• Title/Summary/Keyword: Arrhenius function

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Thermal cracking analysis of concrete with cement hydration model and equivalent age method

  • Tian, Ye;Jin, Xianyu;Jin, Nanguo
    • Computers and Concrete
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    • v.11 no.4
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    • pp.271-289
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    • 2013
  • In this research, a developed microstructural model of cement particles was presented to describe the cement hydration procedure. To simplify the hydration process, the whole hydration was analyzed in a series of sub-steps. In each step, the hydration degree, as well as the microstructural size of the hydration cell, was calculated as a function of the radius of the unreacted cement particles. With the consideration of the water consumption and the reduction of the interfacial area between water and hydration products, the micro-level expressions of the cement hydration kinetics were established. Then the heat released and temperature history of the concrete was carried out with the hydration degree obtained from each sub-steps. The equivalent age method based on the Arrhenius law was introduced in this research. Based on the equivalent age method, a maturity model was applied to describe the evolution of the mechanical properties of the material during the hydration process. The finite element program ANSYS was used to analyze the temperature field in concrete structures. Then thermal stress field was calculated using the elasticity modulus obtained from code formulate. And the risk of thermal cracking was estimated by the comparison of thermal stress and concrete tensile strength.

Temperature Dependence of Self-Diffusion of THO in Copolymer Hydrogel Membrane as a Function of Gel Compositions

  • Soon Hong Yuk;Sang Il Jeon;Mu Shik Jhon
    • Bulletin of the Korean Chemical Society
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    • v.5 no.3
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    • pp.104-108
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    • 1984
  • The self-diffusion experiment of THO was performed across a series of copolymer hydrogel membranes at different temperatures. Copolymer hydrogel membranes were prepared by copolymerizing 2-hydroxyethyl methacrylate (HEMA) and 2-aminoethyl methacrylate (AEMA) in the presence of the solvent and the crosslinker, ethylene glycol dimethacrylate (EGDMA). By changing the crosslinker content and the ratio of HEMA and AEMA monomer, two series of copolymer hydrogel membranes were synthesized. The tagging material was THO and efflux of THO was counted on a Liquid Sc-intillation Counter. The experimental data show that the permeability decreases as the amount of EGDMA and the mole fraction of HEMA increase, and the permeability is proportional to the temperature. The partition coefficient shows a parallel trend with permeability. Using the relationship between viscosity and diffusivity, the viscosity of water within the membrane was obtained. According to the result, the viscosity of watler within the membrane has the same value with those of supercooling water. And we obtained the activation energy of THO for transport in the membrane by using Arrhenius plotting.

An NMR Study on Complexation of Ortho-Xylyl-17-Crown-5 with $^{7}Li\;and\;^{23}Na$ Ions in Acetonitrile

  • 윤신영;안상두;이조웅
    • Bulletin of the Korean Chemical Society
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    • v.16 no.3
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    • pp.265-269
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    • 1995
  • Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

A Study on the Vulcanization Reaction of Modified NR Blends by In-Situ Electrical Property Measurement (전기적 특성의 in-situ 측정에 의한 개질된 NR 블랜드의 가황 반응에 관한 연구)

  • Ha, Ki-Ryong;Suh, Soong-Hyuck;Rho, Seung-Baik;Lee, Seung-Hyun;Ahn, Won-Sool
    • Elastomers and Composites
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    • v.38 no.3
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    • pp.235-242
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    • 2003
  • A vulcanization reaction characteristics of an isoprene rubber (IR)-modified natural rubber/carbon black (NR/CB) composite was studied using in-situ electrical property measuring technique. Since the electrical conductivity of the sample composite would be changed continuously during the vulcanization reaction by rearranging of the carbon black particles within the sample, volume resistivity (${\rho}$) might be obtained as a function or reaction time. A stabilization time ($t_i$), maximum reaction speed time ($t_p$), and volume resistivity at that time(${\rho}_p$) were defined from the data for the Arrhenius analysis. Volume resistivity ${\rho}$ showed a comparatively high value of ${\sim}10^8$ order before the reaction started, and dramatically decreased to be stabilized within $1{\sim}2$ minutes as soon as the reaction started. As the more time elapsed, thereafter, ${\rho}$ decreased monotonously to a certain constant value through a peak, ${\rho}_p$ at time $t_p$, which was considered as the maximum reaction rate. As a result, while $t_i$ values were comparatively constant as $1{\sim}2$ minutes, $t_p$ values showed to become shorter and shorter as the reaction temperature.

