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).

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.

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.

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 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 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.

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 KNO₃ 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 KNO₃ solutions of different concentrations from 10^-3 to 10^-1M. The data are interpreted by the surface dissociation and complexation model of Davis, et als. and the modified model.

Theoretical Prediction of the Thermodynamic Properties of Liquid-Crystalline p-Azoxyanisole

도영규,전무식,이태규,Youngkyu Do,Mu Shik Jhon,Taikyue Ree Korean Chemical Society 1976 대한화학회지 Vol.20 No.2

액체에 대한 significant structure theory 와 상의 전이에 대한 Bragg-Williams근사를 사용하여 액정 화합물인 p-azoxyanisole의 열역학적 성질을 nematic phase와 isotropic phase의 온도범위에 걸쳐 계산하였다. Isotropic phase는 일반적인 액체로 보았으며 nematic phase는 액체적인 성질외에도 분자쌍극자의 배열에 의한 영향도 고려하였다. p-Azoxyanisole의 액체적인 성질은 significant structure theory로 기술하였으며 분자쌍극과 배열에 의한 영향은 Bragg-Williams 근사로써 고려하였다. 부피, 증기압, 정압비열, 열팽창계수, nematic-isotropic 전이점에서의 엔트로피 엔탈피 변화, 절대엔트로피, Helmholtz free energy등을 계산하여 실험치와 비교하였다. The significant structure theory of liquids and the Bragg-Williams approximation of phase transition theory have been applied to the calculation of the thermodynamic properties of p-azoxyanisole which exhibits a liquid crystal phase of the nematic type. The isotropic phase was treated as a normal liquid; and for the nematic phase, in addition to its liquidity, the effect due to the arrangement of molecular-dipoles was considered. The liquidity of the p-azoxyanisole was described by the significant structure theory of liquids, and the Bragg-Williams approximation was used to consider the effect due to the arrangement of molecular-dipoles. The molar volume, vapor pressure, heat capacity at constant pressure, thermal expansion coefficient, compressibility, entropy and enthalpy change at the nematic-isotropic phase transition point, absolute entropy, and absolute Helmholtz free energy were calculated over the temperature range of the nematic and isotropic phases. The calculated results of the thermodynamic properties were compared with the experimental data.

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.