Effect of pressure on gas permeability coefficients. A new application of “free volume” theory

The present work is a continuation of a general study of the effect of pressure on gas and vapor permeation through nonporous polymeric membranes. Permeability coefficients have been measured for 1,1-difluoroethylene (C₂H₂F₂) and fluoroform (CHF₃) in polyethylene at penetrant pressures up to 35 atm and at temperatures between -18 and 70°C. The permeability coefficient P? for the 1,1-difluoroethylene—polyethylene system was found to increase with increasing pressure differential Δp across the membrane. Isothermal plots of log ΔP versus Δp are generally linear and can be represented by empirical relations of the form ΔP = P(0)exp{m Δp}, where P(0) and m are constants. The slope m of these isotherms decreases with increasing temperature. Plots of log P? versus Δp for the fluoroform—polyethylene system are also linear, but exhibit negative slopes, i.e., P? decreases with increasing Δp. An extension of Fujita's “free volume” theory of diffusion in polymers shows that the dependence of P? on pressure reflects how the free volume of the polymer is affected by this pressure. An increase in the penetrant pressure may result in two opposing effects: (a) the concentration of the penetrant dissolved in the membrane is increased, thereby increasing the free volume, and (b) the hydrostatic pressure on the membrane is also increased, which causes a decrease in the free volume. If the overall effect is an increase in the free volume of the polymer, then P? will also increase, and vice versa.     

On the damped nonlinear evolution equation wtt = σ(w)xx − ywt

Initial boundary value problems for the damped nonlinear wave equation w_tt = σ(w)_xx ? yw_t arise in several areas of applied mathematics and, in particular, in studies of shearing flow in a nonlinear viscoelastic fluid; the problems of global existence and nonexistence of smooth solutions have been extensively studied in the strictly hyperbolic case σ′(δ) ? ε > 0, ?δ?R¹ as well as in the case where σ′(0) > 0 and the initial data are chosen so small that σ′(w) > 0 for as long as a smooth solution w(x, t) exists. In this paper the global nonexistence problem is studied for the cases σ′(0) = 0 and σ′(0) > 0 but σ′(δ) < 0 for ¦δ¦ sufficiently large and growth estimates which are valid on the maximal interval of existence of a sufficiently smooth solution are derived.     

Tests of a “free-volume” model of gas permeation through polymer membranes. I. Pure CO2, CH4, C2H4, and C3H8 in polyethylene

Permeability coefficients have been measured for CO₂, CH₄, C₂H₄, and C₃H₈ in polyethylene membranes at temperatures of 5, 20, and 35°C and at applied gas pressures of up to 30 atm. The temperature and pressure dependence of the permeability coefficients was represented satisfactorily by an extension of Fujita's free-volume model of diffusion of small molecules in polymers. The results of the present steady-state permeability measurements provide further support for the conclusion reached from previous unsteady-state diffusivity measurements that Fujita's model is applicable to the transport of small molecules, such as CO₂, CH₄, C₂H₄, and C₃H₈, in polyethylene. It was previously thought that this model is applicable only to the transport of larger molecules, such as of organic vapors, in polymers.     

A comparison of T2*-weighted magnitude and phase imaging for measuring the arterial input function in the rat aorta following intravenous injection of gadolinium contrast agent

The arterial input function (AIF) is important for quantitative MR imaging perfusion experiments employing Gd contrast agents. This study compared the accuracy of T(2)*-weighted magnitude and phase imaging for noninvasive measurement of the AIF in the rat aorta. Twenty-eight in vivo experiments were performed involving simultaneous arterial blood sampling and MR imaging following Gd injection. In vitro experiments were also performed to confirm the in vivo results. At 1.89 T and TE=3 ms, the relationship between changes in 1/T(2)* in blood (estimated from MR signal magnitude) and Gd concentration ([Gd]) was measured to be approximately 19 s(-1) mM(-1), while that between phase and [Gd] was approximately 0.19 rad mM(-1). Both of these values are consistent with previously published results. The in vivo phase data had approximately half as much scatter with respect to [Gd] than the in vivo magnitude data (r(2)=.34 vs. r(2)=.17, respectively). This is likely due to the fact that the estimated change in 1/T(2)* is more sensitive than the phase to a variety of factors such as partial volume effects and T(1) weighting. Therefore, this study indicates that phase imaging may be a preferred method for measuring the AIF in the rat aorta compared to T(2)*-weighted magnitude imaging.     

