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Ettect of Electrolytes on Flow Properties of Aqueous Bentonite Suspension
Kisoon Park,Taikyue Ree,Henry Eyring Korean Chemical Society 1971 대한화학회지 Vol.15 No.6
Dependence of the flow behavior of aqueous suspension of Black Hills bentonite on the concentration and the types of electrolytes was stydied. The flow properties were measured with a Couette-type totational viscometer. On addition of monovalent cations, the apparent viscosity determined from the reproducible flow curves (shear rate vs. shear stress) decreased followed by a rise as the ionic concentration further increased. Addition of multivalent cations (di- and tri-) resulted in the viscosity which increased to a maximum then decreased to a constant value. Anions of different chatges produced essentially the same relationship between viscosity and electrolyte concentration. The flow behavior of the electrolyte-containing suspensions was rationalized in terms of the Derjaguin-Landau-Verwey-Overbeek theory of colloidal stability and the generalized theory of viscosity.
Kinitics of Thixotropy of Aqueous Bentonite Suspension
Kisoon Park,Taikyue Ree Korean Chemical Society 1971 대한화학회지 Vol.15 No.6
The theological properties of aqueous suspensions of Black Hills bentonite were measured by using a Couette-type viscometer. Three kinds of flow units in aqueous bentonite suspension were postulated. Each has a different average relaxation time, one Newtonian. One of the non-Newtonian types is thixotropic, and the other is non-thixotropic. The thixotropic non-Newtonian unit is transformed to a Newtonian unit by shear stress. If the stress is relieved, the transformed unit returns to its original state. Two flow equations were derived by introducing chemical kinetics consideration for such a transition into the generalized theory of viscous flow. One equation describes the "upcurve," a diagram of rate of sheat versus shear stress, obtained by increasing the rate of shear, and the other relates to the "downcurve" obtained by decreasing the shear rate. The equations satisfactorilly describe the experimental thixotropic hysteresis of bentonite suspensions. The equations also were successfully applied to the flow curves of the suspensions containing various amounts of monovalent electrolyte (KCI).
Significant Structure Theory of Physical Adsorption
Yun-liang Wang,Taikyue Ree,Henry Eyring Korean Chemical Society 1971 대한화학회지 Vol.15 No.5
A significant structure theory of monolayer physical adsorption is developed. The theory is tested with the adsorptions on graphite of gases Ar, $N_2$, $CHCl_3$, and $CCl_4$. A restricted rotation model is used for the polyatomic molecules $N_2$, $CHCl_3$, and $CCl_4$. The computed isotherms and heats of adsorption are in good agreement with experiment in all cases studied.
Molecular Dynamic Study of a Polymeric Solution (I). Chain-Length Effect
Lee Young Seek,Ree Taikyue Korean Chemical Society 1982 Bulletin of the Korean Chemical Society Vol.3 No.2
Dynamic and equilibrium structures of a polymer chain immersed in solvent molecules have been investigated by a molecular dynamic method. The calculation employs the Lennard-Jones potential function to represent the interactions between two solvent molecules (SS) and between a constituent particle (monomer unit) of the polymer chain and a solvent molecule (CS) as well as between two non-nearest neighbor constituent particles of the polymer chain (CC), while the chemical bond for nearest neighbor constituent particles was chosen to follow a harmonic oscillator potential law. The correlation function for the SS, CS and CC pairs, the end-to-end distance square and the radius of gyration square were calculated by varying the chain length (= 5, 10, 15, 20). The computed end-to-end distance square and the radius of gyration square were found to be in a fairly good agreement with the corresponding results from the random-flight model. Unlike earlier works, the present simulation rsesult shows that the autocorrelation function of radius of gyration square decays slower than that of the end-to-end distance square.
