• Journal of the Korean Electrochemical Society
• /
• v.3 no.1
• /
• pp.49-56
• /
• 2000

In the present we.k, temperature dependence of oxygen diffusivity in the polyvinyl chloride (PVC) film $D_f$ formed on gold electrode was investigated using steady-state rotating disk electrode (RDE) technique and modulated electrohydrodynamic (EHD) impedance technique. Both the diffusion rate defined as the ratio of oxygen diffusivity in the PVC film to the film thickness $D_f/\delta_f$ and the time constant $\delta_f^2/D_f$ for oxygen diffusion through the PVC film were obtained from plot of the limiting current versus disk rotation speed and from filing the EHD impedance spectra experimentally measured to those theoretically calculated on the basis of the diffusion equation for mass transport through the non-conductive and porous film, respectively. By combining measured $D_f/\delta_f$ with $\delta_f^2/D_f$, we determined $\delta_f\;and\;D_f$ at room temperature separately. As temperature increased, it appeared that the $D_f$ value measured for the PVC film-covered gold RDE was enhanced more rapidly than that $D_s$ value in the solution measured for the PVC film-free gold RDE. This means that the pores glowing with increasing temperature act as effective diffusion paths within the film. The present in-situ steady-state and modulated EHD measurements prove to be effective for determining $\delta_f\;and\;D_f$, separately and at the same time the porosity of the PVC film at temperatures below glass temperature $T_g$ of the film.

• Proceedings of the Korea Water Resources Association Conference
• /
• 2015.05a
• /
• pp.103-103
• /
• 2015

유류유출사고와 같이 하천 수표면의 흐름에 따라 이동 확산하는 부유성 오염물질의 혼합해석을 위해 많은 연구자들은 입자추적모형을 사용한 혼합모의를 수행해왔다. 입자추적모형에서 오염물질의 혼합은 평균 유속 분포에 의한 결정론적인 이동과 난류유동에 의한 무작위적인 혼합으로 나타내며, 난류혼합에 의한 수평확산은 난류확산계수로 조절한다. 따라서 표면흐름에 의한 난류확산계수의 산정을 위해 많은 연구자들은 부유성 입자를 이용한 실내실험을 수행하여 수평확산계수를 산정했고(Engelund, 1969; Cederwall, 1971), 최근에는 GPS의 발전으로 인해 해양영역에서 GPS를 장착한 표면부자를 활용한 확산실험을 통해 수평확산계수를 산정한 바 있다(Kjellson and $D{\ddot{o}}{\ddot{o}}s$, 2012; Alpers 등, 2013). 하천수질오염사고의 약 43.5%가 유류유출에 의한 것이며(환경부, 2013), 이에 따라 표면흐름에 의한 오염물질 혼합해석이 필요하나, 하천에서 수평확산계수 산정을 위한 현장실험연구는 부족한 상황이다. 따라서 본 연구에서는 낙동강 본류에서 GPS부자를 이용한 입자추적실험을 수행하여 표면흐름에 의한 확산계수를 산정했다. GPS부자를 이용한 입자추적실험은 낙동강의 강정고령보 하류와 구미보 하류의 각각 세 지점에서 수행되었다. GPS부자는 바람에 의한 교란을 최소화하기 위해 지름 10 cm의 구형으로 제작하였으며 시범테스트를 통해 입자의 주 궤적 변화가 크지 않은 지점에 GPS부자를 투입했다. GPS부자는 오염물질의 사고유출을 가정하여 한 지점에 투입했고 GPS부자 사이의 간섭을 최소화하기 위해 25 ~ 35개의 GPS부자를 이용했다. 표면흐름에 의해 이동하는 부자의 위치는 GPS에 시계열로 저장됐고 ADCP를 이용하여 실험당시의 수리량을 측정했다. 입자위치의 시계열자료로부터 GPS부자의 확산범위의 시간변화를 계산했고 단순 모멘트법을 이용하여 종, 횡 방향 확산계수를 계산했다. 그 결과, 종 방향 확산계수는 $0.003{\sim}0.041m^2/s$로 계산되었고 횡 방향 확산 계수는 $0.001{\sim}0.012m^2/s$로 계산되어, 흐름방향의 유속성분에 의한 확산이 지배적인 것으로 나타났다. 지류 합류부에서는 이송이 지배적인 혼합이 발생되었고(Pe>1) Pe의 증가에 따라 수평확산계수가 감소되었다. 25~35개 GPS부자 궤적의 앙상블 평균으로부터 계산한 Integral time scale은 모멘트법으로부터 계산한 종, 횡 방향 확산계수와 비례하는 것으로 나타나, Taylor(1921)의 이론과 일치했다. 또한 실험수로에서 수행된 기존연구결과와 비교한 결과, 하폭 대 수심비, 마찰항의 증가에 따라 수평확산계수가 증가하는 경향을 나타내었다.

