Transitions a-crystalline

The salt undergoes a crystalline transition from tetragonal to cubic at 412 K AH for the transition is 2.49 kJ mol-1. The temperature dependence of the lattice parameters and thermal expansion coefficient has been carefully studied.100... 

Poly(ethylene-co-tetrafluoroethylene) does not reveal a crystalline transition and could not be extruded in the solid state ... 

Ziegler-Natta catalyst systems being mostly heterogeneous in nature, adsorption reactions are most likely to occur in such polymerizations and feature in their kinetic schemes (Erich and Mark, 1956). A number of kinetic schemes have thus been proposed based on the assumption that the polymerization centers are formed by the adsorption of metal alkyl species on to the surface of a crystalline transition metal halide and that chain propagation occurs between the adsorbed metal alkyl and monomer. In this regard the Rideal rate law and the Langmuir-Hinshelwood rate law for adsorption and reaction on solids assume importance see Problem 9.4). 

Specific interactions in binary blends of ethylene-vinyl acetate copolymer with various low molecular weight terpene-phenol tackifying resins (TPR) were systematically investigated, as a function of the composition of the blend and of the electron acceptor ability of the resin, by using attenuated total reflection FTIR spectroscopy. Molecular acid-base were evidenced between TPR hydroxyl groups and EVA carbonyl groups. Quantitative information on the fraction of acid-base bonded entities, the enthalpy and equilibrium constant of pair formation were obtained. A crystalline transition of the EVA copolymer was observed and discussed in terms of enthalpy and entropy considerations based on FTIR and calorimetric DSC investigations. Fundamental results are then summarised to predict the interfacial reactivity of such polymer blends towards acid or basic substrates. 16 refs. 

Takahashi Y, Osaki Y and Tadokoro H (1980) Structures of three crystal modifications of poly(3,3-dimethyloxacyclobutane), J Polym Sci Polym Phys Ed 18 1863-1878. Miyasaka K and Ishikawa K (1968) Effects of temperature and water on the -y —>a crystalline transition of nylon 6 caused by stretching in the chain direction, J Polym Sci Part A-2 6 1317-1329. 

Clear evidence for a crystalline transition at about 90"C is presented in a series of papers by Araki, Refs. 3-5. He also presents evidence for doublets in the transitions Ref 4, and points out that the alpha and gamma transitions follow the so called 2/3 (Trouton) rule when compared with the first order crystalline transitions at 19 and 327°C, Ref. 3. See also evidence for a doublet in the freezing-point plot shown in Ref 65. 

The melting point of commercial Teflon PEA is 305°C, ie, between those of PTEE and EEP. Second-order transitions are at —100, —30, and 90°C, as determined by a torsion pendulum (21). The crystallinity of the virgin resin is 65—75%. Specific gravity and crystallinity increase as the cooling rate is reduced. An ice-quenched sample with 48% crystallinity has a specific gravity of 2.123, whereas the press-cooled sample has a crystallinity of 58% and a specific gravity of 2.157. 

In 1921, a discontinuous index of refraction of vitreous Si02 near the a—P transition of quart2 (crystalline Si02) was noted (17). These data and subsequent x-ray investigations of vitreous siHca led to the suggestion (18) that crystaUites on the order of 1.5 nm were present. It was demonstrated, however, that the crystal size would be less than 0.8 nm, and it was suggested that the term crystal loses meaning for these dimensions (19,20). 

The number of examples of Uquid crystalline systems is limited. A simple discotic system, hexapentyloxytriphenylene (17) (Fig. 4), has been studied for its hole mobUity (24). These molecules show a crystalline to mesophase transition at 69°C and a mesophase to isotropic phase transition at 122°C (25). 

No coherent threadline could be maintained and the extmdate flew off the windup as short, brittle, crystalline lengths. Not until many years later did other workers show that this polymer on cooling exhibits a mesophase transition directly from the isotropic melt to a smectic A phase. Good sources of information on Hquid crystals and Hquid crystal polymers are available (212—216). 

As-polymerized PVDC does not have a well-defined glass-transition temperature because of its high crystallinity. However, a sample can be melted at 210°C and quenched rapidly to an amorphous state at <—20°C. The amorphous polymer has a glass-transition temperature of — 17°C as shown by dilatometry (70). Glass-transition temperature values of —19 to — 11°C, depending on both method of measurement and sample preparation, have been determined. 

Glass-Transition Temperature. When a typical Hquid is cooled, its volume decreases slowly until the melting point, T, where the volume decreases abmpdy as the Hquid is transformed into a crystalline soHd. This phenomenon is illustrated by the line ABCD in Eigure 3. If a glass forming Hquid is cooled below (B in Eig. 3) without the occurrence of crystallization, it is considered to be a supercooled Hquid until the glass-transition temperature, T, is reached. At temperatures below T, the material is a soHd. 

In the case of a crystalline polymer the maximum service temperature will be largely dependent on the crystalline melting point. When the polymer possesses a low degree of crystallinity the glass transition temperature will remain of paramount importance. This is the case with unplasticised PVC and the polycarbonate of bis-phenol A. 

Figure 13.6 shows the influence of temperature on specific volume (reciprocal specific gravity). The exaet form of the eurve is somewhat dependent on the crystallinity and the rate of temperature change. A small transition is observed at about 19°C and a first order transition (melting) at about 327°C. Above this temperature the material does not exhibit true flow but is rubbery. A melt viseosity of 10 -10 poises has been measured at about 350°C. A slow rate of decomposition may be detected at the melting point and this increases with a further inerease in temperature. Processing temperatures, exeept possibly in the case of extrusion, are, however, rarely above 380°C. 

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