Polymer glass temperature

We will consider the specific system of a non-ionic diffusant in an amorphous or semi-crystalline polymer (in contact with a liquid) at temperatures above the polymer glass temperature Tg. 

In the case of semicrystalline polymers, glass temperature is not easily determined with the usual measurements. For such polymers, an indirect technique can be used. Basically, this involves taking two semicrystalline homopolymers and preparing a group of amorphous copolymers that have varying mass fractions of each of the homopolymer materials. Then, according to the equation... 

Small molecules are usually evaporated in vacuum while polymeric semiconductors are solution processed and deposited, usually, by spin coating. In order to prevent operational failures, grain boundaries and aggregation should be avoided. Amorphous films are usually desired in order to have better performances for devices operating below the polymer glass temperature. As discussed later, oriented systems with polarized emission are requested for specific applications. 

Nagasawa Y, Passino S A, Joo T and Fleming G R 1997 Temperature dependence of optical dephasing in an organic polymer glass J. Chem. Phys. 106 4840-52... 

Properties. One of the characteristic properties of the polyphosphazene backbone is high chain dexibility which allows mobility of the chains even at quite low temperatures. Glass-transition temperatures down to —105° C are known with some alkoxy substituents. Symmetrically substituted alkoxy and aryloxy polymers often exhibit melting transitions if the substituents allow packing of the chains, but mixed-substituent polymers are amorphous. Thus the mixed substitution pattern is deUberately used for the synthesis of various phosphazene elastomers. On the other hand, as with many other flexible-chain polymers, glass-transition temperatures above 100°C can be obtained with bulky substituents on the phosphazene backbone. 

This combination of monomers is unique in that the two are very different chemically, and in thek character in a polymer. Polybutadiene homopolymer has a low glass-transition temperature, remaining mbbery as low as —85° C, and is a very nonpolar substance with Htde resistance to hydrocarbon fluids such as oil or gasoline. Polyacrylonitrile, on the other hand, has a glass temperature of about 110°C, and is very polar and resistant to hydrocarbon fluids (see Acrylonitrile polymers). As a result, copolymerization of the two monomers at different ratios provides a wide choice of combinations of properties. In addition to providing the mbbery nature to the copolymer, butadiene also provides residual unsaturation, both in the main chain in the case of 1,4, or in a side chain in the case of 1,2 polymerization. This residual unsaturation is useful as a cure site for vulcanization by sulfur or by peroxides, but is also a weak point for chemical attack, such as oxidation, especially at elevated temperatures. As a result, all commercial NBR products contain small amounts ( 0.5-2.5%) of antioxidant to protect the polymer during its manufacture, storage, and use. 

Fig. 6.2. How Young s modulus increases witl) increasing density of covalent cross-links in polymers, including rubbers above tbe glass temperature. Below To, be modulus of rubbers increases markedly because tbe Van der Waals bonds take hold. Above Tq they melt, and the modulus drops.

Many of the most floppy polymers have half-melted in this way at room temperature. The temperature at which this happens is called the glass temperature, Tq, for the polymer. Some polymers, which have no cross-links, melt completely at temperatures above T, becoming viscous liquids. Others, containing cross-links, become leathery (like PVC) or rubbery (as polystyrene butadiene does). Some typical values for Tg are polymethylmethacrylate (PMMA, or perspex), 100°C polystyrene (PS), 90°C polyethylene (low-density form), -20°C natural rubber, -40°C. To summarise, above Tc. the polymer is leathery, rubbery or molten below, it is a true solid with a modulus of at least 2GNm . This behaviour is shown in Fig. 6.2 which also shows how the stiffness of polymers increases as the covalent cross-link density increases, towards the value for diamond (which is simply a polymer with 100% of its bonds cross-linked. Fig. 4.7). Stiff polymers, then, are possible the stiffest now available have moduli comparable with that of aluminium. 

Polymers, too, creep - many of them do so at room temperature. As we said in Chapter 5, most common polymers are not crystalline, and have no well-defined melting point. For them, the important temperature is the glass temperature, Tq, at which the Van der Waals bonds solidify. Above this temperature, the polymer is in a leathery or rubbery state, and creeps rapidly under load. Below, it becomes hard (and... 

Creep of polymers is a major design problem. The glass temperature Tq, for a polymer, is a criterion of creep-resistance, in much the way that is for a metal or a ceramic. For most polymers, is close to room temperature. Well below Tq, the polymer is a glass (often containing crystalline regions - Chapter 5) and is a brittle, elastic solid -rubber, cooled in liquid nitrogen, is an example. Above Tq the Van der Waals bonds within the polymer melt, and it becomes a rubber (if the polymer chains are cross-linked) or a viscous liquid (if they are not). Thermoplastics, which can be moulded when hot, are a simple example well below Tq they are elastic well above, they are viscous liquids, and flow like treacle. 

Elastomers are a special sort of cross-linked polymer. First, they are really linear polymers with just a few cross-links - one every hundred or more monomer units - so that a molecule with a DP of 500 might have fewer than five cross-link points along its length. And second, the polymer has a glass temperature which is well below room temperature, so that (at room temperature) the secondary bonds have melted. Why these two features give an elastomer is explained later (Chapter 23). 

The glass temperature, T, you will remember, is the temperature at which the secondary bonds start to melt. Well below the polymer molecules pack tightly together, either in an amorphous tangle, or in poorly organised crystallites with amorphous... 

MPa. The temperature, normalised by the glass temperature T, is plotted linearly on the horizontal axis it runs from 0 (absolute zero) to 1.6 (below which the polymer decomposes). 

When dipoles are directly attached to the chain their movement will obviously depend on the ability of chain segments to move. Thus the dipole polarisation effect will be much less below the glass transition temperature, than above it Figure 6.4). For this reason unplasticised PVC, poly(ethylene terephthalate) and the bis-phenol A polycarbonates are better high-frequency insulators at room temperature, which is below the glass temperature of each of these polymers, than would be expected in polymers of similar polarity but with the polar groups in the side chains. 

Since the incorporation of plasticisers into a polymer compound brings about a reduction in glass temperature they will also have an effect on the electrical properties. Plasticised PVC with a glass temperature below that of the testing temperature will have a much higher dielectric constant than unplasticised PVC at the same temperature (Figure 6.6). 

The dielectric properties of polar materials will depend on whether or not the dipoles are attached to the main chain. When they are, dipole polarisation will depend on segmental mobility and is thus low at temperatures below the glass transition temperatures. Such polymers are therefore better insulators below the glass temperature than above it. 

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)... 

The effective molecular mass Mc of the network strands was determined experimentally from the moduli of the polymers at temperatures above the glass transition (Sect. 3) [11]. lVlc was derived from the theory of rubber elasticity. Mc and the calculated molecular mass MR (Eq. 2.1) of the polymers A to D are compared in Table 3.1. 

---