• Title/Summary/Keyword: Arrhenius plots

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Life-time Prediction of a FKM O-ring using Intermittent Compression Stress Relaxation (CSR) and Time-temperature Superposition (TTS) Principle (간헐 압축응력 완화와 시간-온도 중첩 원리를 이용한 FKM 오링의 수명 예측 연구)

  • Lee, Jin-Hyok;Bae, Jong-Woo;Kim, Jung-Su;Hwang, Tae-Jun;Park, Sung-Doo;Park, Sung-Han;Min, Yeo-Tae;Kim, Won-Ho;Jo, Nam-Ju
    • Elastomers and Composites
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    • v.45 no.4
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    • pp.263-271
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    • 2010
  • Intermittent CSR testing was used to investigate the degradation of an FKM O-ring, also the prediction of its life-time. An intermittent CSR jig was designed taking into consideration the O-ring's environment under use. The testing allowed observation of the effects of friction, heat loss, and stress relaxation by the Mullins effect. Degradation of O-rings by thermal aging was observed between 60 and $160^{\circ}C$. In the high temperature of range ($100-160^{\circ}C$) O-rings showed linear degradation behavior and satisfied the Arrhenius relationship. The activation energy was about 60.2 kJ/mol. From Arrhenius plots, predicted life-times were 43.3 years and 69.9 years for 50% and 40% failure conditions, respectively. Based on TTS (time-temperature superposition) principle, degradation was observed at $60^{\circ}C$, and could save testing time. Between 60 and $100^{\circ}C$ the activation energy decreased to 48.3 kJ/mol. WLF(William-Landel-Ferry) plot confirmed that O-rings show non-linear degradation behavior under $80^{\circ}C$. The life-time of O-rings predicted by TTS principle was 19.1 years and 25.2 years for each failure condition. The life-time predicted by TTS principle is more conservative than that from the Arrhenius relationship.

Influence of Temperature on Chloride Ion Diffusion of Concrete (콘크리트의 염화물이온 확산성상에 미치는 온도의 영향)

  • So, Hyoung-Seok;Choi, Seung-Hoon;Seo, Chung-Seok;Seo, Ki-Seog;So, Seung-Young
    • Journal of the Korea Concrete Institute
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    • v.26 no.1
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    • pp.71-78
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    • 2014
  • The long term integrity of concrete cask is very important for spent nuclear fuel dry storage system. However, there are serious concerns about early deterioration of concrete cask from creaking and corrosion of reinforcing steel by chloride ion because the cask is usually located in seaside, expecially by combined deterioration such as chloride ion and heat, carbonation. This study is to investigate the relation between temperature and chloride ion diffusion of concrete. Immersion tests using 3.5% NaCl solution that were controlled in four level of temperature, i.e. 20, 40, 65, and $90^{\circ}C$, were conducted for four months. The chloride ion diffusion coefficient of concrete was predicted based on the results of profiles of Cl- ion concentration with the depth direction of concrete specimens using the method of potentiometric titration by $AgNO_3$. Test results indicate that the diffusion coefficient of chloride ion increases remarkably with increasing temperature, and there was a linear relation between the natural logarithm values of the diffusion coefficients and the reciprocal of the temperature from the Arrhenius plots. Activation energy of concrete in this study was about 46.6 (W/C = 40%), 41.7 (W/C = 50%), 30.7 (W/C = 60%) kJ/mol under a temperature of up to $90^{\circ}C$, and concrete with lower water-cement ratio has a tendency towards having higher temperature dependency.