Molecular Theory of Plastic Deformation (II). Applications
김창홍,이태규,Kim, Chang Hong,Ree Taikyue Korean Chemical Society 1977 대한화학회지 Vol.21 No.5
소성변형에 대한 저자들의 이론(제1보)을 요업재료, 금속, 합금 및 단결정들에 적용하였다. 그 결과 다중 결정에서는 dislocation 운동과 grain boundary 운동이 실험조건에 따라 함께 또는 분리되어 나타나는 반면 단결정에서는 dislocation 운동만 나타났다. 유동식에 나타나는 파라미터$({\alpha}_{d1},\;1/{\beta}_{d1})와\;({\alpha}_{gj}/X_{gj},\;1/{\beta}_{gj})$ (j = 1 or 2) 및 활성화엔탈피 ${\Delta}H_{k1}^{\neq}$ (k = d 혹은 g)를 구하여 예측한 소성변형은 실험과 잘 일치함을 보았다. 여기서 첨자 d1는 첫번째의 dislocation 유동단위, gj는 j번째 grain boundary 유동단위를 나타낸다. 활성화엔탈피에 대하여 ${\Delta}H_{d1}^{\neq}$는 bulk의 자체확산에 대한 활성화엔탈피와 일치하고 ${\Delta}H_{g1}^{\neq}$는 grain boundary 자체확산에 대한 활성화엔탈피와 일치하였다. 이 사실은 저자들의 이론의 정당성을 보이고 있다. The authors' theory developed in the preceding Paper 1 was applied to plastic deformation of ceramics, metals, alloys and single crystals. For polycrystalline substances, the flow mechanisms due to dislocation movement and grain boundary movement appear together or separately according to the experimental conditions whereas for single crystals, only the mechanism of dislocation movement appears. The parameters appearing in the flow equations $({\alpha}_{d1},\;1/{\beta}_{d1})and\;({\alpha}_{gj}/X_{gj},\;1/{\beta}_{gj})$ (j = 1 or 2), and the activation enthalpies ${\Delta}H_{k1}^{\neq}$ (k = d or g) were determined and tabulated. Here, the subscript d1 indicates the first kind of dislocation flow units and gj expresses the jth kind of grain boundary flow units. The predictions of the theory were compared with experiment with good agreement. Concerning the activation enthalpies, it was found that ${\Delta}H_{d1}^{\neq}$ 〉{\Delta}H_{g1}^{\neq}$ and that the former agrees with the activation enthalpy for bulk self-diffusion whereas the latter agrees with the activation enthalpy for grain boundary self-diffusion. These facts support the adequacy of the authors' theory which is considered as a generalized theory of plastic deformation.
Molecular Theory of Superplastic Deformation
김창홍,이태규,Chang Hong Kim,Taikyue Lee Korean Chemical Society 1979 대한화학회지 Vol.23 No.4
소성변형에 대한 著者들의 이론을 초소성합금(Zn-Al eutectoid, A1-Cu, Pb-Sn, Sn-Bi, Mg-Al eutectics)에 적용하였다. 그 결과 초소성합금의 소성변형은 두 개의 grain boundary流動單位의 平行連結로 나타낼 수 있었다. 이 두 개의 流動單位는 流動式에 나타나는 parameter $X_{gj}/{\alpha}_{gj}$와 ${\beta}_{gj}$(j=1 혹온 2)로 表現할 수 있으며 이들을 實驗的으로 求할 수 있었다. 著者들의 流動式은 實驗과 잘 一致하였다. Strain rate sensitivity 對 -In(strain rate) 곡선을 이론으로 구한 결과 유동단위수만큼의 peak가 ${\beta}_{gj}$(j=1 or 2) 값에 따라 분리되어 나타났고 초소성의 조건도 ${beta}_{gj}$값에 의하여 결정됨을 알았다. ${\beta}_{gj}값의 粒子크기 依存性을 구하였고 온도변화에 따른 ${\beta}_{gj}$값 변화로부터 각 流動單位의 활성화엔탈피, ${\Delta}H_{gj}^{\neq}$도 구하였다. 그 결과 ${\Delta}H_{gj}^{\neq}$는 재료성분원소들의 grain boundary 자체확산에 의한 활성화엔탈피와 같이 나타났고 또 이들은 粒子 크기 증가에 마라 증가함을 보였다 The author's theory for plastic deformation was applied to superplastic alloys (Zn-Al eutectoid, Al-Cu, Pb-Sn, Sn-Bi, Mg-Al eutectics). The plastic deformation of the superplastic alloys could be described by two Maxwell models connected in parallel which represent two grain boundary flow units. The flow units are characterized by the two parameters $X_{gj}/{\alpha}_{gj}\;and\;{\beta}_{gj}$ (j=l or 2, g signifies the grain boundary) the values of which were obtained by applying our flow equation [Eq. (5)] to experiment. We confirmed that our flow equation describes the superplasticity very well. The curve of strain rate sensitivity m (=${\partial}\;In\;f/{\partial}\;In\;\dot{s})\;vs.\;-In\dot{s}$, where f and s are stress and strain rate, respectively, showed two peaks corresponding to flow unit gl and g2, the separation of the two peaks is determined by the difference between ${\beta}_{g1}\;and\;{\beta}_{g2}$. The condition of superplasticity is also determined by ${\beta}_{gj}$, which satisfies $\dot{s}_{mj}{\leqslant}1.53}{\beta}_{gj}$ [Eq.(13)], where $\dot{s}_{mj}$ is the s of the jth unit at the peak. The grain size dependence of ${\beta}_{gj}$ is described by $ln({\beta}_{gj})^{-1}$=alnx+b [Eq. (16)], where x is the grain size, and a and b are constants. The activation enthalpy for each flow unit, ${\Delta}H_{gj}^{\neq}$ was also determined from the temperature dependence of ${\beta}_{gj}$ which is proportional to the relaxation time of the j th unit. Since the superplasticity is determined by Eq. (13), and since ${\beta}_{gj}$ and ${\Delta}H_{gj}^{\neq}$ are related, we obtained the conclusion that superplasticity occurs in the system having small ${\Delta}H_{gj}^{\neq}$ values. The Aej values were equal to the activation enthalpies of grain boundary self-diffusion of the component atoms of the alloys, this accords with our proposed flow mechanism. The ${\Delta}H_{gj}^{\neq}$ value increases with grain size as expected from Eq. (16).
