• Textile Coloration and Finishing
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• v.16 no.1
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• pp.48-52
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• 2004

Diffusion/penetration rates of finishing agents are not a major criterion in the design of low molecular weight finishing agents. However, in the case of polymeric finishing agents, high molecular weights result in large hydrodynamic volumes and diffusion/penetration of the finishing agent into the substrate may become a critical factor in the design of textile finishing agents. Thus the effect of the molecular weight of a model compound, polyethylene glycol, on its diffusion through a cellulose membrane or cotton fabric is studied. Diffusion experiments of polyethylene glycol of molecular weight 400, 1000, 2000, 4600, 8000, and 10000 through cellulose membrane or fabric was carried out in a glass U-tube diffusion apparatus and the half penetration times and the penetration coefficients were determined. Both the half penetration times and the penetration coefficients exhibited a significant change between molecular weight 2000 and 2500 as the molecular weight of polyethylene glycol increased, suggesting that there is a critical molecular weight above which diffusion/penetration becomes difficult. Based on this study on a model compound, it is suggested that polymeric textile finishing agents can be expected to exhibit similar behavior.

• Proceedings of the KSME Conference
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• 2003.04a
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• pp.1584-1589
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• 2003

This work applies the equilibrium molecular dynamics simulation method to study a Lennard-Jones liquid thin film suspended in the vapor and calculates diffusion coefficients by Green-Kubo equation derived from Einstein relationship. As a preliminary test, the diffusion coefficients of the pure argon fluid are calculated by equilibrium molecular dynamics simulation. It is found that the diffusion coefficients increase with decreasing the density and increasing the temperature. When both argon liquid and vapor phases are present, the effects of the system temperature on the diffusion coefficient are investigated. It can be seen that the diffusion coefficient significantly increases with the temperature of the system.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1697-1704
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• 2007

We present results for transport properties of diatomic fluids by isothermal-isobaric (NpT) equilibrium molecular dynamics (EMD) simulations using Green-Kubo and Einstein formulas. As the molecular elongation of diatomic molecules increases from the spherical monatomic molecule, the diffusion coefficient increases, indicating that longish shape molecules diffuse more than spherical molecules, and the rotational diffusion coefficients are almost the same in the statistical error since random rotation decreases. The calculated translational viscosity decreases with the molecular elongation of diatomic molecule within statistical error bar, while the rotational viscosity increases. The total thermal conductivity decreases as the molecular elongation increases. This result of thermal conductivity for diatomic molecules by EMD simulations is again inconsistent with the earlier results of those by non-equilibrium molecular dynamics (NEMD) simulations even though the missing terms related to rotational degree of freedom into the Green-Kubo and Einstein formulas with regard to the calculation of thermal conductivity for molecular fluids are included.

• Bulletin of the Korean Chemical Society
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• v.24 no.6
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• pp.843-852
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• 2003

We present a brief account of the theory of diffusion-influenced kinetics of reactions involving polymers. The review will be based on the recent contributions from the authors. Both intrapolymer and interpolymer reactions are considered, and the effects of various physical factors, such as the chain length, chain stiffness, and hydrodynamic interactions, are described within a unified theoretical framework.

• Proceedings of the Membrane Society of Korea Conference
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• 1997.10a
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• pp.27-30
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• 1997

1. Introduction : Molecular diffusion of small molecules in polymers plays an important role in many areas where polymers are acting as barriers, and in separation processes, such as selective diffusion. Different applications of polymers have different requirements on their transport properties. Therefore, reliable predictions of diffusion coefficients for small molecules in polymeric materials could be a useful tool to design appropriate materials. For many years, the theories based on free-volume concepts have been widely used to correlate and predict diffusion behavior in polymer/solvent systems. In the theory derived by Vrentas and Duda, the empty space between molecules that is available for molecular transport, referred to as hole free-volume, is being redistributed. Molecular transport will occur only when a free-volume of sufficient size appears adjacent to a molecule and the molecule has enough energy to jump into this void. The diffusive jump is considered complete when the void left behind is closed before the molecule returns to its original position. In this paper, the Vrentas-Duda free-volume theory is presented and the methods to estimate free-volume parameters for predicting polymer/ solvent diffusion coefficients are described in detail.

• Bulletin of the Korean Chemical Society
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• v.29 no.8
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• pp.1554-1560
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• 2008

The probe diffusion and friction constants of methyl yellow (MY) in liquid n-alkanes of increasing chain length were calculated by equilibrium molecular dynamics (MD) simulations at temperatures of 318, 418, 518 and 618 K. Lennard-Jones particles with masses of 225 and 114 g/mol are modeled for MY. We observed that the diffusion constant of the probe molecule follows a power law dependence on the molecular weight of nalkanes, DMY${\sim}M^{-\gamma}$ well. As the molecular weight of n-alkanes increases, the exponent $\gamma$ shows sharp transitions near n-dotriacontane ($C_{32}$) for the large probe molecule (MY2) at low temperatures of 318 and 418 K. For the small probe molecule (MY1) $D_{MY1}$ in $C_{12}$ to C80 at all the temperatures are always larger than Dself of n-alkanes and longer chain n-alkanes offer a reduced friction relative to the shorter chain n-alkanes, but this reduction in the microscopic friction for MY1 is not large enough to cause a transition in the power law exponent in the log-log plot of DMY1 vs M of n-alkane. For the large probe molecule (MY2) at high temperatures, the situation is very similar to that for MY1. At low temperatures and at low molecular weights of n-alkanes, $D_{MY2}$ are smaller than $D_{self}$ of n-alkanes due to the relatively large molecular size of MY2, and MY2 experiences the full shear viscosity of the medium. As the molecular weight of n-alkane increases, $D_{self}$ of n-alkanes decreases much faster than $D_{MY2}$ and at the higher molecular weights of n-alkane, MY2 diffuses faster than the solvent fluctuations. Therefore there is a large reduction of friction in longer chains compared to the shorter chains, which enhances the diffusion of MY2. The calculated friction constants of MY1 and MY2 in liquid n-alkanes supported these observations. We deem that this is the origin of the so-called“solventoligomer”transition.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2237-2242
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• 2011

Anomalous scaling behaviors such as significantly large growth exponent (${\beta}$) and small reciprocal of dynamic exponent (1/z) values for many molecular crystalline thin films have been reported. In this study, the variation of scaling exponent values and consequent growth behaviors of molecular thin films were more quantitatively analysed using a (1+1)-dimensional surface lateral diffusion model. From these simulations, influence of step edge barriers and grain boundaries of molecular thin films on the various scaling exponent values were elucidated. The simulation results for the scaling exponents were also well consistent with the experimental data for previously reported molecular thin film systems.

• Bulletin of the Korean Chemical Society
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• v.20 no.11
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• pp.1323-1328
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• 1999

Interdiffusion between two partially miscible polymers of similar chemical structures with different molecular weights is characterized theoretically by using the reptation model for the interdiffusion. This model provides more reliable results than the early Rouse model for same molecular weights, compared with the experiments. Furthermore, by introducing the molecular weight ratio R into the reptation model, we can see the dynamic effect of molecular weight on the diffusion behaviors of the asymmetric system. Near the critical point the diffusion behaviors of asymmetric binary polymer mixtures are well characterized by the interfacial width W(t), the mass transport M(t) for the different values of the Flory Χ parameter and different molecular weight ratios ofpolymers of the diffusion couple. These two quantities and composition profiles by this model give betteragreement with experiments.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.2158-2160
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• 2009

• Bulletin of the Korean Chemical Society
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• v.29 no.7
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• pp.1409-1411
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• 2008