Chains crystallization

Mechanical and Thermal Properties. The first member of the acrylate series, poly(methyl acrylate), has fltde or no tack at room temperature it is a tough, mbbery, and moderately hard polymer. Poly(ethyl acrylate) is more mbberflke, considerably softer, and more extensible. Poly(butyl acrylate) is softer stiU, and much tackier. This information is quantitatively summarized in Table 2 (41). In the alkyl acrylate series, the softness increases through n-octy acrylate. As the chain length is increased beyond n-octy side-chain crystallization occurs and the materials become brittle (42) poly( -hexadecyl acrylate) is hard and waxlike at room temperature but is soft and tacky above its softening point. 

The macroscopic orientation of their extended-chain crystals depends on the orientation imparted by flow during mol ding. Because of the fibrous nature of the extended-chain crystals, these materials behave as self-reinforcing composites, with excellent mechanical properties. 

The Pink model is found to exhibit a gel-fluid transition for lipids with sufficiently long chains, which is weakly first order. The transition disappears in bilayers of shorter lipids, but it leaves a signature in that one observes strong lateral density fluctuations in a narrow temperature region [200,201]. In later studies, the model has been extended in many ways in order to explore various aspects of gel-fluid transitions [202]. For example, Mouritsen et al. [203] have investigated the interplay between chain melting and chain crystallization by coupling a two-state Doniach model or a ten-state Pink model to a Potts model. (The use of Potts models as models for... 

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. 

Extended- and folded-chain crystallization are mutually independent processes, and extended-chain crystallization can take place prior to folded-chain crystallization [6,19-25]. 

Formation of Extended-Chain Crystals (ECC) Under Equilibrium Conditions. 229... 

Usually, crystallization of flexible-chain polymers from undeformed solutions and melts involves chain folding. Spherulite structures without a preferred orientation are generally formed. The structure of the sample as a whole is isotropic it is a system with a large number of folded-chain crystals distributed in an amorphous matrix and connected by a small number of tie chains (and an even smaller number of strained chains called loaded chains). In this case, the mechanical properties of polymer materials are determined by the small number of these ties and, hence, the tensile strength and elastic moduli of these polymers are not high. 

The most widely used method for preparing extended-chain crystals involves solid-phase polymerization when the monomer exists as a single crystal. The polymerization of single crystals of the monomer permits the preparation of a polymer material with a maximum orientation a polymeric single crystal composed of fully extended macromolecules. Such polymer crystals are needle-shaped22. ... 

It should be noted that the concept extended-chain crystal (ECC) does not mean a crystal, in which not a single molecule can form a told. ECC can contain some molecules with folded conformation but the folds play a role of defects... 

A characteristic feature of the structure of samples obtained under the conditions of molecular orientation is the presence of folded-chain crystals in addition to ECC. Kawai22 has emphasized that the process of crystallization from the melt under the conditions of molecular orientation can be regarded as a bicomponent crystallization in which, just as in the case of fibrous structures in the crystallization from solutions, the formation of crystals of the packet type (ECC) occurs in the initial stage followed by the crystallization with folding . 

Wunderlich30 and Zubov33 suppose that ECC under high pressures occur as a result of an isothermal thickening of folded-chain lamellae. However, this contradicts the later data of Wunderlich and of Japanese authors31 who have shown that folded-chain crystals (FCC) are formed after ECC, when the melt is cooled. According to Kawai22, crystallization under hydrostatic compression can he considered as a variant of the bicomponent crystallization. 

Fig. 5 a, b. Models of the crystallization of flexible-chain polymers with the formation of a folded-chain crystals and b extended-chain crystals b... 

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. 

Hence, it can be concluded that the formed intermediate oriented phase is an indispensable stage preceding extended-chain crystallization so that this type of crystallization occurs in two stages the first stage involves formation of the oriented phase during melt deformation and the second formation of ECC from this phase on cooling. 

If this sample contains also folded-chain crystals (reasons for their appearance during orientational crystallization were stated before), under isometric conditions they undergo melting at a higher temperature (at point 1 with respect to the oriented melt with transition to line A2) than under the conditions of free heating (point 1 with transition in the isotropic melt to line At). 

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