The Interfacial Properties of Ferrosoferric Oxide in Aqueous Potassium Nitrate Solution
심규식 ( Kyoo Shik Shim ),이태규 ( Taikyue Ree ) 대한화장품학회 1986 대한화장품학회지 Vol.12 No.1
The interfacial properties of ferrosoferric oxide suspended in aqueous KNO<sub>3</sub> solution are investigated by studying the zeta potentials and surface charge densities at 25°C. The zeta potentials are obtained by measuring the electrophoretic mobility and the surface charge densities by potentiometric titrations in the aqueous KNO<sub>3</sub> solutions of different concentrations from 10<sup>-3</sup> to 10<sup>-1</sup>M. The data are interpreted by the surface dissociation and complexation model of Davis, et als. and the modified model.
Molecular Theory of Plastic Deformation (I). Theory
김창홍,이태규,Kim Chang Hong,Ree Taikyue Korean Chemical Society 1977 대한화학회지 Vol.21 No.5
In order to elucidate the plastic deformation of solids, the following assumptions were made: (1) the plastic deformation of solids is classified into two main types, the one which is caused by dislocation movement and the other caused by grain boundary movement, each movement being restricted on a different shear surface, (2) the dislocation movement is expressed by a mechanical model of a parallel connection of various kinds of Maxwell dislocation flow units whereas the grain boundary movement is also expressed by a parallel connection of various kinds of Maxwell grain boundary flow units; the parallel connection in each type of movements indicates that all the flow units on each shear surface flow with the same shear rate, (3) the latter model for grain boundary movement is connected in series to the former for dislocation movement, this means physically that the applied stress distributes homogeneously in the flow system while the total strain rate distributes heterogeneously on the two types of shear planes (dislocation or grain boundary shear plane), (4) the movement of dislocation flow units and grain boundary units becomes possible when the atoms or molecules near the obstacles, which hinder the movement of flow units, diffuse away from the obstacles.Using the above assumptions in conjunction with the theory of rate processes, generalized equations of shear stress and shear rate for plastic deformation were derived. In this paper, four cases important in practice were considered.ted N${\cdot}{\cdot}{\cdot}$O hydrogen bond and the second of two normal N${\cdot}{\cdot}{\cdot}$O hydrogen bonds, both of which exist between the amino group and the perchlorate, groups. A p-phenylenediamine group is approximately planar within an experimental error and bonded to twelve perchlorates: ten perchlorates forming hydrogen bonds and two being contacted with the van der Waals forces. A perchlorate group is surrounded by six p-phenylenediamines and four perchlorates; among the six p-phenylenediamines, five of them are hydrogen-bonded, and the rest contacted with the van der Waals force. 고체의 소성변형을 설명하기 위하여 다음과 같은 가정을 하였다. (1) 고체의 소성변형은 크게 두 가지 기구 즉 dislocation 운동과 grain boundary 운동에 의하여 일어난다. (2) Dislocation 운동에 있어서 유동 단위들은 역학적 모형으로 나타내면 다종의 Maxwell 단위들의 평행연결형으로 되고 grain boundary 유동단위들도 다종의 Maxwell 단위들의 평행연결로 표현된다. 이를 물리적으로 설명하면 같은 부류의 유동단위들은 모두 같은 shear plane에서 같은 shear rate로 흐름을 의미한다. (3) Grain boundary 유동단위들과 dislocation 유동단위들 같은 서로 직렬 연결되어 있다. 이는 물리적으로 고체내에서 stress는 균일하게 작용하나 shear rate는 shear plane 의 종류(dislocation 운동면과 grain boundary 운동면)에 따라 달리 나타남을 의미한다. (4) Dislocation 유동단위들과 grain boundary 운동단위들의 운동은 그들의 흐름을 방해하는 장애물 근방의 원자 또는 분자들이 확산해 나가므로써 가능하게 된다. 이러한 가정하에 반응속도론을 적용하여 shear rate와 shear stress를 구하는 일반식을 도출하였다. 본 연구에서는 실제로 중요한 네가지 경우에 대하여 상기 도출한 일반식을 고찰하였다.