Mathematical Modelling of Phenol Desorption from Spent Activated Carbon by Acetone (활성탄에 흡착된 페놀의 아세톤 탈착 모델에 대한 연구)

  • Kim, Seungdo;Oh, Young-Jin
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.12
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    • pp.2115-2123
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    • 2000
  • This research was designed to investigate the mathematical model and kinetics of phenol desorption from spent activated carbon. elucidating the desorption characteristics of phenol in the case of using acetone. The Freundlich isotherm constant ($k_e$) is expressed as a function of temperature: $k_e(T)=0.1exp(797.297/T)$. The Freundlich isotherm constant(n) is a weak temperature function and is rarely affected by temperature below $50^{\circ}C$. whereas it is necessary to correct the n value with respect to temperature above $100^{\circ}C$ owing to significant deviation (~5%). Based on the assumption that the surface desorption reaction of phenol is rate limiting, the desorption model was developed. Desorption reaction constant($k_d$) was determined by means of fitting the theoretical results best to experimental ones. The Arrhenius relationships for $k_d$ was expressed by: $k_d(sec^{-1})=0.0479{\cdot}exp(-3037/T)$. The model was verified by comparing the experimental ones under different reaction conditions with the theoretical results determined by the previously estimated $k_d$. Since the difference between them is with 5%, it is expected that the desorption model of this research seems to be appropriate to explain the desorption of phenol from activated carbon by acetone. According to studies of the model. regeneration time and ratio was estimated as a function of temperature under present conditions as follows: (1) regeneration time : ${\tau}_{reg}(hr)=-0.08130T_c+8.4775$. (2) regeneration ratio : ${\eta}(%)=0.2210T_c+83.745$. The regeneration time at 15, 55, and $100^{\circ}C$. respectively. was 7, 4.2, and 0.35 hours, whereas the regeneration ratio was 87. 96. and 99%. respectively. Also. studies of the model would make it possible to determine the regeneration time and ratio under other specific conditions (temperature, applied acetone volume, amount of activated carbon, and initially adsorbed phenol amount).

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Size Distribution and Temperature Dependence of Magnetic Anisotropy Constant in Ferrite Nanoparticles

  • Yoon, Sunghyun
    • Proceedings of the Korean Magnestics Society Conference
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    • 2012.11a
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    • pp.104-105
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    • 2012
  • The temperature dependence of the effective magnetic anisotropy constant K(T) of ferrite nanoparticles is obtained based on the measurements of SQUID magnetometry. For this end, a very simple but intuitive and direct method for determining the temperature dependence of anisotropy constant K(T) in nanoparticles is introduced in this study. The anisotropy constant at a given temperature is determined by associating the particle size distribution f(r) with the anisotropy energy barrier distribution $f_A(T)$. In order to estimate the particle size distribution f(r), the first quadrant part of the hysteresis loop is fitted to the classical Langevin function weight-averaged with the log?normal distribution, slightly modified from the original Chantrell's distribution function. In order to get an anisotropy energy barrier distribution $f_A(T)$, the temperature dependence of magnetization decay $M_{TD}$ of the sample is measured. For this measurement, the sample is cooled from room temperature to 5 K in a magnetic field of 100 G. Then the applied field is turned off and the remanent magnetization is measured on stepwise increasing the temperature. And the energy barrier distribution $f_A(T)$ is obtained by differentiating the magnetization decay curve at any temperature. It decreases with increasing temperature and finally vanishes when all the particles in the sample are unblocked. As a next step, a relation between r and $T_B$ is determined from the particle size distribution f(r) and the anisotropy energy barrier distribution $f_A(T)$. Under the simple assumption that the superparamagnetic fraction of cumulative area in particle size distribution at a temperature is equal to the fraction of anisotropy energy barrier overcome at that temperature in the anisotropy energy barrier distribution, we can get a relation between r and $T_B$, from which the temperature dependence of the magnetic anisotropy constant was determined, as is represented in the inset of Fig. 1. Substituting the values of r and $T_B$ into the $N{\acute{e}}el$-Arrhenius equation with the attempt time fixed to $10^{-9}s$ and measuring time being 100 s which is suitable for conventional magnetic measurement, the anisotropy constant K(T) is estimated as a function of temperature (Fig. 1). As an example, the resultant effective magnetic anisotropy constant K(T) of manganese ferrite decreases with increasing temperature from $8.5{\times}10^4J/m^3$ at 5 K to $0.35{\times}10^4J/m^3$ at 125 K. The reported value for K in the literatures is $0.25{\times}10^4J/m^3$. The anisotropy constant at low temperature region is far more than one order of magnitude larger than that at 125 K, indicative of the effects of inter?particle interaction, which is more pronounced for smaller particles.

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Electric Conduction Mechanisms Study within Zr Doped Mn3O4 Hausmannite Thin Films through an Oxidation Process in Air

  • Said, L. Ben;Boughalmi, R.;Inoubli, A.;Amlouk, M.
    • Applied Microscopy
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    • v.47 no.3
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    • pp.131-147
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    • 2017
  • In this work further optical and electrical investigations of pure and Zr doped $Mn_3O_4$ (from 0 up to 20 at.%) thin films as a function of frequency. First, the refractive index, the extinction coefficient and the dielectric constants in terms of Zr content are reached from transmittance and reflectance data. The dispersion of the refractive index is discussed by means of Cauchy model and Wemple and DiDomenico single oscillator models. By exploiting these results, it was possible to estimate the plasma pulse ${\omega}_p$, the relaxation time ${\tau}$ and the dielectric constant ${\varepsilon}_{\infty}$. Second, we have performed original ac and dc conductivity studies inspired from Jonscher model and Arrhenius law. These studies helped establishing significant correlation between temperature, activation energy and Zr content. From the spectroscopy impedance analysis, we investigated the frequency relaxation phenomenon and hopping mechanisms of such thin films. Moreover, a special emphasis has been putted on the effect of the oxidation in air of hausmannite thin films to form $Mn_2O_3$ ones at $350^{\circ}C$. This intrigue phenomenon which occurred at such temperature is discussed along with this electrical study. Finally, all results have been discussed in terms of the thermal activation energies which were determined with two methods for both undoped and Zr doped $Mn_3O_4$ thin films in two temperature ranges.

