• Title/Summary/Keyword: Diffusion coefficients

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Characteristics of Electrode Potential and AC Impendance of Perchlorate Ion-Selective Electrodes Based on Quaternary Phosphonium Salts in PVC Membranes (제4급 인산염을 이용한 과염소산 이온선택성 PVC막 전극의 전극전위와 AC 임피던스 특성)

  • 안형환
    • Membrane Journal
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    • v.9 no.4
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    • pp.230-239
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    • 1999
  • Perchlorate ion-selective electrodes in PVC membranes that respond linearly to concentration 106 M were developed by incorporating the quaternary phosphonium salts as a canier. The effects of the chemical structure, the contents of canier, the kind of plasticizer and the membrane thickness on electrode characteristics such as the electrode slope, the linear respone range and the detection limit were studied. With this results, the detectable pH range, selectivity coefficients and AC impedance characteristics were compared and investigated. The perchlorate ion substituents of the quaternary phosphonium salts like tetraoctylphosphonium perchlorate (TOPP) , tetraphenylphosphonium perchlorate(TPPP), and tetrabutylphosphonium perchlorate(TBPP) as a canier were used. The electrode characteristics were better in the ascending order of TBPP < TPPP < TOPP, with the increase of carbon chain length of the alkyl group. Dioctylsebacate(OOS) was best as a plasticizer, the canier contents were better with 11.76 wt% and the optimum membrane thickness was 0.19 mm. Under the above condition, the electrode slope was 56.58 mV/$^P{ClO}_4$,the linear response range was $10^{-1}$\times$10^{-6}$ M, the detection limit was 9.66 x $10^{-7}$ M. The performance of electrode was better than Orion electrode. The electrode potential was stable within the pH range from 3 to 11. The order of the selectivity coefficients for the perchlorate ion was sol < F < Br < 1. With the result of impedance spectrum, it was found that the equivalent circuit for the electrode could be expressed by a series combination of solution resistance, parallel circuit consisting of the double layer capacitance and bulk resistance and Warburg impedance. And solution resistance was almost not appeared and Warburg impedance was highly appeared by diffusion. Then Warburg coefficient was 1.32$\times$$10^74 $\Omega$ $\cdot$ ${cm}^2/s^{1/2}$.

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An Exploratory Study on Forecasting Sales Take-off Timing for Products in Multiple Markets (해외 복수 시장 진출 기업의 제품 매출 이륙 시점 예측 모형에 관한 연구)

  • Chung, Jaihak;Chung, Hokyung
    • Asia Marketing Journal
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    • v.10 no.2
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    • pp.1-29
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    • 2008
  • The objective of our study is to provide an exploratory model for forecasting sales take-off timing of a product in the context of multi-national markets. We evaluated the usefulness of key predictors such as multiple market information, product attributes, price, and sales for the forecasting of sales take-off timing by applying the suggested model to monthly sales data for PDP and LCD TV provided by a Korean electronics manufacturer. We have found some important results for global companies from the empirical analysis. Firstly, innovation coefficients obtained from sales data of a particular product in other markets can provide the most useful information on sales take-off timing of the product in a target market. However, imitation coefficients obtained from the sales data of a particular product in the target market and other markets are not useful for sales take-off timing of the product in the target market. Secondly, price and product attributes significantly influence on take-off timing. It is noteworthy that the ratio of the price of the target product to the average price of the market is more important than the price ofthe target product itself. Lastly, the cumulative sales of the product are still useful for the prediction of sales take-off timing. Our model outperformed the average model in terms of hit-rate.

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Hydraulic-Thermal-Mechanical Properties and Radionuclide Release-Retarding Capacity of Kyungju Bentonite (경주 벤토나이트의 수리-열-역학적 특성 및 핵종 유출 저지능)