A Study for the Viscous Flow of Sodium Chloride Through a Cuprophane Membrane
Jee Jong-Gi,Kwun Oh Cheun,Jhon Mu Shik,Ree Taikyue Korean Chemical Society 1982 Bulletin of the Korean Chemical Society Vol.3 No.1
For the study of transport phenomena of an aqueous NaCl solution through a cuprophane membrane, a new apparatus was constructed. The volumc flow rate Q, the permeability coefficient U, and the permeability constant K were measured or determined by using this apparatus. The experimental temperature range was 5 to $35^{\circ}C$, and the applied pressure increments were 10 to 40 psi. By assuming that the cuprophane membrane is composed of n parallel cylindrical capillaries of circular cross-section and that the flow of the solution through the capillaries follows the Poiseulle law, the mean radius r of the capillaries and the number n of the latter in the membrane were evaluated. By using a reasonable assumption concerning the radius ${\eta}'$ of the species diffusing through the membrane, it was concluded that the contribution of the diffusive flow to the total flow rate Q is less than 10%. Thus, the Q was treated as the rate due to the viscous flow, and the viscosity ${\eta}_m$ of the solution in the membrane phase was evaluted, and it was found that ηm is nearly equal to ${\eta}_b$, the bulk viscosity of the solution. From this fact, it was concluded that in the capillaries, no change occurs in the physical state of the NaCl solution. The value of ( = 4.27 kcal/mole) and ${\Delta}Sm^{\neq}$(4.28 eu) were obtained for the viscous flow. A possible explanation was given.
Theoretical Calculation of Activity Coefficients of Liquid Mixtures
문대원,전무식,이태규,Moon Dae-Won,Jhon Mu Shik,Lee Taikyue Korean Chemical Society 1977 대한화학회지 Vol.21 No.6
액체이론(Significant Structure Theory)를 단원자 분자로부터 다원자 분자에 이르는 여러 액체혼합물에 적용하여 전 농도 범위에서 액체 혼합물의 활동도 계수를 계산했다. 단원자 분자계(Ar-Kr, Kr-Xe)와 이원자 분자계$(Ar-O_2,\;N_2-CO)$와 메탄-크립톤계의 액체혼합물의 활동도 계수는 ${\delta}E_s$ 수정 변수에 의해 좋은 결과를 얻었다. 아르곤-질소, 산소-질소, 그리고 메탄-프로판계에 대해서는 이 외에 ${\delta}$V, ${\delta}$n 수정 변수가 더 필요했다. Significant structure theory was applied to some liquid mixture systems ranging from simple monatomic molecule systems to polyatomic molecule systems, and the activity coefficients ${\gamma}$ of the liquid mixture systems were calculated over whole mole fractions using the following thermodynamic relation $RTln_{{\gamma}i} = (\frac{{\partial A}^E}{{\partial N}_i})_{T,V,N_i} $ where $A^E$ represents the excess Helmholtz free energy, and $N_i$ is the number of molecules of component i. The activity coefficients of the solutions such as monatomic molecule systems (Ar-Kr, Kr-Xe) and diatomic molecule systems $(Ar-O_2,\;N_2-CO)$ and $CH_4-Kr$ systems whose components have similar shapes for intermolecular potential curves were calculated successfully only with the ${\delta}E_s$, correction parameter for energy $E_s$, for mixture systems. For other systems such as $Ar-N_2,\;O_2-N_2\;and\;CH_4-C_3H_8$ whose components have dissimilar intermolecular potential curve shapes an additional correction parameters ${\delta}$V and even one more parameter ${\delta}$n were necessary [see Eqs.(10)∼(12)].