Physical properties glass transition

PHYSICAL AND GLASS TRANSITION BEHAVIOR 6.7.1. General Properties... 

Homogeneous alloys have a single glass transition temperature which is determined by the ratio of the components. The physical properties of these alloys are averages based on the composition of the alloy. 

Polymeric materials are unique owing to the presence of a glass-transition temperature. At the glass-transition temperatures, the specific volume of the material and its rate of change changes, thus, affecting a multitude of physical properties. Numerous types of devices could be developed based on this type of stimuli—response behavior however, this technology is beyond the scope of this article. 

In the area of moleculady designed hot-melt adhesives, the most widely used resins are the polyamides (qv), formed upon reaction of a diamine and a dimer acid. Dimer acids (qv) are obtained from the Diels-Alder reaction of unsaturated fatty acids. Linoleic acid is an example. Judicious selection of diamine and diacid leads to a wide range of adhesive properties. Typical shear characteristics are in the range of thousands of kilopascals and are dependent upon temperature. Although hot-melt adhesives normally become quite brittle below the glass-transition temperature, these materials can often attain physical properties that approach those of a stmctural adhesive. These properties severely degrade as the material becomes Hquid above the melt temperature. 

The iatroduction of a plasticizer, which is a molecule of lower molecular weight than the resia, has the abiUty to impart a greater free volume per volume of material because there is an iucrease iu the proportion of end groups and the plasticizer has a glass-transition temperature, T, lower than that of the resia itself A detailed mathematical treatment (2) of this phenomenon can be carried out to explain the success of some plasticizers and the failure of others. Clearly, the use of a given plasticizer iu a certain appHcation is a compromise between the above ideas and physical properties such as volatiUty, compatibihty, high and low temperature performance, viscosity, etc. This choice is appHcation dependent, ie, there is no ideal plasticizer for every appHcation. 

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. 

Relatively few processible polyimides, particularly at a reasonable cost and iu rehable supply, are available commercially. Users of polyimides may have to produce iutractable polyimides by themselves in situ according to methods discussed earlier, or synthesize polyimides of unique compositions iu order to meet property requirements such as thermal and thermoxidative stabilities, mechanical and electrical properties, physical properties such as glass-transition temperature, crystalline melting temperature, density, solubility, optical properties, etc. It is, therefore, essential to thoroughly understand the stmcture—property relationships of polyimide systems, and excellent review articles are available (1—5,92). 

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... 

Alloys exhibit physical properties, the values of which are typically the weighted average of those of its constituents. In particular, the blend exhibits a single glass-transition temperature, often closely obeying semitheoretically derived equations. Blends of two compatibiLized immiscible polymers exhibit physical properties which depend on the physical arrangement of the constituents and thus maybe much closer to those of one of the parent resins. They will also typically exhibit the two glass-transition temperatures of their constituent resins. 

In the case of an amorphous polymer the glass transition temperature will define whether or not a material is glass-like or rubbery at a given temperature. If, however, the polymer will crystallise, rubbery behaviour may be limited since the orderly arrangement of molecules in the crystalline structure by necessity limits the chain mobility. In these circumstances the transition temperature is of less consequence in assessing the physical properties of the polymer. 

In this approach, connectivity indices were used as the principle descriptor of the topology of the repeat unit of a polymer. The connectivity indices of various polymers were first correlated directly with the experimental data for six different physical properties. The six properties were Van der Waals volume (Vw), molar volume (V), heat capacity (Cp), solubility parameter (5), glass transition temperature Tfj, and cohesive energies ( coh) for the 45 different polymers. Available data were used to establish the dependence of these properties on the topological indices. All the experimental data for these properties were trained simultaneously in the proposed neural network model in order to develop an overall cause-effect relationship for all six properties. 

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