Unitarily Inequivalent Representations in Algebraic Quantum Theory

It has been maintained that the physical content of a model of a system is completely contained in the C∗-algebra of quasi-local observables that is associated with the system. The reason given for this is that the unitarily inequivalent representations of are physically equivalent. But, this view is dubious for at least two reasons. First, it is not clear why the physical content does not extend to the elements of the von Neumann algebras that are generated by representations of . It is shown here that although the unitarily inequivalent representations of are physically equivalent, the extended representations are not. Second, this view detracts from special global features of physical systems such as temperature and chemical potential by effectively relegating them to the status of fixed parameters. It is desirable to characterize such observables theoretically as elements of the algebra that is associated with a system rather than as parameters, and thereby give a uniform treatment to all observables. This can be accomplished by going to larger algebras. One such algebra is the universal enveloping von Neumann algebra, which is generated by the universal representation of ; another is the direct integral of factor representations that are associated with the set of values of the global features. Placing interpretive significance on the von Neumann algebras mentioned earlier sheds light on the significance of unitarily inequivalent representations of , and it serves to show the limitations of the notion of physical equivalence.     

Pronounced enhancement of the lower critical field and critical current deep in the superconducting state of PrOs4Sb12

We have observed an unexpected enhancement of the lower critical field H(c1)(T) and the critical current I(c)(T) deep in the superconducting state below T approximately 0.6 K (T/T(c) approximately 0.3) in the filled skutterudite heavy fermion superconductor PrOs(4)Sb(12). From a comparison of the behavior of H(c1)(T) with that of the heavy fermion superconductors U(1-x)Th(x)Be(13) and UPt(3), we speculate that the enhancement of H(c1)(T) and I(c)(T) in PrOs(4)Sb(12) reflects a transition into another superconducting phase that occurs below T/T(c) approximately 0.3. An examination of the literature reveals unexplained anomalies in other physical properties of PrOs(4)Sb(12) near T/T(c) approximately 0.3 that correlate with the features we have observed in H(c1)(T) and I(c)(T).     

Localized excitations at the Mott insulator-superfluid interfaces for confined Bose-Einstein condensates

In this Letter, we derive the dispersion relation of the surface waves at the interfaces between Mott-insulating and superfluid domains for a two-dimensional Bose-Einstein condensate in an optical lattice subjected to a confining potential. We then calculate their contribution to the heat capacity of the system and show how its low-temperature scaling allows an experimental test of the existence and properties of Mott insulator-superfluid domains.     

Combining energetic and informational masking for speech identification

This study examined combinations of energetic and informational maskers in speech identification. Speech targets and maskers (speech or noise) were processed and filtered into sets of 15 narrow frequency bands. The target was the sum of eight randomly selected bands. More masking occurred for speech maskers than for spectrally matched noise maskers regardless of whether the masker bands overlapped the target bands. The greater effect of the speech maskers was interpreted as due to informational masking. When the masker was comprised of nonoverlapping bands of speech, the addition of bands of noise overlapping the speech masker, but not the speech target, reduced the overall amount of masking. Surprisingly, presenting the noise to the ear contralateral to the target and masker produced an even greater release from masking. The contralateral noise was apparently sufficient to cause a slight change in the image of the ipsilateral speech masker, possibly pulling it away from the target enough to allow the focus of attention on the target. This finding is consistent with the interpretation that in some conditions small binaural differences may be sufficient to cause, or significantly strengthen, the perceptual segregation of sounds.