Lamellar Polymer Crystals

Fig. 17. Schematic representation of the sup-ramolecular structure of polymers containing lamellar crystals...

At this point a third intermediate approach deserves mentioning. It is due to Allegra [43] who proposed that polymer crystallization is controlled by a metastable equilibrium distribution of intramolecular clusters, the so-called bundles , forming in the liquid phase. These subsequently aggregate to the side surfaces of the crystals, driven by van der Waals interactions. The lamellar thickness is determined by the average contour length of the loops within the bundles. Although the model can... 

The importance of twinned crystals in demonstrating that nucleation is the relevant growth mechanism has been realized since 1949 [64, 99]6. They were first investigated extensively in polymer crystals by Blundell and Keller [82] and they have recently received increased attention as a means of establishing, or otherwise, the nucleation postulate for lamellar growth [90, 91, 95,100-102]. The diversity of opinion in the literature shows that it is very difficult to draw definite conclusions from the experimental evidence, and the calculations are often founded upon implicit assumptions which may or may not be justified. We therefore restrict our discussion to an introduction to the problem, the complicating features which make any a priori assumptions difficult, and the remaining information which may be fairly confidently deduced. 

One of the most remarkable features of polymer crystallization is that such chain molecules can form lamellar crystals that contain heavily folded polymer chains. In experiments, the structural analysis of these lamellar crystals became possible when polyethylene single crystals were first prepared from a solution [100-102]. It was found that the orientation of the polymer chains... 

In the classical Lauritzen-Hoffman theory for the mechanism of polymer crystal growth [106], it is assumed that the observed lamellar thickness corresponds to those crystallites that happen to have the largest growth velocity. However, this picture is hard to reconcile with the experimental observation that the thickness of polyethylene single crystals can be modulated by varying the temperature at which they are grown [117,118]. In fact, simulations by Doye et al. [119,120] suggest that the observed lamellar thickness does... 

The polymer crystallization depends sensitively on the temperature Tc at which it occurs, more precisely on the degree of undercooling A T=Tm-Tc below the melting temperature Tm. Since we have to estimate Tm, at least roughly, of our lamellar crystal model, we first study the melting process of a lamella during the temperature increase at a constant rate. 

Among the numerous challenges faced in understanding the formation and evolution of hierarchical structures in polymer crystallization, we restrict ourselves to explain the essential basic features of folded lamellae. Specihcally, we consider (1) molecular origin of enhanced scattered intensity before any crystallographic features are apparent, (2) spontaneous selection of small lamellar thickness, (3) molecular details of growth front, and (4) formation of shish-kebab structures in the presence of a flow. 

The molecular processes that take place during polymer crystallization can be investigated from different viewpoints. A global approach determines the shape and conformation of chains in the polymer melt, and infers processes that lead to the lamellar chain folded crystal. Alternatively, analysis of the final crystal structure may help us to work backwards and gain insights into processes that take place in the last stages of crystal build-up. It is clear, however, that the two approaches should lead to the same conclusions, since the crystallization processes that occur should not, and certainly do not, depend on the viewpoint adopted for their analysis. 

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