Confinement and free-volume requirements.
Free internal volume requirements of space vehicles for long duration missions from studies of human confinement with elements of isolation and perceptual deprivation
Fraser, T. M.↗
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Free volume variation with molecular weight of polymers
Free volume measurements were made in several molecular weight fractions of two different geometries of poly(arylene ether ketone)s. Free volumes were measured using positron lifetime spectroscopy. It has been observed that the free volume cell size V(sub f) varies with the molecular weight M of the test samples according to an equation of the form V(sub f) = AM(B), where A and B are constants. The molecular weights computed from the free volume cell sizes are in good agreement with the values measured by gel permeation chromatography.
Singh, Jag J.↗
Free volume in contact lens polymers
We have measured the free volume and gas permeability in several contact lens specimens as part of a Space Commercialization Program. Free volume was measured using positron lifetime spectroscopy, while permeability for O2, N2, and CO2 gases was measured using mass spectrometry and polarography. It has been noted that permeability for all gases increases with the mean free volume cell size in the test samples. As might be expected, the specimens with the highest free volume fraction also exhibit the lowest Rockwell Hardness Number. An interesting corollary of this study is the finding that the presence of fluorine atoms in the lens chemical structure inhibits filling up of their free volume cells. This is expected to allow the lenses to breathe freely while in actual use.
Singh, Jag J.↗
Free volume model for molecular weights of polymers
A free volume model has been developed for determining molecular weights of linear polymers. It is based on the size of free volume cells in two geometries of poly(arylene ether ketone)s. Free volume cell sizes in test samples were measured using positron lifetime spectroscopy. The molecular weights computed from free volume cell sizes are in good agreement with the values measured by gel permeation chromatography, with a low angle laser light scattering photometer as the detector. The model has been further tested on two atactic polystyrene samples, where it predicted the ratio of their molecular weights with reasonable accuracy.
Singh, J. J.↗
Thermodynamic properties derived from the free volume model of liquids
An equation of state and expressions for the isothermal compressibility, thermal expansion coefficient, heat capacity, and entropy of liquids have been derived from the free volume model partition function suggested by Turnbull. The simple definition of the free volume is used, and it is assumed that the specific volume is directly related to the cube of the intermolecular separation by a proportionality factor which is found to be a function of temperature and pressure as well as specific volume. When values of the proportionality factor are calculated from experimental data for real liquids, it is found to be approximately constant over ranges of temperature and pressure which correspond to the dense liquid phase. This result provides a single-parameter method for calculating dense liquid thermodynamic properties and is consistent with the fact that the free volume model is designed to describe liquids near the solidification point.
Miller, R. I.↗
Free-volume characteristics of epoxies
Positron annihilation spectroscopy was used to measure free-volume characteristics of selected epoxies. Fluorene resins, a new family of high-temperature thermosetting resins, were selected as the test medium. Experimental results indicate that the free-volume cell size V sub f varies with the molecular weight between the cross-links M sub c according to an equation of the form V sub f = AM sub c sup B, where A and B are structural constants. In two of the samples, the concentration of bulky fluorene groups was increased in the network backbone by replacement of some of the conventional bisphenol A epoxy resin with fluorene-derived epoxy resin. This resulted in an increase in their glass transition temperature for a given level of cross-linking. It was found that in these samples, the Doppler broadening of the annihilation peak decreases with the increasing fluorene content, presumably due to enhanced damping of the chain motions.
Singh, Jag J.↗
Effect of annealing history on free volume in thermoplastics
Two different types of thermoplastic glassy polymers have been investigated for the effects of thermal annealing on their free volumes. It has been observed that free volumes in glassy polymers decrease asymptotically to a steady level after about four thermal anneals lasting for 24 hours at a temperature about 50 C below their glass transition temperatures. These results indicate that composites incorporating properly annealed thermoplastic matrices may not experience any additional internal stresses due to subsequent thermal excursions experienced while in service.
Singh, J. J.↗
Annealing Reduces Free Volumes In Thermoplastics
Investigation conducted to determine free volumes and water-absorption characteristics of two types of thermoplastic polymide as functions of annealing histories. Reductions reach asymptotic values after several annealing cycles. High-temperature thermoplastics excellent candidates for use in aerospace applications. Graphite-fiber composites containing thermoplastic matrices have wide applicability.
Singh, Jag J.↗
Free Volume in Glassy Poly(arylene Ether Ketone)s
Amorphous polyarylene ether ketones were examined in the glassy state by positron annihilation lifetime spectroscopy ( PALS ) and in the melt by standard rheological techniques. Specimens were well-characterized fractions of two isomeric structures. PALS clearly shows that the polymer with meta linkages in its backbone contains larger voids (greater than 0.25 nm radius). Thus despite their similar bulk densities, the two materials must pack very differently on a local scale. On the other hand, the free volumes inferred from the WLF treatment of melt viscosity data are practically identical in both materials ca. 4% at T(sub g). The comparison between techniques sheds some light on the distribution of free volume.
