Activation barriers for oxygen diffusion in polystyrene and polycarbonate glasses: effects of codissolved argon, helium, and nitrogen

1995 ◽  
Vol 73 (11) ◽  
pp. 1831-1840 ◽  
Author(s):  
Bojie Wang ◽  
Peter R. Ogilby

A recently developed spectroscopic technique was used to determine oxygen diffusion coefficients as a function of temperature for polystyrene and polycarbonate films. Data were recorded at total pressures <300 Torr over the temperature range 5–45 °C under conditions in which argon, helium, and nitrogen, respectively, were copenetrants. In all cases, the presence of the additional gas caused an increase in the oxygen diffusion coefficient. Arrhenius plots of the data yield (a) a diffusion activation barrier, Eact, and (b) a diffusion coefficient, D0, that represents the condition of "barrier-free" gas transport for the temperature domain over which the Arrhenius plot is linear. For all cases examined in both polystyrene and polycarbonate, D0 increased with an increase in the partial pressure of added gas. In polystyrene, the presence of an additional gas did not change Eact. In polycarbonate, Eact obtained in the presence of helium and argon likewise did not differ from that obtained in the absence of the copenetrant. When nitrogen was the added gas, however, a larger value of Eact was obtained. This latter observation is interpreted to reflect the plasticization of polycarbonate by nitrogen. Eact and D0 data are discussed within the context of a model that distinguishes between dynamic and static elements of free volume in the polymer matrix. Keywords: oxygen diffusion, polystyrene, polycarbonate, activation barrier.

Author(s):  
K Miura

AbstractOxygen diffusion coefficients in normal and decomposed cigarette papers were measured, and oxygen transfer through the cigarette papers was estimated. The oxygen diffusion coefficient varied with the properties of the cigarette papers, however, the differences in the oxygen transfer coefficient were not very large. The oxygen diffusivity of the cigarette papers did not increase after thermal decomposition. No correlation was found between the oxygen transfer coefficient of the normal paper and the decomposed paper.


1998 ◽  
Vol 37 (4-5) ◽  
pp. 171-175
Author(s):  
Artem Khlebnikov ◽  
Falilou Samb ◽  
Paul Péringer

p-toluenesulphonic acid degradation by Comamonas testosteroni T-2 in multi-species biofilms was studied in a fixed bed biofilm reactor. The polypropylene static mixer elements (Sulzer Chemtech Ltd., Switzerland) were used as a support matrix for biofilm formation. Biofilm respiration was estimated using the dynamic gassing-out oxygen uptake method. A strong relation between oxygen uptake and reactor degradation efficiency was observed, because p-toluenesulphonate degradation is a strictly aerobic process. This technique also allowed us to estimate the thickness of the active layer in the studied system. The mean active thickness was in order of 200 μm, which is close to maximum oxygen penetration depth in biofilms. A transient mathematical model was established to evaluate oxygen diffusitivity in non-steady-state biofilms. Based on the DO concentration profiles, the oxygen diffusion coefficient and the maximum respiration activity were calculated. The oxygen diffusion coefficient obtained (2 10−10-1.2 10−9 m2 s−1) is in good agreement with published values. The DO diffusion coefficient varied with biofilm development. This may be, most likely, due to the biofilm density changes during the experiments. The knowledge of diffusivity changes in biofilms is particularly important for removal capacity estimation and appropriate reactor design.


Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 4030
Author(s):  
Gengbiao Chen ◽  
Zhiwen Liu

The diffusion behavior of fluid water in nanochannels with hydroxylation of silica gel and silanization of different modified chain lengths was simulated by the equilibrium molecular dynamics method. The diffusion coefficient of fluid water was calculated by the Einstein method and the Green–Kubo method, so as to analyze the change rule between the modification degree of nanochannels and the diffusion coefficient of fluid water. The results showed that the diffusion coefficient of fluid water increased with the length of the modified chain. The average diffusion coefficient of fluid water in the hydroxylated nanochannels was 8.01% of the bulk water diffusion coefficient, and the diffusion coefficients of fluid water in the –(CH2)3CH3, –(CH2)7CH3, and –(CH2)11CH3 nanochannels were 44.10%, 49.72%, and 53.80% of the diffusion coefficients of bulk water, respectively. In the above four wall characteristic models, the diffusion coefficients in the z direction were smaller than those in the other directions. However, with an increase in the silylation degree, the increased self-diffusion coefficient due to the surface effect could basically offset the decreased self-diffusion coefficient owing to the scale effect. In the four nanochannels, when the local diffusion coefficient of fluid water was in the range of 8 Å close to the wall, Dz was greater than Dxy, and beyond the range of 8 Å of the wall, the Dz was smaller than Dxy.


