Transition temperature, chemical

In an ideal Bose gas, at a certain transition temperature a remarkable effect occurs a macroscopic fraction of the total number of particles condenses into the lowest-energy single-particle state. This effect, which occurs when the Bose particles have non-zero mass, is called Bose-Einstein condensation, and the key to its understanding is the chemical potential. For an ideal gas of photons or phonons, which have zero mass, this effect does not occur. This is because their total number is arbitrary and the chemical potential is effectively zero for tire photon or phonon gas. 

The glass-transition temperature, T, of dry polyester is approximately 70°C and is slightly reduced ia water. The glass-transitioa temperatures of copolyesters are affected by both the amouat and chemical nature of the comonomer (32,47). Other thermal properties, including heat capacity and thermal conductivity, depend on the state of the polymer and are summarized ia Table 2. 

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. 

Since successful commercialization of Kapton by Du Pont Company in the 1960s (10), numerous compositions of polyimide and various new methods of syntheses have been described in the Hterature (1—5). A successful result for each method depends on the nature of the chemical components involved in the system, including monomers, intermediates, solvents, and the polyimide products, as well as on physical conditions during the synthesis. Properties such as monomer reactivity and solubiHty, and the glass-transition temperature,T, crystallinity, T, and melt viscosity of the polyimide products ultimately determine the effectiveness of each process. Accordingly, proper selection of synthetic method is often critical for preparation of polyimides of a given chemical composition. 

Table 1. Chemical Structures and Glass-Transition Temperatures, 7, of PSF, PES, and PPSF...

Dynamic techniques are used to determine storage and loss moduli, G and G respectively, and the loss tangent, tan 5. Some instmments are sensitive enough for the study of Hquids and can be used to measure the dynamic viscosity T 7 Measurements are made as a function of temperature, time, or frequency, and results can be used to determine transitions and chemical reactions as well as the properties noted above. Dynamic mechanical techniques for sohds can be grouped into three main areas free vibration, resonance-forced vibrations, and nonresonance-forced vibrations. Dynamic techniques have been described in detail (242,251,255,266,269—279). A number of instmments are Hsted in Table 8. Related ASTM standards are Hsted in Table 9. 

The Rheometric Scientific RDA II dynamic analy2er is designed for characteri2ation of polymer melts and soHds in the form of rectangular bars. It makes computer-controUed measurements of dynamic shear viscosity, elastic modulus, loss modulus, tan 5, and linear thermal expansion coefficient over a temperature range of ambient to 600°C (—150°C optional) at frequencies 10 -500 rad/s. It is particularly useful for the characteri2ation of materials that experience considerable changes in properties because of thermal transitions or chemical reactions. 

Two resin systems based on this chemical concept are commercially available from Shell Chemical Company/Technochemie under the COMPIMIDE trademark COMPIMIDE 183 (34) [98723-11-2], for use in printed circuit boards, and COMPIMIDE 796 [106856-59-1], as a resin for low pressure autoclave mol ding (35). Typical properties of COMPIMIDE 183 glass fabric—PCB laminates are provided in Table 8. COMPIMIDE 183 offers a combination of advantageous properties, such as a high glass transition temperature, low expansion coefficient, and flame resistance without bromine compound additives. 

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. 

Silicones. Polydimethylsiloxanes, polydiphenylsiloxanes, and polymethylphenylsHoxanes are generally called siUcones (see Silicon COMPOUNDS, silicones). With a repeating unit of alternating siUcon-oxygen, the siloxane chemical backbone stmcture, siUcone possesses excellent thermal stabiUty and flexibility that are superior to most other materials. Polydimethjisiloxane provides a very low glass-transition temperature T material but is suitable for use... 

Polyisobutylene has a similar chemical backbone to butyl rubber, but does not contain double carbon-carbon bonds (only terminal unsaturation). Many of its characteristics are similar to butyl rubber (ageing and chemical resistance, low water absorption, low permeability). The polymers of the isobutylene family have very little tendency to crystallize. Their strength is reached by cross-linking instead of crystallization. The amorphous structure of these polymers is responsible for their flexibility, permanent tack and resistance to shock. Because the glass transition temperature is low (about —60°C), flexibility is maintained even at temperatures well below ambient temperature. 

By a variation of chemistry and/or chain length the different time regimes can be shifted. From a simulation point of view we are again faced by the decision what kind of information we want to get out of the simulation. If one wants to look at very local properties, depending on the local chemistry of the individual monomers, there is no way around a simulation with all chemical details. However, one should keep in mind that by such a technique it is impossible to equilibrate the system near the glass transition temperature. 

A major development in fluoroplastks is the recent small scale production of Teflon AF, a noncrystaUme (amorphous) fluorocarbon polymer with a high glass transition temperature (240 °C) This optically transparent TFE copolymer is soluble m certan fluorocabons and has the same chemical and oxidative stability as crystallme TFE homopolymers [5]... 

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