Kinetics of Lipid Oxidation in Dried Fish Meat Stored under Different Conditions of Water Activity and Temperature (건어육 저장중의 온도와 수분활성에 따른 지방의 산화속도)

  • YOU Beoyng-Jin;LEE Kang-Ho
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.15 no.1
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    • pp.83-93
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    • 1982
  • In this work, lipid oxidation and the kinetics of the oxidation reaction in fried file-fish meat were investigated when sun-dried file-fish was stored under the conditions of various water activities and temperature, 35, 45, 55 and $35/55^{\circ}C$. The storage stability and the development of browning by oxidative rancidity were also discussed. Monolayer coverage value of water content in dried file-fish was $8.03\%$ at $0.21\;a_w$Lipid oxidation at $35^{\circ}C$ was developed with increasing water activity but at $45^{\circ}C$and $55^{\circ}C$ it was rapidly progressed without clear differences between water activities except $0.44\;a_w$. The rate of reaction was more sensitive to storage temperature than to water activity. Browning in methanol-chloroform fraction was developed linearly by the progress of lipid oxidation which suggested that lipid oxidation was greatly influential to the development of browning in dried fish meat. In kinetical analysis the oxidation followed a zero order reaction mechanism as a function of carbonyl value. The activation energies obtained from the Arrhenius plot ranged 9.0 to 10.8 Kcal/mol and $Q_10$ values, 1.6-1.7. Shelf-lives at the storage of 35,45 and $55^{\circ}C$ ranged 58 days to 8 days. And in the fluctuating temperature storage at $35/55^{\circ}C$, shelf-lives were 17, 16, 15 and 13 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively. The shelf-lives for assessed from the accelerated shelf-life test were 125, 123, 120 and 106 days at 0.44, 0.52, 0.65 and $0.75\;a_w$, respectively, in the case of storage at $25^{\circ}C$.

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Rheological Properties and Cure Kinetics of Cycloaliphatic/DGEBA Epoxy Blend System Initiated by Cationic Latent Curing Agent (잠재성 경화제를 이용한 Cycloaliphatic/DGEBA계 에폭시 블렌드 시스템의 유변학적 특성 및 경화 동력학)

  • 곽근호;박수진;이재락;김영근
    • The Korean Journal of Rheology
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    • v.10 no.4
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    • pp.227-233
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    • 1998
  • The effects of 1 mol% N-benzylpyrazinium hexafluoroantimonate(BPH) as a thermal latent initiator and blend compositions composed of cycloaliphatic and DGEBA epoxies were investigated in the rheological properties and cure kinetics. Latent properties were performed by measurement of the conversion as a function of reaction time using isothermal DSC at $150^{\circ}C$ and $50^{\circ}C$ Rheological properties of the blend systems were investigated in terms of isothermal experiments using a rheometer. The gelation time was obtained from the evaluation of storage modulus (G'), loss modulus (G") and damping factor (tan$\delta$)). Cross-linking activation energy ($E_c$) was also determined from the Arrhenius equation based on gel time and curing temperature. As a result, the gel time and cross-linking activation energy increased with increasing DGEBA composition. The cure activation energies ($E_a$) were obtained by Kissinger method using dynamic DSC thermograms. In this work, the cure activation energy decreased with increasing CAE concentration, which might be resulted from the short repeat units, simple side-groups and viscosity of reaction media.edia.

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Kinetics of Pyrolysis Degradation of Cured Phenol Resin (SC-1008) (I). (경화된 페놀 수지 (SC-1008)의 열분해 반응에 관한 연구(I).)

  • 김연철;강희철;예병한;배주찬
    • Proceedings of the Korean Society of Propulsion Engineers Conference
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    • 1996.11a
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    • pp.137-144
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    • 1996
  • The kinetic coefficients far decomposition of the cured phenol resin (SC-1008) using a modified Arrhenius relationship have been determined from thermogavimetric analyses (TGA). The kinetic parameters were determined by multiple heating rate technique developed by Freideman and Henderson. Weight loss (decomposition) and weight loss rate (decomposition rate)were measured and recorded for three heating rates; $5^{\circ}C$/min ,$10^{\circ}C$/min, and $20^{\circ}C$/min. Relatively good agreement was obtained between measured and calculated decomposition as a function of temperature. By separating the reaction, the reaction order and pre exponential factor become empirical parameters which provide a "best fit" of the data. However, this method yields an extremely accurate reproduction of the thermograms over a wide range of heating rates. This is the desired result for kinetic parameters used in thermal models.al models.

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