Flow transition temperature

Below T polymers are stiff, hard, britde, and glass-like above if the molecular weight is high enough, they are relatively soft, limp, stretchable, and can be somewhat elastic. At even higher temperatures they flow and are tacky. Methods used to determine glass-transition temperatures and the reported values for a large number of polymers may be found in References 7—9. Values for the T of common acrylate homopolymers are found in Table 1. 

Stabilization of the Cellular State. The increase in surface area corresponding to the formation of many ceUs in the plastic phase is accompanied by an increase in the free energy of the system hence the foamed state is inherently unstable. Methods of stabilizing this foamed state can be classified as chemical, eg, the polymerization of a fluid resin into a three-dimensional thermoset polymer, or physical, eg, the cooling of an expanded thermoplastic polymer to a temperature below its second-order transition temperature or its crystalline melting point to prevent polymer flow. 

Poly(vinylchloride). Cellular poly(vinyl chloride) is prepared by many methods (108), some of which utili2e decompression processes. In all reported processes the stabili2ation process used for thermoplastics is to cool the cellular state to a temperature below its second-order transition temperature before the resia can flow and cause coUapse of the foam. 

In methacrylic ester polymers, the glass-transition temperature, is influenced primarily by the nature of the alcohol group as can be seen in Table 1. Below the the polymers are hard, brittle, and glass-like above the they are relatively soft, flexible, and mbbery. At even higher temperatures, depending on molecular weight, they flow and are tacky. Table 1 also contains typical values for the density, solubiHty parameter, and refractive index for various methacrylic homopolymers. 

T and are the glass-transition temperatures in K of the homopolymers and are the weight fractions of the comonomers (49). Because the glass-transition temperature is directly related to many other material properties, changes in T by copolymerization cause changes in other properties too. Polymer properties that depend on the glass-transition temperature include physical state, rate of thermal expansion, thermal properties, torsional modulus, refractive index, dissipation factor, brittle impact resistance, flow and heat distortion properties, and minimum film-forming temperature of polymer latex... 

As the temperature is decreased, free-volume is lost. If the molecular shape or cross-linking prevent crystallisation, then the liquid structure is retained, and free-volume is not all lost immediately (Fig. 22.8c). As with the melt, flow can still occur, though naturally it is more difficult, so the viscosity increases. As the polymer is cooled further, more free volume is lost. There comes a point at which the volume, though sufficient to contain the molecules, is too small to allow them to move and rearrange. All the free volume is gone, and the curve of specific volume flattens out (Fig. 22.8c). This is the glass transition temperature, T . Below this temperature the polymer is a glass. 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

While phenol is the most common monomer for novolac manufacture, it is far more common to see incorporation of other phenolic materials with novolacs than with resoles. Cresols, xylenols, resorcinol, catechols, bisphenols, and a variety of phenols with longer alkyl side chains are often used. While most resoles are made with a single phenolic monomer, two or more phenolic materials are often seen in novolac formulae. These additional monomers may be needed to impart special flow characteristics under heat, change a glass transition temperature, modify cure speed, or to adjust solubility in the application process among others. 

A ductile material can be stretched uniformly only when stable flow occurs. The stable flow of materials has been investigated by Hart who described the transition from the stable to unstable flow. The beginning of geometrical instability and localisation of strain is the limit of the stable flow. At temperatures above 0.5 T (at equilibrium between recovery and hardening) the strain rate sensitivity parameter "m" may be derived from the expression ... 

The maximum rate of polymerization has been confirmed to occur at the laminar-turbulent flow transition. The rate of polymerization was observed to be maximum at the transition for both straight reactors as well as for the helically-coiled reactor for which the transition is at a Reynolds number higher than that of the straight tube. The helically coiled tubular reactor is of industrial interest since it is much more compact and, consequently, the cost and the temperature control problems are more tractable. 

No material is perfectly elastic in the sense of strictly obeying Hooke s law. Polymers, particularly when above their glass transition temperature, are certainly not. For these macromolecular materials there is an element of flow in their response to an applied stress, and the extent of this flow varies with time. Such behaviour, which may be considered to be a hybrid of perfectly elastic response and truly viscous flow, is known as viscoelasticity. 

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