Fluids ◽  
2018 ◽  
Vol 3 (4) ◽  
pp. 99 ◽  
Author(s):  
Kazuma Yamanaka ◽  
Takayuki Narumi ◽  
Megumi Hashiguchi ◽  
Hirotaka Okabe ◽  
Kazuhiro Hara ◽  
...  

The properties of chaotic advection arising from defect turbulence, that is, weak turbulence in the electroconvection of nematic liquid crystals, were experimentally investigated. Defect turbulence is a phenomenon in which fluctuations of convective rolls arise and are globally disturbed while maintaining convective rolls locally. The time-dependent diffusion coefficient, as measured from the motion of a tagged particle driven by the turbulence, was used to clarify the dependence of the type of diffusion on coarse-graining time. The results showed that, as coarse-graining time increases, the type of diffusion changes from superdiffusion → subdiffusion → normal diffusion. The change in diffusive properties over the observed timescale reflects the coexistence of local order and global disorder in the defect turbulence.


2007 ◽  
Vol 263 ◽  
pp. 189-194
Author(s):  
Ivo Stloukal ◽  
Jiří Čermák

Coefficient of 65Zn heterodiffusion in Mg17Al12 intermetallic and in eutectic alloy Mg - 33.4 wt. % Al was measured in the temperature region 598 – 698 K using serial sectioning and residual activity methods. Diffusion coefficient of 65Zn in the intermetallic can be written as DI = 1.7 × 10-2 m2 s-1 exp (-155.0 kJ mol-1 / RT). At temperatures T ≥ 648 K, where the mean diffusion path was greater than the mean interlamellar distance in the eutectic, the effective diffusion coefficient Def = 2.7 × 10-2 m2 s-1 exp (-155.1 kJ mol-1 / RT) was evaluated. At two lower temperatures, the diffusion coefficients 65Zn in interphase boundaries were estimated: Db (623 K) = 1.6 × 10-12 m2 s-1 and Db (598 K) = 4.4 × 10-13 m2 s-1.


2011 ◽  
Vol 79 ◽  
pp. 77-82
Author(s):  
Yi Min ◽  
Jian Huang ◽  
Cheng Jun Liu ◽  
Mao Fa Jiang

Based on the silicate structure theory, the molten slag structure and the existential state of and during micro-carbon Cr-Fe alloy production process were analysised, and then their diffusion coefficients were calculated. The results showed that, during the initial stage, the average diffusion coeffecient of and is close to the , the reaction process is controlled by the diffusion of () and corporately, during the later stage, the diffusion coefficient of is less than average diffusion coefficient of and , the controlling step is the diffusion of . According to the evolution of diffusion coefficient, molten slag composition optimization method was advised to increase the diffusion ability of and for enhancing the reaction efficiency and the recovery rate of chromium.


Geophysics ◽  
2016 ◽  
Vol 81 (5) ◽  
pp. D519-D526 ◽  
Author(s):  
Andreas Weller ◽  
Zeyu Zhang ◽  
Lee Slater ◽  
Sabine Kruschwitz ◽  
Matthias Halisch

Permeability estimation from induced polarization (IP) measurements is based on a fundamental premise that the characteristic relaxation time [Formula: see text] is related to the effective hydraulic radius [Formula: see text] controlling fluid flow. The approach requires a reliable estimate of the diffusion coefficient of the ions in the electrical double layer. Others have assumed a value for the diffusion coefficient, or postulated different values for clay versus clay-free rocks. We have examined the link between a widely used single estimate of [Formula: see text] and [Formula: see text] for an extensive database of sandstone samples, in which mercury porosimetry data confirm that [Formula: see text] is reliably determined from a modification of the Hagen-Poiseuille equation assuming that the electrical tortuosity is equal to the hydraulic tortuosity. Our database does not support the existence of one or two distinct representative diffusion coefficients but instead demonstrates strong evidence for six orders of magnitude of variation in an apparent diffusion coefficient that is well-correlated with [Formula: see text] and the specific surface area per unit pore volume [Formula: see text]. Two scenarios can explain our findings: (1) the length scale defined by [Formula: see text] is not equal to [Formula: see text] and is likely much longer due to the control of pore-surface roughness or (2) the range of diffusion coefficients is large and likely determined by the relative proportions of the different minerals (e.g., silica and clays) making up the rock. In either case, the estimation of [Formula: see text] (and hence permeability) is inherently uncertain from a single characteristic IP relaxation time as considered in this study.


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