Separation Characteristics of $CH_4/CO_2$ Mixed Gas by Polyamide Composite Membrane (Polyamide 복합막을 이용한 메탄/이산화탄소 혼합기체의 분리 특성)

  • Lee, Jae-Hwa;Lee, Geon-Ho;Choi, Kyung-Seok;Poudel, Jeeban;Kim, Soo-Ryong;Oh, Sea-Cheon
    • Journal of the Korean Applied Science and Technology
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    • v.29 no.3
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    • pp.478-485
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    • 2012
  • Polymers are widely used as membrane material for performing the separation of various gaseous mixtures due to their attractive permselective properties and high processability. The separation characteristics of $CH_4$ and $CO_2$ mixed gas using polyamide composite membrane has been studied in this work. The sample gas was prepared by mixing pure methane and carbon dioxide. Permeation tests were carried out at different operation conditions. Feed flow rates were varied between 800~1000 $cm^3/min$, and the stage cuts were varied between 50~60%. The gas inlet pressure and the temperature were varied as 6 bar and $30{\sim}70^{\circ}C$, respectively. The effects of the above mentioned parameters were investigated to estimate the permeability of $CH_4$ and $CO_2$, and the selectivity of $CO_2$ was also calculated for all conditions. The Arrhenius plots were also performed to obtaine the activation energies of $CH_4$ and $CO_2$ permeabilities.

Chemical Reaction of Solvated Electrons in Binary Mixture (이성분계 $(THF-H_2O)$에서 용매화전자의 화학반응속도)

  • Yu-Chul Park
    • Journal of the Korean Chemical Society
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    • v.27 no.3
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    • pp.201-207
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    • 1983
  • The rate constants for solvated electrons with benzene in the binary mixture (tetrahydrofuran-water) were measured at a various temperatures$(-18{\circ}C{\sim}+51{\circ}C)$ by photolysis. From Arrhenius plots of rate constants it was observed that the activation energies were decreased with increasing tetrahydrofuran(THF) content. Decreasing the viscosity of solvent mixtures by adding water, the rate constants were also decreased. It indicates that the reaction of solvated electrons are not controlled by diffusion. The change of activation enthalpy in kcal $M^{-1}$ and the rate constants in$ M^{-1}sec^{-1}$ were 4.90 and $8.80{\times}10^8$ for 30M% of THF, 2.80 and $5.14{\times}10^8$ for 49M% of THF, and -0.30 and %1.43{\times}10^8$ for 75M% of THF, respectively. The slope of the linear plot of activation enthalpies against activation entropies was $244{\circ}K$, which supports the reaction parameter is the change of activation entropy in the range of the experimental temperature. From the solvent effect on the activation energy, it was found that the step of the reaction, ${e_s}^-+B{\rightleftharpoons}B^-$ shifted to the exothermic reaction with increasing THF content.

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Purification and Characterization of Cellulolytic Enzymes from Aspergillus niger (Aspergillus niger가 생산(生産)하는 섬유소(纖維素) 분해효소(分解酵素)의 정제(精製) 및 특성(特性))

  • Park, Kwan-Hwa;Oh, Tae-Kwang;Shin, Jae-Doo
    • Applied Biological Chemistry
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    • v.24 no.3
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    • pp.186-193
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    • 1981
  • Three fractions of carboxymethyl-cellulase (F-I, F-II, and F-III) and ${\beta}-glucosidase$ form Aspergillus niger were partially purified by ammonium sulfate fractionation. Sephadex G-150 and DEAE-Sephadex column chromatography. The optimum conditions such as pH and temperature and thermal inactivation properties of the enzymes were investigated. Arrhenius plots of F-II and F-III appeared as straight lines, whereas that of F-I was biphasic. The Z-values of F-II and F-III were $8^{\circ}C$ and $10^{\circ}C$ respectively, while that of F-I was $4^{\circ}C$ over $60{\sim}70^{\circ}C$ and $383^{\circ}C$ over $70{\sim}98^{\circ}C$. Three fractions and the crude extract of carboxymethyl-cellulase exhibited a similar optimum pH 4.3 and temperature of $60^{\circ}C$, while Z-value of crude extract $(21.5^{\circ}C)$ was much higher than that of the purified enzyme. Maximum activity of both purified and crude extract of ${\beta}-glucosidase$ was shown at pH 4.7 and $60^{\circ}C$, and z-value of the enzyme was $7^{\circ}C$.

