains are packed as in the form II.

Conformational disorder and kink-bands structures have recently been found also in random copolymers of syndiotactic polypropylene with small amounts of ethylene.192 193 The ethylene units are included in the crystalline regions193 and induce the crystallization of the metastable form II of sPP with conformationally disordered chains characterized by kink bands. Portions of chains containing the ethylene units tend, indeed, to assume a trans planar conformation, producing the kink-band defects in chains in the prevailing twofold helical conformation.192193... 

This implies a modification of the chain direction and, finally, a generation of a helix with a larger cross section than that of the trans planar chain.218 Such phase transitions are often associated with the onset of some conformational disorder characterized by the occurrence of kink bands (Figure 2.48b), similar to those found in sPP samples quench crystallized from solutions189,190 (Figures 2.46 and 2.47) or in polyethylene.219 It is apparent from Figure 2.48... 

Figure 2.48 Possible cooperative mechanism of crystal-crystal transition from (a) trans planar form III of sPP into (c) isochiral helical form II. Transition occurs through formation of (b) intermediate conformationally disordered modifications containing kink bands, characterized by helical sequences having same chirality (R = right-handed helix). Formation of helical sequences of opposite chirality (right- and left-handed) produces (if) steric interactions between neighboring chains.

Gohil, R. M. and Petermann, J. Chain conformational defects in polyvinylidene fluoride. Polymer 22, 1612 (1981) Takahashi, Y. and Tadokoro, H. Formation mechanism of kink bands in modification II of poly(vinylidene fluoride). Evidence for flip-flop motion between TGTG and TGTG conformations. Macromolecules 13, 1316 (1980) Takahashi, Y., Tadokoro,... 

H. and Odajima, A. Kink bands in form I of poly(vinylidene fluoride). Macromolecules 13, 1318(1980)... 

In many applications materials are subjected to compressive stresses. The macroscopic phenomena of collapse under an axial compression are the well-known shear and kink bands. In polymers they are caused by the buckling of chains, accompanied by changes in the chain conformation. The resistance against buckling is expressed by the yield strength under axial compression, ac max. Northolt (1981) found a relationship between c,max and Tg. 

Also visible in Fig.2(a) are diffusely etched bands coincident with and extending beyond the rays containing the slip bands. This etching effect represents a type of kink band (20), i. e., an area at die edges of which the orientation changes abruptly. Similar kink bands have also been observed in abraded surfaces of zinc (37), and can be expected to be general. 

There are a number of processes that create fast pathways of exchange and effectively short-circuit volume diffusion into a crystal. Thus, the real world may be influenced by crystal defects and dislocations, mineral inclusions, exsolution lamellae, kink bands, microcracks, and other cryptic features (Fig. 12C). Diffusion is always active on a scale that can be modeled (Fig. 12B) and thus a world-view where all minerals are perfectly equilibrated and homogeneous (Fig. 12A) is generally a figment of imagination. In thermometry, these factors all potentially contribute to the compositions that are measured. Major advances have been made in determining when the macroscopic model world accurately predicts the microscopic real world situation. However, more work may be necessary to accurately deconvolute complex cases and tests should always be applied to evaluate thermometry. 

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