Specific volume, polymeric material

In summary, in Volume 1 of this book we present the fundamental aspects of polymer rheology and the rheological behavior of different types of polymeric materials. In so doing, examples will be given that show relationships between the rheological properties and the molecular parameters of specific polymeric materials. In Volume 2... 

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. 

Figure 2. Specific volume and "free volume" of polymeric material.

Tg can be determined by studying the temperature dependence of a number of physical properties such as specific volume, refractive index, specific heat, etc. First-order transitions, such as the melting of crystals, give rise to an abrupt change or discontinuity in these properties. However, when a polymeric material undergoes a second-order transition, it is not the primary property (the volume), but its first derivative with respect to temperature, (the coefficient of expansion), which becomes discontinuous. This difference between a first and second-order transition is illustrated in Figure 10. 

The density or its reciprocal, the specific volume, is a commonly used property for polymeric materials. The specific volume is often plotted as a function of pressure and temperature in what is known as a pvT diagram. A typical pvT diagram for an unfilled and filled amorphous polymer is shown, using polycarbonate as an example, in Figs. 2.10 and 2.11 The two slopes in the curves represent the specific volume of the melt and of the glassy amorphous polycarbonate, separated by the glass transition temperature. 

Standard test method for rubber property-volume resistivity of electrically conductive and antistatic products Specification for electrical properties of conducting and antistatic products made from flexible polymeric material... 

Figure 4. Specific volume and free volume of polymeric material. (Reproduced with permission from Ref. 10. Copyright 1985 Cambridge University Press.)...

Data of low-temperature nitrogen adsorption were used to evaluate the parameters characterizing the pore structure of the obtained polymeric materials in dry state. The BET specific surface area, Sbet, and the total pore volume, V, were estimated by applying the standard methods Sbet from the linear BET plots and F/ from adsorption at relative pressure p/po=0.975) [7]. The mesopore structure was characterized by the distribution function of mesopore volume calculated by the Barret-Joyner-Halenda (BJH) method [27]. In Table 2 the values of these parameters are given for both synthesized polymers. The melamine-formaldehyde resin MEA has a more developed pore structure (5 B 7=220mVg, F,=0.45cm /g) and narrower mesopores (D=7.3nm) in comparison to the phenolic-formaldehyde polymer PHD. 

SC CO2 used as a carrier of drug molecules into a polymer matrix has a number of advantages such as the plasticizing ability of CO2 (based on specific interactions between CO2 and polymer moieties), which both enhances the diffusion rates of drug molecules into the polymer and facilitates solvent removal. Polymer plasticization is accompanied by the swelling of the polymer matrix, with a concomitant increase in the free volume of the polymer. Moreover, SC CO2 can reduce the melting temperature of semicrystalline polymers. These effects are crucial to the impregnation and modification of polymeric materials. 

Materials Compatibility Einally, any lubricant is required to be compatible with non-metallic components used in the engine, such as plastics, resins and elastomers. In particular, polymeric materials used in seals and plastics need to retain their integrity when in contact with the lubricant. ACEA and most OEMs have material compatibility tests to ensure that the lubricant will not cause undue degradation in key physical parameters of the polymer. These parameters include tensile strength, hardness, volume and crack formation. Any such loss of polymer integrity could be manifest as oil seal leaks or in more extreme cases as a blown gasket. Current engine test examples for American, European and selected OEM specifications are shown in Table 9.5. 

According to Rosenbaum (14), the experimentally determined dry wool density could actually be the density of a polymeric material containing "small static voids" originally occupied by the water molecules in the native state of the hydrated protein for wool, Rosenbaum s "specific volume without voids" is 7% smaller than the experimental specific volume. 

The application of polymeric materials in medicine is a fairly specialized area with a wide range of specific applications and requirements. Although the total volume of polymers used in this application may be small compared to the annual production of polyethylene, for example, the total amount of money spent annually on prosthetic and biomedical devices exceeds 16 billion in the United States alone. These applications include over a million dentures, nearly a half billion dental fillings, about six million contact lenses, over a million replacement joints (hip, knee, finger, etc.), about a half million plastic surgery operations (breast prosthesis, facial reconstruction, etc.), over 25,000 heart valves, and 60,000 pacemaker implantations. In addition, over AO,000 patients are on hemodialysis units (artificial kidney) on a regular basis, and over 90,000 coronary bypass operations (often using synthetic polymers) are performed each year (]J. 

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