Crystal structure polytetrafluoroethylene

The first published study of the diffraction of x-rays by the crystal structure of polytetrafluoroethylene was by Bunn and Howells. Later, Pierce, Clark, Whitney, and Bryant described the crystal structure... 

Clark, E. S., and L. T. Muus Unusual features in the crystal structure of polytetrafluoroethylene. Meeting of the American Chemical Society, New York, September 1957. 

In this paper we examine electron diffraction fiber patterns of the homopolymer polytetrafluoroethylene (-CF2 CF2-)n PTFE, in which the resolution is sufficient to yield much more accurate values of layer line heights than were available from the previous x-ray diffraction experiments (1) on the crystal structure of Phase II, the phase below the 19°C transition (2). On the basis of x-ray data, the molecule was assigned the conformation 13/6 or thirteen CF2 motifs regularly spaced along six turns of the helix. This is equivalent to a 132 screw axis. The relationship between the molecular conformation and the helical symmetry has been studied by Clark and Muus (3) and is illustrated in Figure 1. The electron diffraction data of high resolution enabled us to determine if this unusual 13-fold symmetry was exact or an approximation of the true symmetry. We have also... 

Weeks JJ, Eby RK, Clark ES (1981) Crystal structure of the low temperature phase (II) of polytetrafluoroethylene. Polymer 22 1496, and references therein... 

Conformationally disordered crystals (condis crystals) were discovered in the 1980 s. They show positional and orientational order, but are partially or fully conformationally mobile. The condis crystals complete the comparison of mesophases in Figs. 2.103 and 2.107. Linear, flexible molecules can show chain mobility that leaves the position and orientation of the molecule unchanged, but introduces large-amplitude conformational motion about the chain axis. Again, the symmetry of the molecule is in this case increased. Condis crystals have often a hexagonal, columnar crystal structure. Typical examples of condis crystals are the high-temperature phase of polyethylene, polytetrafluoroethylene, frawj-1,4-polybutadiene, and the low-temperature phases of soaps, lipids and other liquid-crystal forming, flexible molecules. 

The most relevant property of stereoregular polymers is their ability to crystallize. This fact became evident through the work of Natta and his school, as the result of the simultaneous development of new synthetic methods and of extensive stractural investigations. Previously, the presence of crystalline order had been ascertained only in a few natural polymers (cellulose, natural rubber, bal-ata, etc.) and in synthetic polymers devoid of stereogenic centers (polyethylene, polytetrafluoroethylene, polyamids, polyesters, etc.). After the pioneering work of Meyer and Mark (70), important theoretical and experimental contributions to the study of crystalline polymers were made by Bunn (159-161), who predicted the most probable chain conformation of linear polymers and determined the crystalline structure of several macromolecular compounds. 

Polymers such as polystyrene, poly(vinyl chloride), and poly(methyl methacrylate) show very poor crystallization tendencies. Loss of structural simplicity (compared to polyethylene) results in a marked decrease in the tendency toward crystallization. Fluorocarbon polymers such as poly(vinyl fluoride), poly(vinylidene fluoride), and polytetrafluoroethylene are exceptions. These polymers show considerable crystallinity since the small size of fluorine does not preclude packing into a crystal lattice. Crystallization is also aided by the high secondary attractive forces. High secondary attractive forces coupled with symmetry account for the presence of significant crystallinity in poly(vinylidene chloride). Symmetry alone without significant polarity, as in polyisobutylene, is insufficient for the development of crystallinity. (The effect of stereoregularity of polymer structure on crystallinity is postponed to Sec. 8-2a.)... 

Polytetrafluoroethylene (PTFE) is an attractive model substance for understanding the relationships between structure and properties among crystalline polymers. The crystallinity of PTFE (based on X-ray data) can be controlled by solidification and heat treatments. The crystals are large and one is relieved of the complexity of a spherulitic superstructure because, with rare exceptions, spherulites are absent from PTFE. What is present are lamellar crystals (XL) and a noncrystalline phase (NXL) both of which have important effects on mechanical behavior. 

The outline of the paper is as follows. In Sect. 2 we describe the basic RISM and PRISM formalisms, and the fundamental approximations invoked that render the polymer problem tractable. The predicticms of PRISM theory for the structure of polymer melts are described in Sect. 3 for a variety of single chain models, including a comparison of atomistic calculations for polyethylene melt with diffraction experiments. The general problem of calculating thermodynamic properties, and particularly the equation-of-state, within the PRISM formalism is described in Sect. 4. A detailed application to polyethylene fluids is summarized and compared with experiment. The develojanent of a density functional theory to treat polymer crystallization is briefly discussed in Sect. 5, and numerical predictions for polyethylene and polytetrafluoroethylene are summarized. 

Polytetrafluoroethylene is unusual in possessing a transition in crystal form near 20°C and another transition near 30 attributed to random chain motions. These structural modifications are accompanied by marked changes in viscoelastic... 

Spherulites are considered to be the polymer analogue of grains in polycrystalline metals and ceramics. Flowever, as discussed earher, each spheruhte is really composed of many different lamellar crystals and, in addition, some amorphous material. Polyethylene, polypropylene, poly(vinyl chloride), polytetrafluoroethylene, and nylon form a spherulitic structure when they crystalhze from a melt. 

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