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N-Oxidation of Pyrazines by Bromamine-B in Perchloric Acid Medium: Kinetic and Mechanistic Approach

  • Puttaswamy;Shubha, J.P.
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.1939-1945
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    • 2009
  • Kinetic investigations on the oxidation of pyrazine and four 2-substituted pyrazines viz., 2-methylpyrazine, 2-ethylpyrazine, 2-methoxypyrazine and 2-aminopyrazine by bromamine-B (BAB) to the respective N-oxides have been studied in HCl$O_4$ medium at 303 K. The reactions show identical kinetics being first-order each in $[BAB]_o\;and\;[pyrazine]_o$, and a fractional- order dependence on $[H^+]$. Effect of ionic strength of the medium and addition of benzenesulfonamide or halide ions showed no significant effect on the reaction rate. The dielectric effect is positive. The solvent isotope effect was studied using $D_2$O. The reaction has been studied at different temperatures and activation parameters for the composite reaction have been evaluated from the Arrhenius plots. The reaction showed 1:1 stoichiometry and the oxidation products of pyrazines were characterized as their respective N-oxides. Under comparable experimental conditions, the oxidation rate of pyrazines increased in the order: 2-aminopyrazine > 2-methoxypyrazine > 2-ethylpyrazine > 2-methylpyrazine > pyrazine. The rates correlate with the Hammett $\sigma$ relationship and the reaction constant $\rho$ was found to be -0.8, indicating that electron donating centres enhance the rate of reaction. An isokinetic temperature of $\beta$ = 333 K, indicated that the reaction was enthalpy controlled. A mechanism consistent with the experimental results has been proposed in which the rate determining step is the formation of an intermediate complex between the substrate and the diprotonated species of the oxidant. The related rate law in consistent with observed results has been deduced.

NOx Gas Detection Characterization with Vgs in the MWCNT Gas Sensor of MOS-FET Type (MOS-FET구조의 MWCNT 가스센서에서 Vgs의 변화에 따른 NOx 가스 검출 특성)

  • Kim, Hyun-Soo;Park, Yong-Seo;Jang, Kyung-Uk
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.27 no.4
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    • pp.257-261
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    • 2014
  • Carbon nanotubes (CNT) has the excellent physical characteristics in the sensor, medicine, manufacturing and energy fields, and it has been studied in those fields for the several years. We fabricated the NOx gas sensors of MOS-FET type using the MWCNT. The fabricated sensor was used to detect the NOx gas for the variation of $V_{gs}$ (gate-source voltage) with the ambient temperature. The gas sensor absorbed the NOx gas molecules showed the decrease of resistance, and the sensitivity of sensor was reduced by the NOx gas molecules accumulated on the MWCNT surface. Furthermore, when the voltage ($V_{gs}$) was applied to the gas sensor, the term of the decrease in resistance was increased. On the other hand, the sensor sensitivity for the injection of NOx gas was the highest value at the ambient temperature of $40^{\circ}C$. We also obtained the adsorption energy ($40^{\circ}C$) using the Arrhenius plots by the reduction of resistance due to the $V_{gs}$ voltage variations. As a result, we obtained that the adsorption energy also was increased with the increasement of the applied $V_{gs}$ voltages.

Detection Characteristics for the Ultra Lean NOx Gas Concentration Using the MWCNT Gas Sensor Structured with MOS-FET (MOS-FET 구조의 MWCNT 가스센서를 이용한 초희박 NOx 가스 검출 특성)

  • Kim, Hyun-Soo;Lee, Seung-Hun;Jang, Kyung-Uk
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.26 no.9
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    • pp.707-711
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    • 2013
  • Carbon nanotubes(CNT) has strength and chemical stability, greatly conductivity characteristics. In particular, MWCNT (multi-walled carbon nanotubes) show rapidly resistance sensitive for changes in the ambient gas, and therefore they are ideal materials to gas sensor. So, we fabricated NOx gas sensors structured MOS-FET using MWCNT (multi-walled carbon nanotubes) material. We investigate the change resistance of NOx gas sensors based on MOS-FET with ultra lean NOx gas concentrations absorption. And NOx gas sensors show sensitivity on the change of gate-source voltage ($V_{gs}=0[V]$ or $V_{gs}=3.5[V]$). The gas sensors show the increase of sensitivity with increasing the temperature (largest value at $40^{\circ}C$). On the other hand, the sensitivity of sensors decreased with increasing of NOx gas concentration. In addition, We obtained the adsorption energy($U_a$), $U_a$ = 0.06714[eV] at the NOx gas concentration of 8[ppm], $U_a$ = 0.06769[eV] at 16[ppm], $U_a$ = 0.06847[eV] at 24[ppm] and $U_a$ = 0.06842[eV] at 32[ppm], of NOx gas molecules concentration on the MWCNT gas sensors surface with using the Arrhenius plots. As a result, the saturation phenomena is occurred by NOx gas injection of concentration for 32[ppm].