• Applied Chemistry for Engineering
• /
• v.10 no.6
• /
• pp.876-880
• /
• 1999

The surfactant self-diffusion coefficients of mixed micellar solutions of ionic and nonionic surfactants have been measured by the NMR pulsed field gradient spin echo(FT-PGSE) method. In addition, the line widths of $^1H$ NMR signal have been monitored. The system investgated are $C_{12}EO_5/SDS/D_2O$, $C_{12}EO_5/DTAC/D_2O$, and $C_{12}EO_8/SDS/D_2O$. In the sample series, the molar ratios of $D_2O$ to surfactant(ionic+nonionic) were kept constant while the surfactant mixing ratio was varied. For the $C_{12}EO_5$ system, the surfactant self-diffusion coefficient indicates minimum when the surfactant mixing ratio is about 20% ionic surfactant. The observed decrease in self-diffusion coefficients as nonionic surfactant was replaced by ionic surfactant is interpreted to mainly be due to an increased micelle-micelle repulsion. The increase in self-diffusion coefficients occurring at higher fraction of ionic surfactant is shown to be due to a decrease in micelle size. For the $C_{12}EO_8$ system, the effect of the surfactant mixing ratio is much weaker which can be understood by considering the molecular geometry and large headgroup area. The proton NMR line widths correlate well with the self-diffusion coefficients and broadening of the alkyl chain methylene signals is found when the self-diffusion coefficients is low.

• Journal of Ocean Engineering and Technology
• /
• v.11 no.2
• /
• pp.39-47
• /
• 1997

Creep rate the elevated temperature is known to be controller by the softening process of microstructure especially in the solid solution alloys such as 125 Cr rotor steel. The change of structure is a decreasing process of the free energy of the state including stress, diffusivity of the material, and tmeperature. This study shows that diffusion coefficient, D of 12% Cr rotor steel at 953K with 74.8 MPa is 1.084~3.140*$10^{15}mm^2sec^1$ compared to $1.658*10^{24}mm^2sec^1$at 963K without stress. During creep, the growth of martensite laths accelerates the diffusion coefficient under stress due to incoherency of interface between carbides and matrix.

• Journal of the Korea institute for structural maintenance and inspection
• /
• v.17 no.6
• /
• pp.104-111
• /
• 2013

Deterioration is accelerated due to additional intrusion of chloride ion in crack width in cracked concrete. In this paper, modeling on equivalent diffusion coefficient in cracked concrete is performed for 1-D (Anisotropic) and 2-D (Isotropic) diffusion based on steady state condition. In the previous research, rectangular shape of crack was considered but the shape was modified to wedge shape with torturity. For verification of the proposed model, crack is induced in concrete sample and migration test in steady state is performed for 1-D diffusion. For 2-D diffusion, previous test results are adopted for verification. Through considering wedge shape of crack with torturity, diffusion coefficients in 1-D and 2-D diffusion are reduced, and the more reasonable prediction is obtained. The results from the proposed model with torturity of 0.10~0.15 are shown to be in the best agreement with the test results.

• Tuberculosis and Respiratory Diseases
• /
• v.59 no.4
• /
• pp.374-379
• /
• 2005

Background : The single-breath carbon monoxide diffusion capacity (DLCO) and the per unit alveolar volume (KCO; $D_LCO/VA$) gave discordant values when there was an abnormal alveolar volume (VA). However, the clinical significance of the discordant values in patients with airflow limitation has not been examined. This study investigated the $D_LCO$ and KCO changes after improving the airflow limitation. Methods : The baseline $D_LCO$ and KCO with lung volume were measured in patients with an airflow obstruction. The effective alveolar volume was measured using the single-breath $CH_4$ dilution method. The patients divided into two groups according to the baseline values: (1) increased KCO in comparison with the $D_LCO$ (high discordance) (2) decreased or not increased KCO in comparison with the $D_LCO$ (low discordance). The diffusion capacity and lung volume were measured after treatment. Results : There was no significant difference in the baseline lung volumes including the $FEV_1$ and FVC between the two groups. The $FEV_1$ and FVC were significantly increased in the high discordance group compared with the low discordance group after treating the airflow limitation. The $D_LCO$ and alveolar volume were significant higher in the high discordance group compared with the low discordance group while the TLC was not. Conclusion : The discordance between the $D_LCO$ and KCO could be translated into an airflow reversibility in patients with an airflow limitation.

