Poly free volume

The time-temperature superpositioning principle was applied f to the maximum in dielectric loss factors measured on poly(vinyl acetate). Data collected at different temperatures were shifted to match at Tg = 28 C. The shift factors for the frequency (in hertz) at the maximum were found to obey the WLF equation in the following form log co + 6.9 = [ 19.6(T -28)]/[42 (T - 28)]. Estimate the fractional free volume at Tg and a. for the free volume from these data. Recalling from Chap. 3 that the loss factor for the mechanical properties occurs at cor = 1, estimate the relaxation time for poly(vinyl acetate) at 40 and 28.5 C. 

Fig. 15. Oxygen permeability versus 1/specific free volume at 25 °C (30). 1. Polybutadiene 2. polyethylene (density 0.922) 3. polycarbonate 4. polystyrene 5. styrene-acrylonitrile 6. poly(ethylene terephthalate) 7. acrylonitrile barrier polymer 8. poly(methyl methacrylate) 9. poly(vinyl chloride) 10. acrylonitrile barrier polymer 11. vinyUdene chloride copolymer 12. polymethacrylonitrile and 13. polyacrylonitrile. See Table 1 for unit conversions.

Fouling Industrial streams may contain condensable or reactive components which may coat, solvate, fill the free volume, or react with the membrane. Gases compressed by an oil-lubricated compressor may contain oil, or may be at the water dew point. Materials that will coat or harm the membrane must be removed before the gas is treated. Most membranes require removal of compressor oil. The extremely permeable poly(trimethylsilylpropyne) may not become a practical membrane because it loses its permeability rapidly. Part of the problem is pore collapse, but it seems extremely sensitive to contamination even by diffusion pump oil and gaskets [Robeson, op. cit., (1994)]. 

Fluorinated poly(arylene edier)s are of special interest because of their low surface energy, remarkably low water absorption, and low dielectric constants. The bulk—CF3 group also serves to increase the free volume of the polymer, thereby improving various properties of polymers, including gas permeabilities and electrical insulating properties. The 6F group in the polymer backbone enhances polymer solubility (commonly referred to as the fluorine effect ) without forfeiture of die thermal stability. It also increases die glass transition temperature with concomitant decrease of crystallinity. 

Equation (23) was found to be obeyed by a number of systems such as poly(ethyl acrylate)-benzene, rubber-benzene, and poly(methyl acrylate)-ethyl acetate [12], According to the equation, a plot of [In(DT/D0)] l versus ([)[ will yield a straight line, and from its slope the free volume parameter p can be determined. To construct this plot,/( / , 0) is first calculated as [27]... 

Figure 14 The free volume theory of Yasuda and coworkers holds for the diffusion of acetaminophen in swollen 10 X 4 poly(lV-isopropyl acrylamide) gel. (Adapted from Ref. 176.)...

Hybrid membranes composed of poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS), synthetised via hydrolysis and a co-condensation reaction for the pervaporation separation of water-isopropanol mixtures has also been reported [32], These hybrid membranes show a significant improvement in the membrane performance for water-isopropanol mixture separation. The separation factor increased drastically upon increasing the crosslinking (TEOS) density due to a reduction of free volume and increased chain stiffness. However, the separation factor decreased drastically when PVA was crosslinked with the highest amount of TEOS (mass ratio of TEOS to PVA is 2 1). The highest separation selectivity is found to be 900 for PVA TEOS (1.5 1 w/w) at 30°C. For all membranes, the selectivity decreased drastically up to 20 mass % of water in the feed and then remained almost constant beyond 20 mass %, signifying that the separation selectivity is much influenced at lower composition of water in the feed. 

The method is based on the fact that the rate of conformational change required for excimer formation depends on the free volume induced by the segmental motions of the polymer occurring above the glass transition. DIPHANT (compound 3 in Figure 8.3) was used as an excimer-forming probe of three polymer samples consisting of polybutadiene, polyisoprene and poly(dimethylsiloxane).a)... 

Kakizaki, M. and Hideshima, T., Effect of distribution of free volume on concentration dependence of dielectric relaxation in water mixtures with poly(ethylene glycol) and glucose, Jpn. J. Appl. Phys., Part 1, 1998, 37, 900. 

In this system the a relaxation can be analyzed by the symmetric equation of Fuoss-Kikwood and a new model which is similar to Havriliak- Negami equation used in the analysis of dielectric spectroscopy. According to the Tg values calculated for these systems, the free volume can be appropriately described by the free volume theory. The analysis of these families of poly(methacrylate)s allow to understand in a good way the effect of the structure and nature of the side chain on the viscoleastic behavior of polymers [33],... 

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