This paper describes a membrane permeability measuring setup based on photoacoustic spectroscopy using continuous carrier gas flow to transport the permeated analyte molecules into a photoacoustic detection cell. The permeability parameters of the sample were determined from the measured permeation curves by using a numerical curve fitting algorithm. The method was applied to different membrane samples for determining methane and carbon-dioxide permeability at various carrier gas flow rates (CFRs). For each sample, a characteristic threshold flow rate (TFR) value can be identified below which a strong dependency of the determined permeation parameters on the CFR was found. For those cases when the CFR value cannot be set to be sufficiently high (i.e. above the TFR value), an extrapolation method was presented giving an accurate estimation of the permeation parameters.
a b s t r a c tAccuracy of the gas permeability parameters (GPPs), i.e. solubility, diffusivity and permeability deduced from permeation measurements, is investigated for the case of homogeneous polymer sheet samples. The widely used time-lag method (TLM) and the recently introduced full curve-fitting method (FCFM) are compared on simulated and on measured permeation curves artificially distorted in various ways in order to mimic potential deficiencies of permeation measurements. Accuracy of the methods is defined as the relative deviation of the calculated from the real GPPs, i.e. those which are deduced from the distorted and the original, non-distorted curves, respectively. The following distortions have been applied: temporal truncation of the permeation curves, increasing the noise level of the measurement and shifting the permeation curve either along the concentration or the time axis. (The latter two transformations correspond to an unnoticed background shift in the readings of the concentration detection unit and an uncertainty in the actual inception of the permeation process, respectively). While all these distortions mimic realistic deficiencies of permeation measurements, the last one is relevant only in case of fast permeation processes through highly permeable membranes. For all but the last transformation, FCFM has been found to yield more accurate GPPs than TLM.
In a carrier flow based permeation system the measured permeation curve is the convolution of two processes: the intrinsic permeation process and the transfer of the permeated molecules through the measuring system. The latter one is quantified by the instrument response function (IRF). The possibility of calculating the IRF from permeation curves measured at various volumetric flow rates of the carrier gas is examined. The results are in partial agreement with preliminary expectations: the dependency of the calculated IRF on the volumetric flow rate of the carrier gas indeed follows roughly the expected tendency; however it is not completely independent from the physical properties of the measured membrane sample. This discrepancy can most probably be attributed to the imperfect design of the applied permeation cell. Overall it is expected that the proposed method for determining the instrument transfer function is a valuable tool for improving the design of permeation measuring systems.
The paper deals with theoretical treatment of physical limits for computation. We are using some statements on base of min energy/bit, power delay product, Shannon entropy and Heisenberg uncertainty principle which result in about kTln(2) energy for a bit of information.
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