Hinkley, J. A.↗
External field effects on diffusion and solidification derived from the free-volume model
Expressions for the diffusion coefficient and the solidification rate from the free-volume model of liquids developed by Turnbull and Cohen have been used to estimate the effects which microgravity and magnetic fields will have on these quantities. The mathematical formalism describing changes of the diffusion coefficient and the solidification rate is the same for both the microgravity and magnetic field cases, but the difference between the magnitudes of the two effects is quite large. The change in the two parameters is found to be less than .0001% for the microgravity case and on the order of 0.1 to 1.1% for the magnetic field case for four representative materials. The diffusion coefficient and the solidification rate are found to increase under the influence of an applied magnetic field, and this is in agreement with experimental observations.
Miller, R. I.↗
Free Volume Considerations in Thermoplastic and Thermosetting Resins
The direct measurement of physical aging and of the volume changes which go on during the course of this aging is discussed. Data on PMMA showing its physical aging as measured by its stress relaxation response and the accompanying volume changes are presented. An indication of how one can measure the free volume both directly from the volume change itself and relatively directly via a new technique is given. The application of this new technique (electron spin resonance spectroscopy) to other polymer systems is demonstrated.
Landel, R. F.↗
High internal free volume compositions for low-k dielectric and other applications
The present invention provides materials, devices, and methods involving new heterocyclic, shape-persistent monomeric units with internal free volume. In some cases, materials the present invention may comprise monomers, oligomers, or polymers that incorporate a heterocyclic, shape-persistent iptycene. The present invention may provide materials having low dielectric constants and improved stability at high operating temperatures due to the electron-poor character of materials. In addition, compositions of the invention may be easily synthesized and readily modified to suit a particular application.
Swager, Timothy M.↗
The dependence of relaxation times on free volume in high polymers
Shift of mechanical and dielectric relaxation maxima of polyvinyl chloride over wide range of frequency, temperature, and pressure, and extension of Eyring theory
POLYVINYL CHLORIDE↗
Cavities in molecular liquids and the theory of hydrophobic solubilities
Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.
NASA Discipline Exobiology↗
An investigation of microstructural characteristics of contact-lens polymers
The free volume and gas permeability in several contact lens specimens were measured as part of a Space Commercialization Program. Free volume was measured using positron lifetime spectroscopy, while permeability for O2, N2, CO2 gases was measured using mass spectrometry and polarography. Permeability for all gases increases with the mean free volume cell size in the test samples. As might be expected, the specimens with the highest free volume fraction also exhibit the lowest Rockwell Hardness Number. An interesting corollary is the finding that the presence of fluorine atoms in the lens chemical structure inhibits filling up of their free volume cells. This is expected to allow the lenses to breathe freely while in actual use.
Singh, Jag J.↗
Development of a contact lens quality monitoring system
The quality of contact lens samples depends strongly on their free volume fractions. It is expected that the free volume fraction of the test samples will also impact their attenuation coefficients for soft x rays. Samples with larger free volume fractions should have lower linear attenuation coefficients. Linear attenuation coefficients for Cd-109/Ag-109 x rays have been measured in five contact lens samples. It has been shown that the difference in the linear attenuation coefficients of discs from any given sample are entirely due to the difference in their respective volume fractions. It is therefore concluded that an x ray attenuation measurement system can serve as a quality monitor for contact lens polymers.
Singh, Jag J.↗
Investigation of the effects of short chain processing additives on polymers
The effects of low level concentrations of several short chain processing additives on the properties of the 4,4'-bis(3,4-dicarboxyphenoxy) diphenylsulfide dianhydride (BDSDA)/4,4'-diaminodiphenyl ether (ODA)/1,3'-diaminobenzene (m-phenylene diamine) (MPA) (422) copolyimide were investigated. It was noted that 5 percent MPD/phthalic anhydride (PA) is more effective than 5 percent ODA/PA and BDSDA/aniline (AN) in strengthening the host material. However, the introduction of 10 percent BDSDA/AN produces disproportionately high effects on free volume and free electron density in the host copolyimide.
Singh, J. J.↗
Microstructural Characterization of Thin Polyimide Films by Positron Lifetime Spectroscopy
Positron lifetimes have been measured in a series of thin aromatic polyimide films. No evidence of positronium formation was observed in any of the films investigated. All test films exhibited only two positron lifetime components, the longer component corresponding to the positrons annihilating at shallow traps. Based on these trapped positron lifetimes, free volume fractions have been calculated for all the films tested. A free volume model has been developed to calculate the dielectric constants of thin polyimide films. The experimental and the calculated values for the dielectric constants of the films tested are in reasonably good agreement. It has been further noted that the presence of bulky CF(sub 3) groups and meta linkages in the polyimide structure results in higher free volume fraction and, consequently, lower dielectric constant values for the films studied.
Eftekhari, A.↗