  • Jae-Owan Lee;Won-Jin Cho;Pil-Soo Hahn
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.2 no.2
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    • pp.87-96
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    • 2004
  • Studies were conducted to select the candidate buffer material for a high-level waste (HLW) repository in Korea. This paper presents the hydraulic properties, the swelling properties, the thermal properties, and the mechanical properties as well as the radionuclide release-retarding capacity of Kyungju bentonite as part of those studies. Experimental results showed that the hydraulic conductivities of the compacted bentonite were very low and less than $10^{-11}$m/s. The values decreased with increasing the dry density of the compacted bentonite. The swelling pressures were in the range of 0.66 MPa to 14.4 ㎫ and they increased with increasing the dry density. The thermal conductivities were in the range of 0.80 ㎉/m $h^{\circ}C$ to 1.52 ㎉/m $h^{\circ}C$. The unconfined compressive strength, Young's modulus and Poison's ratio showed the range of 0.55 ㎫ to 8.83 ㎫, 59 ㎫ to 1275 ㎫, and 0.05 to 0.20, respectively, when the dry densities of the compacted bentonite were 1.4 Ms/㎥ to 1.8 Mg/㎥. The diffusion coefficients in the compacted bentonite were measured under an oxidizing condition. The values were $1.7{\times}10^{-10}$m^2$/s to 3.4{\times}10^{-10}$m^2$/s for electrically neutral tritium (H-3), 8.6{\times}10^{-14}$m^2$/s to 1.3{\times}10^{-12}$m^2$/s for cations (Cs, Sr, Ni), 1.2{\times}10^{-11}$m^2$/s to 9.5{\times}10^{-11}$m^2$/s for anions (I, Tc), and 3.0{\times}10^{-14} $m^2$/s to 1.8{\times}10^{-13}$m^2$/s $for actinides (U, Am), when tile dry densities were in the range of 1.2 Mg/㎥ to 1.8 Mg/㎥. The obtained results will be used in assessing the barrier properties of Kyungju bentonite as a buffer material of a repository in Korea.n Korea.

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Stabilization and Release Behavior of W1/O/W2-Type Multiple Emulsions Using Various Block Copolymer Emulsifier and Stabilizer (다양한 Block Copolymer를 유화제 및 안정화제로 사용한 W1/O/W2-Type 다중에멀젼의 방출거동 및 안정성)

  • Haw, Jung-Rim;Kim, Cheol-Hun
    • Applied Chemistry for Engineering
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    • v.8 no.4
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    • pp.560-567
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    • 1997
  • A new approach to obtain stable $W_1/O/W_2$ multiple emulsions has been studied ; The basis of the interfacial interaction between a PCL-PEO-PCL triblock copolymer and a lipophilic emulsifier in the dispersed oil phase was examined. $W_1/O/W_2$ multiple emulsions were prepared by the two-step method. Arlacel P-l35 was used as a liphophilic emulsifier and Synperonic PE/F 127 as a hydrophilic one. Eutanol-G was used as an oil phase. NaCl was encapsulated within the multiple emulsion droplets as the internal marker and its release rate studies were carried out. The suability of the multiple emulsions have been assessed by measuring Separation Ratios(%) and microscopic observations. The release of NaCl was significantly reduced in $W_1/O/W_2$ multiple emulsions containing PCL-PEO-PCL triblock copolymer(2k-4k-2k or 6k-4k-6k) in the oil phase. It may be concluded that the copolymer and the emulsifier form effective interfacial complex to enhance stability and to control the release rate. The effective diffusion coefficients of the NaCl were estimated as $2.64{\times}10^{-15}s$and $3.23{\times}10^{-16}gcm^2/s$ for the $W_1/O/W_2$ multiple emulsion containing 1.2 wt % of PCL-PEO-PCL triblock copolymers with compositions of 2k-4k-2k and 6k-4k-2k, respectively. The rate of release decreased with the increase of the initial concentration of NaCl. The results were examined in view of Higuchi mechanism. A kinetic model which is similar to the model for release of dispersed drugs from a polymeric matrix was found to be suitable for the release of NaCl from $W_1/O/W_2$ multiple emulsions.

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The Characteristics of Hydrodynamic Dispersion in a Horizontally Heterogeneous Fractured Rock Through Single Well Injection Withdrawal Tracer Tests (수평적으로 불균질한 단열암반층에서 단공주입양수 추적자시험에 의한 수리분산특성)

  • Kang, Dong-Hwan;Chung, Sang-Yong;Kim, Byung-Woo
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.53-60
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    • 2006
  • Single well injection withdrawal tracer tests with bromide were carried out at two wells developed in a horizontally heterogeneous fractured rock. The hydraulic conductivity of TW-1 well was 5 times larger than TW-2 well, and the average linear velocity of TW-2 well was 1.8 times faster than TW-1 well. The difference of hydrodynamic dispersions of two wells in the fractured rock was studied with the analysis of concentration breakthrough curves and cumulative mass recovery curves of bromide with withdrawal time, and the estimation of average travel distance, pore velocity, longitudinal dispersivity and longitudinal dispersion coefficient. The average travel distances of bromide were estimated to be 3.00 m in TW-1 well and 5.62 m in TW-2 well. The average pore velocities for the injection/withdrawal phase were estimated to be $4.31\;{\times}\;10^{-4}\;m/sec$ in TW-1 well and $8.08\;{\times}\;10^{-4}\;m/sec$ in TW-2 well. Average travel distance and pore velocity were higher in TW-2 well because of small effective porosity. Longitudinal dispersivities were estimated to be 28.73 cm in TW-1 well and 18.49 cm in TW-2 well, and bromide transport was 1.55 times faster in TW-1 well. Longitudinal dispersion coefficients were estimated to be $5.14\;{\times}\;10^{-6}\;m^2/sec$ in TW-1 well and $6.06\;{\times}\;10^{-6}\;m^2/sec$ in TW-2 well, and diffusion area was 1.18 times larger in TW-2 well.