Catalytic Reduction of Nitric Oxide in Oxygen-Rich Exhaust with Methanol over $La_2O_3$ Catalysts (메탄올을 환원제로 사용하는 과잉산소 분위기에서 $La_2O_3$ 촉매를 이용한 NO의 환원에 관한 연구)

  • Kim, Sang-Hwan;Yoo, Hyun-Ju;Park, Jung-Kyu
    • Transactions of the Korean Society of Automotive Engineers
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    • v.13 no.2
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    • pp.135-141
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    • 2005
  • Nitric oxide(NO) reduction by methanol was investigated over $La_2O_3$ catalysts in the presence and absence of oxygen. In the absence of $O_2$, $CH_3OH$ reduced NO to both $N_2$ and $N_2O$, with selectivity to $N_2$ formation decreasing from 81-88% at 623K to 47-71% at 723 K. With 1.2% $O_2$ in the feed, the rates were 4-8 times higher, but the selectivity to $N_2$ dropped from 50% at 623 K to 9% at 723 K. The specific activities with $La_2O_3$ for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of $34\;{\mu}mol\;NO/sec{\cdot}m^2$ was obtained whereas that for methanol was $638\;{\mu}mol\;NO/sec{\cdot}m^2$. The Arrhenius plots were linear under differential reaction conditions, and the apparant activation energy was consistantly near 15 kcal/mol with $CH_3OH$. Linear partial pressure dependencies based on a power rate law were obtained and showed a near-zero order in $CH_3OH$ and a near-first order in $H_2$.

Modeling for Drying of Thin Layer of Native Cassava Starch in Tray Dryer

  • Aviara, Ndubisi A.;Igbeka, Joseph C.
    • Journal of Biosystems Engineering
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    • v.41 no.4
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    • pp.342-356
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    • 2016
  • Purpose: The drying of a thin layer of native cassava starch in a tray dryer was modeled to establish an equation for predicting the drying behavior under given conditions. Methods: Drying tests were performed using samples of native cassava starch over a temperature range of $40-60^{\circ}C$. We investigated the variation in the drying time, dynamic equilibrium moisture content, drying rate period, critical moisture content, and effective diffusivity of the starch with temperature. The starch diffusion coefficient and drying activation energy were determined. A modification of the model developed by Hii et al. was devised and tested alongside fourteen other models. Results: For starch with an initial moisture content of 82% (db), the drying time and dynamic equilibrium moisture content decreased as the temperature increased. The constant drying rate phase preceded the falling rate phase between $40-55^{\circ}C$. Drying at $60^{\circ}C$ occurred only in the falling rate phase. The critical moisture content was observed in the $40-55^{\circ}C$ range and increased with the temperature. The effective diffusivity of the starch increased as the drying temperature increased from 40 to $60^{\circ}C$. The modified Hii et al. model produced randomized residual plots, the highest $R^2$, and the lowest standard error of estimates. Conclusions: Drying time decreased linearly with an increase in the temperature, while the decrease in the moisture content was linear between $40-55^{\circ}C$. The constant drying rate phase occurred without any period of induction over a temperature range of $40-55^{\circ}C$ prior to the falling rate period, while drying at $60^{\circ}C$ took place only in the falling rate phase. The effective diffusivity had an Arrhenius relationship with the temperature. The modified Hii et al. model proved to be optimum for predicting the drying behavior of the starch in the tray dryer.