Free volume measuring

The diffusion of gases through a polymer matrix is determined by the mobility of gas molecules through the matrix. The diffusion coefficient is therefore, at least partially determined by the free volume size of the polymer. It has been shown, for example, that there is a correlation between the free volume measured by PAL and the diffusivity of carbon dioxide in a seriers of polycarbonates [58], In a study of poly (trimethylsilyl propyne) (PTMSP), which has an extremely high gas permeability and diffusion coefficients, it was found that the lifetime data could be resolved into four components [59]. The longest lifetime component (T4) had a lifetime of... 

Hsieh et al [62] found that for a range of thermotropic liquid crystalline polymers, the greater the free volume measured by PAL the greater the chain mobility at Tg and the higher the value of tan S (damping strength) measured by dynamic mechanical analysis. 

J.Y. Dolveck, G.H. Dai, P. Moser, M. Pineri and M. Escoubes, Free volume measurements in polymides by positronium anihilation. Materiab Sci. Forum, 105-110 (1992) 1549. 

Equations (A-22) and (A-23) contain a remarkable discovery, namely, that free volume measurements are unnecessary for obtaining meaningful information by the frequency response technique. Heretofore, when... 

Monge, M. A., Diaz, J. A., and Pareja, R., Slrain-mduced changes of free volume measured by positron lifetime spectroscopy in ultrahigh molecular weight polyethylene. Macromolecules, 37, 7223-7230 (2004). 

Our sorption and diffusion data indicated an apparently more complex behaviour of the blends. We did not observe a clear increase in CO2 solubihty coefficient in the membrane with increasing PEG content but an increase in the CO2 diffusivity. As no free volume measurements were performed in the present study, we can only suggest a similar mechanism of diffusivity enhancement by PEG additive in Pebax 1657 as that proposed by Yave et al. [43]. 

For the evaporation process we mentioned above, the thermodynamic probability of the gas phase is given by the number of places a molecule can occupy in the vapor. This, in turn, is proportional to the volume of the gas (subscript g) 12- oc V In the last chapter we discussed the free volume in a liquid. The total free volume in a liquid is a measure of places for molecules to occupy in the liquid. The thermodynamic probability of a liquid (subscript 1) is thus V, oc V, frgg. Based on these ideas, the entropy of the evaporation process can be written as... 

In discussing Fig. 4.1 we noted that the apparent location of Tg is dependent on the time allowed for the specific volume measurements. Volume contractions occur for a long time below Tg The lower the temperature, the longer it takes to reach an equilibrium volume. It is the equilibrium volume which should be used in the representation summarized by Fig. 4.15. In actual practice, what is often done is to allow a convenient and standardized time between changing the temperature and reading the volume. Instead of directly tackling the rate of collapse of free volume, we shall approach this subject empirically, using a property which we have previously described in terms of free volume, namely, viscosity. 

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 9 3 A simple laboratory set-up for observing the casting process directly. The mould volume measures about 50 X 50 X 6 mm. The walls are cooled by putting the bottom of the block into a dish of liquid nitrogen. The windows are kept free of frost by squirting them with alcohol from a wash bottle every 5 minutes. 

Fig. 22.8. (a) The volume change when a simple melt (like a liquid metal) crystallises defines the melting point, T (b) the spread of molecular weights blurs the melting point when polymers crystallise ( ) when a polymer solidifies to a gloss the melting point disappears completely, but a new temperature at which the free volume disappears (the gloss temperature, TJ con be defined and measured. 

Also, in cases where the dimensions of a regular particle vary throughout a bed of such particles or are not known, but where the fractional free volume and specific surface can be measured or calculated, the shape factor can be calculated and the equivalent diameter of the regular particle determined from Figure 2. 

L. L. Blyler and T. K. Kwei [39] proposed the direct opposite (to 4). In their reasoning, they proceeded from the known and generally acceptable Doolittle equation, which puts liquid viscosity in exponential dependence on the inverse value of the free volume of the latter. According to [39], gas has a volume of its own, the value of which it contributes to the free volume of the polymer when it dissolves therein as a result, viscosity falls. The theoretical formula obtained by the authors was experimentally confirmed in the same work. The authors measured pressure values at the entrance of cylindrical capillaries, through which melts of both pure polyethylene, and polyethylene with gas dissolved in it, extruded at a constant rate. 

The sizes and concentration of the free-volume cells in a polyimide film can be measured by PALS. The positrons injected into polymeric material combine with electrons to form positroniums. The lifetime (nanoseconds) of the trapped positronium in the film is related to the free-volume radius (few angstroms) and the free-volume fraction in the polyimide can be calculated.136 This technique allows a calculation of the dielectric constant in good agreement with the experimental value.137 An interesting correlation was found between the lifetime of the positronium and the diffusion coefficient of gas in polyimide.138,139 High permeabilities are associated with high intensities and long lifetime for positron annihilation. 

In the molten state polymers are viscoelastic that is they exhibit properties that are a combination of viscous and elastic components. The viscoelastic properties of molten polymers are non-Newtonian, i.e., their measured properties change as a function of the rate at which they are probed. (We discussed the non-Newtonian behavior of molten polymers in Chapter 6.) Thus, if we wait long enough, a lump of molten polyethylene will spread out under its own weight, i.e., it behaves as a viscous liquid under conditions of slow flow. However, if we take the same lump of molten polymer and throw it against a solid surface it will bounce, i.e., it behaves as an elastic solid under conditions of high speed deformation. As a molten polymer cools, the thermal agitation of its molecules decreases, which reduces its free volume. The net result is an increase in its viscosity, while the elastic component of its behavior becomes more prominent. At some temperature it ceases to behave primarily as a viscous liquid and takes on the properties of a rubbery amorphous solid. There is no well defined demarcation between a polymer in its molten and rubbery amorphous states. 

Mechanical and chemical methods for qualitative and quantitative measurement of polymer structure, properties, and their respective processes during interrelation with their environment on a microscopic scale exist. Bosch et al. [83] briefly discuss these techniques and point out that most conventional techniques are destructive because they require sampling, may lack accuracy, and are generally not suited for in situ testing. However, the process of polymerization, that is, the creation of a rigid structure from the initial viscous fluid, is associated with changes in the microenvironment on a molecular scale and can be observed with free-volume probes [83, 84]. 

With further understanding how molecular rotors interact with their environment and with application-specific chemical modifications, a more widespread use of molecular rotors in biological and chemical studies can be expected. Ratiometric dyes and lifetime imaging will enable accurate viscosity measurements in cells where concentration gradients exist. The examination of polymerization dynamics benefits from the use of molecular rotors because of their real-time response rates. Presently, the reaction may force the reporters into specific areas of the polymer matrix, for example, into water pockets, but targeted molecular rotors that integrate with the matrix could prevent this behavior. With their relationship to free volume, the field of fluid dynamics can benefit from molecular rotors, because the applicability of viscosity models (DSE, Gierer-Wirtz, free volume, and WLF models) can be elucidated. Lastly, an important field of development is the surface-immobilization of molecular rotors, which promises new solid-state sensors for microviscosity [145]. 

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