Reduction and Equilibrium of Vanadium-Diethylenetriamine Pentaacetates at Mercury Electrode in Aqueous Solution (수용액중의 수은전극에서 바나듐-디에틸렌트리아민 펜타아세트산염의 환원 및 평형연구)

  • Ki-Suk Jung;Se Chul Sohn;Young Kyung Ha;Tae Yoon Eom;Sock Sung Yun
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.55-64
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    • 1989
  • Reduction and equilibrium of vanadium-DTPA (DTPA = diethylenetriaminepentaacetic acid, $H_5A$) complexes at mercury electrodes are studied in 0.5M $NaClO_4$ aqueous solution at 3.2 < pH < 10.5 and 25$^{\circ}$C. At 3.2 < pH < 5.9, the reduction reaction is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}HA^{2-}$, while at 5.9 < pH < 10.5 it is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}A^{3-}$. The stability constants of $V{\cdot}HA^{2-}$ and $V{\cdot}A^{3-}$ are found to be $6.46{\times}10^{9}$ and $3.09{\times}10^{14}$, respectively. V(IV)-DTPA undergoes stepwise complexation as $VO^{2+}+H_2A^{3-}=VO{\cdot}HA^{2+}H^{+}$ and $VO{\cdot}HA^{2-}=VO{\cdot}A^{3+}+H$, where acidity constant of $VO{\cdot}HA^{2-}$- is pKa = 7.15. Stability constants of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $1.41{\times}10^{14}$ and $3.80{\times}10^{17}$, respectively. It is detected that $VO^{2+}-DATA$ is reduced irreversibly to $VO^{2-}$ with the transfer coefficient of $\alpha$ = 0.43. At more cathodic overpotential, the reduction is stepwise as V(IV)${\to}$V(III)${\to}$V(II). The first one corresponds to $VO{\cdot}HA^{2-}+e^{-}{\to}VO{\cdot}HA{3+}$ at 3.2 < pH < 7.2 and $VO{\cdot}A^{3-}+e^{-}{\to}VO{\cdot}A^{4-}$ at 7.2 < pH < 10.5. The second is identical to that of V(III). Diffusion coefficients of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $(9.0{\pm}0.3){\times}10^{-6}cm^2/s$ and $(5.9{\pm}0.4){\times}10^{-6}cm^2/ses$, respectively.

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An Investigation of the Current Squeezing Effect through Measurement and Calculation of the Approach Curve in Scanning Ion Conductivity Microscopy (Scanning Ion Conductivity Microscopy의 Approach Curve에 대한 측정 및 계산을 통한 Current Squeezing 효과의 고찰)

  • Young-Seo Kim;Young-Jun Cho;Han-Kyun Shin;Hyun Park;Jung Han Kim;Hyo-Jong Lee
    • Journal of the Microelectronics and Packaging Society
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    • v.31 no.2
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    • pp.54-62
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    • 2024
  • SICM (Scanning Ion Conductivity Microscopy) is a technique for measuring surface topography in an environment where electrochemical reactions occur, by detecting changes in ion conductivity as a nanopipette tip approaches the sample. This study includes an investigation of the current response curve, known as the approach curve, according to the distance between the tip and the sample. First, a simulation analysis was conducted on the approach curves. Based on the simulation results, then, several measuring experiments were conducted concurrently to analyze the difference between the simulated and measured approach curves. The simulation analysis confirms that the current squeezing effect occurs as the distance between the tip and the sample approaches half the inner radius of the tip. However, through the calculations, the decrease in current density due to the simple reduction in ion channels was found to be much smaller compared to the current squeezing effect measured through actual experiments. This suggests that ion conductivity in nano-scale narrow channels does not simply follow the Nernst-Einstein relationship based on the diffusion coefficients, but also takes into account the fluidic hydrodynamic resistance at the interface created by the tip and the sample. It is expected that SICM can be combined with SECM (Scanning Electrochemical Microscopy) to overcome the limitations of SECM through consecutive measurement of the two techniques, thereby to strengthen the analysis of electrochemical surface reactivity. This could potentially provide groundbreaking help in understanding the local catalytic reactions in electroless plating and the behaviors of organic additives in electroplating for various kinds of patterns used in semiconductor damascene processes and packaging processes.