Lamellae lamellar structures

The single crystal of a polymer is a lamellar structure with a thin plateletlike form, and the chain runs perpendicular to the lamella. The crystal is thinner than the polymer chain length. The chain folds back and forth on the top and bottom surfaces. Since the fold costs extra energy, this folded chain crystal (FCC) should be metastable with respect to the thermodynamically more stable extended chain crystal (ECC) without folds. 

Well-ordered lamellar structures. The lamellae are arranged in parallel, giving rise to long-range order. Examples are soaps, phosphoUpids and clays. 

Nylon crystallites consist of sheets of chains that are hydrogen-bonded to their neighbors. On a supermolecular scale, crystallites have a lamellar structure, that is they are many times longer and broader than they are thick. When nylon crystallizes from an isotropic molten state, it generally forms spherulites, which consist of ribbon-like lamellae radiating in all directions... 

Figure 7.17 AFM image of polyethylene grown at 160 °C and subsequently crystalli/.ed during cooling on the surface of a planar CrOVSiOj catalyst. The left hand inset indicates schematically how polyethylene molecules fold into lamellar structures. The AFM image shows how these lamellae have a tendency to order locally. The right hand inset is a measurement at higher magnification in phase contrast, and shows that lamellae contain substructure, attributed to ordered and amorphous domains (courtesy of J. Loos and P. Thiine [48]).

When lamellar structures are formed, it is necessary to ensure that the dimensions of the simulation cell are commensurate with the intrinsic periodicity of the lamellae. This process prevents unintentionally subjecting the system to artificial pressure as a result of the geometric constraints. Subjecting the system to a predetermined pressure, or stress, in a controlled manner can be achieved by allowing the system to fluctuate parallel to solid directions, which are introduced in Figure 14. For these directions, it would be appropriate to employ the usual techniques related to constant stress simulations.52,53... 

Lattice Model Carlo simulations of a block copolymer confined between parallel hard walls by Kikuchi and Binder (1993,1994) revealed a complex interplay between film thickness and lamellar period. In the case of commensurate length-scales (f an integral multiple of d), parallel ordering of lamellae was observed. On the other hand, tilted or deformed lamellar structures, or even coexistence of lamellae in different orientations, were found in the case of large incommensurability. Even at temperatures above the bulk ODT, weak order was observed parallel to the surface and the transition from surface-induced order to bulk ordering was found to be gradual. The latter observations are in agreement with the experimental work of Russell and co-workers (Anastasiadis et al. 1989 Menelle et al. 1992) and Foster et al. (1992). 

Very high molar mass polyethylene (M>2,000,000 g mol-1) crystallises without the, formation of a clear superstructure, sometimes referred to as the random lamellar structure [116]. The great many chain entanglements present in high molar mass polymers obstruct crystallisation and the crystals become small and their orientation less correlated with surrounding crystal lamellae. 

The twisting lamellar structure of banded spherulites has been debated for decades without obtaining any satisfactory answer until recently. The nature of the isochiral (certain uniform handedness) lamellar twisting and the synchronic character of the twisting of a group of adjacent dominant lamellae both require an explanation. The permanganic etching technique provided... 

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