• Journal of the Korean Chemical Society
• /
• v.22 no.5
• /
• pp.304-310
• /
• 1978

The relative permeabilities, distribution coefficients and diffusion coefficient of some salts which are important components in blood plasma through a poly(HEMA) membrane were measured. The crosslinker which was used for preparing the membrane was tetraethylene glycol dimethacrylate(TEGDMA), the weight percentage of the latter was about 2.8. We found that the diffusion coefficients ($D_m$) of the solutes decrease exponentially with increasing molecular weight, and also that $D_m$'s decrease linearly (except urea) with cylindrical radius (a). These facts were explained by a sieve pore flow model. The relative permeability and diffusion coefficient of urea at various temperature were larger than those of other solutes such as glycine, ${\beta}$-alanine, D-glucose, saccharose and maleic acid. The result indicates that the poly(HEMA) membrane might be suitable for hemodialysis application.

• Membrane Journal
• /
• v.10 no.3
• /
• pp.139-147
• /
• 2000

Non-Fickian (or anomalous) diffusion was observed in transient sorption of aromatic solvents(such as benzene, toluene, and chlorobenzene) in fluoropolymers (such as ETFE, ECTFE and PVDF). In this study, five other transient sorption models (Crank, Long ＆ Richman, Berens ＆ Hopfenberg, Neogi, Li) based on Fick's law were employed to fit the anomalous sorption data for aromatic solvents. The adjustable parameters were determined by least square analysis of the measured and predicted fractional uptake. For ETFE sorption data slightly deviating from Fickian behavior, all the models exhibited satisfactory results in fitting the anomalous sorption data. In particular, Neogj model predicted intrinsic diffusivity (0.4～0.8$\times$10$^{-5}$ $\textrm{cm}^2$/day) and equilibrium diffusivity (0.13～0.31$\times$10$^{-4}$ $\textrm{cm}^2$/day) as well as relaxation kinetics related to non-Fickain diffusion. For a typical sigmoidal sorption behavior in PVDF, only Crank's model could give the reasonable evaluation on transport properties. The ratio of intial diffusivity (D$_{i}$) to final equilibrium diffusivity (D$_{\infty}$) was ranged from 80 to 200. For the final stage of uptake In ECTFE with drastic acceleration, all the models exhibited significant deviations from the sorption data. New diffusion models based on thermodynamics and continuum mechanics should be employed to get valuable information on transport properties as well as relaxation kinetics coupled with non-Fickian diffusion.

• Journal of the Korean Chemical Society
• /
• v.41 no.8
• /
• pp.385-391
• /
• 1997

Diffusion Coefficient$(D_0)$ and electrode reaction rate Constant$(K_0)$ of Co$(dimethyl bipyridine)_3(ClO_4)_2$ were determined by cyclic voltammetry and chronoamperometry. It was also investigated that the effects of solvent, concentration, and scan rate, etc. on the diffusion coefficient and the temperature effect on the rate constant. The peak currents and diffusion coefficients were dcreased as increasing the viscosity of solvent. Diffusion coefficient was $5.54{\times}10^{-6 }cm^2/sec$ and the reaction rate constant was $2.39{\times}10^{-3 }/s$ at 25$^{\circ}C$. The thermodynamic parameters such as ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;and\;{\Delta}S$ were calculated from plotting the reaction rate constants versus the solution temperatures. This compound was shown the catalytic effect on the oxygen reduction that the reduction peak current of oxygen was greatly enhanced and the peak potential was shifted to +0.2 volt.

• Analytical Science and Technology
• /
• v.9 no.3
• /
• pp.292-301
• /
• 1996

The synthesis of poly(ether)tailed bipyridine complex as redox reaction probes has advanced attempts to interpret very slow diffusion and heterogeneous electron transfer. Diffusion coefficients as low as $1.5{\times}10^{-15}cm^2/s$ have been observed for the oxidation of neat $Co(bpy(ppgm)_2)_{3^-}(ClO_4)_2$ with $LiClO_4$ electrolyte. Heterogeneous electron transfer rate constants of materials were found to vary with diffusion coefficient. The decrease in k as the diffusion coefficient decreases was actually caused by the decreasing D. Diffusion coefficient for compound of strong ion pairing anion($ClO{_4}^-$) was much smaller than the diffusion coefficient for compound of weak ion pairing anion($CF_3COO^-$).