• Title/Summary/Keyword: free volume

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Free Volume in polymers. Note I。 : Theoretical background

  • Consolati, G.;Pegoraro, M.;Zanderighi, L.
    • Korean Membrane Journal
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    • v.1 no.1
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    • pp.8-24
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    • 1999
  • free volume in polymers is defined as the difference of the specific volume and the volume which is not available for the particular molecular motion which is responsible or the process that is considered . Relations between free volume and viscosity free volume and diffusion coefficient are pre-sented both in the case of simple low molecular weight liquids and in the case of polymers. Molecular models and free volume models are reminded starting from the equilibrium state equation of Simha and Somcynski. The non equilibrium situations of specific volume of glass polymers below Tg are shown introducing different relaxation volume equations which involve different material's parameters and con-cept of the fictitious temperature. The diffusivity equations of Vrentas and Duda are introduced both for the glassy and rubbery states. The possibility of introducing time relaxation functions is also suggested. The importance of finding experimental evidences of the free volume is stressed. highlights of the free volume measurement methods are given in particular as to dilatometry photocromy fluorescence electron spin resonance small angle X-ray scattering positron annihilation spectroscopy.

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Prediction of PolymerSolvent Diffusion Coefficients Using Free-Volume Theory (자유부피이론을 이용한 고분자/용매 확산계수의 예측)

  • 홍성욱
    • 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.

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Estimation of the Lubricating Oil Rheology at High Pressure Based on Phase Diagram

  • Rahman, Md.Z.;Ohno, N.
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 2002.10b
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    • pp.85-86
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    • 2002
  • For rheology investigation of lubricating oils, first phase diagrams were made from determined free volume based on density measurements and the temperature-pressure relation was estimated using the expansion coefficient of free volume and the temperature-pressure relation of the viscoelastic transition point. Next, the authors proposed the density-pressure-temperature relation and the viscosity-pressure-temperature relation of the tested oils based on the free volume and the phase diagrams. Moreover, it was shown that the Ehrenfest equation or the gradient of the phase diagram is closely related to the expansion coefficient of free volume.

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Effect of Isothermal annealing on the Corrosion Resistance of an Amorphous Alloy (비정질 합금의 부식저항성에 미치는 열처리의 영향)

  • Shin, Sang-Soo;Lee, Chang-Myeon;Yang, Jae-Woong;Lee, Jae-Chul
    • Korean Journal of Metals and Materials
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    • v.46 no.2
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    • pp.53-57
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    • 2008
  • This study examined the role of excess free volume on the corrosion resistance of an amorphous alloy. Corrosion behaviors were monitored on the amorphous alloys, of which amount of free volume was controlled via the isothermal annealing below the glass transition temperature, using immersion tests and potentiodynamic polarization tests in HCl aqueous solutions. It was found that the corrosion resistance of the amorphous alloy is improved by reducing the amount of excess free volume. The possible reason explaining the experimental result was discussed from the viewpoint of the internal energy associated with the annihilation of excess free volume.

Free Volume Formation in Amorphous Alloys: a Molecular Dynamics Study (비정질 합금의 자유부피 생성기구: 분자동력학적 고찰)

  • Lee, Chang-Myeon;Park, Kyoung-Won;Lee, Byeong-Joo;Shim, Jae-Hyeok;Lee, Jae-Hoon;Lee, Jae-Chul
    • Korean Journal of Metals and Materials
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    • v.46 no.11
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    • pp.701-707
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    • 2008
  • This study examined the creation mechanism of free volume during homogeneous deformation induced by the elastostatic compression at room temperature. Experiments demonstrated that amorphous alloys subjected to the elastostatic compression underwent structural disordering, during which densely packed polyhedra breakdown to form new, loosely packed ones, resulting in the creation of excess free volume. A combination of experiments and molecular dynamics simulations are used to explore fundamental issues on how free volume is created during elastostatic compression.

The Study on Water Permeation Improvement of Disulfonated Poly(Arylene Ether Sulfone) Random Copolymers with High Free Volume (높은 자유부피를 가지는 Disulfonated poly(arylene ether sulfone) 랜덤 공중합체의 수투과도 향상에 관한 연구)

  • Kang, Seungkyu;Hwang, Kyungho
    • Membrane Journal
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    • v.22 no.5
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    • pp.352-358
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    • 2012
  • In this study, we found structure-property relationship for pressure retarded osmosis (PRO) membrane, between BPS-XX and BisA-XX having similar structure but different free volume. And this comparison was subdivided by controlling its sulfonation degree. BPS-XX and BisA-XX were prepared via a polycondensation reaction. The degree of sulfonation were 20 to 60 mol.%. And they were fabricated to membrane. Characteristics were analyzed to verify of free volume. And the results showed that increase of free volume normally lead to increase permeability and decrease selectivity in equivalent molecule structure. Finally, in the permeability-selectivity results, we conclude high permeability and selectivity membrane can be prepared by controlling molecular structure and free volume.

The Distribution of Residual Stresses in Quenched Plastic Parts including Fee Volume Theory (자유체적이론을 고려한 플라스틱의 급냉시 잔류응력의 분포)

  • 김종선
    • Proceedings of the Korean Society for Technology of Plasticity Conference
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    • 2000.04a
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    • pp.106-111
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    • 2000
  • The residual stresses in molded plastic parts can be divided into the flow induced residual stresses produced in flowing stages and the thermally induced residual stresses produced in cooling state. Reducing residual stresses in the final parts is one of the goals in recent study. The present study focused on comparing the predicted values for thermal residual stresses in freely and constrained quenched plastic plates with and without free volume theory. As a result the final residual stresses showed the opposite pattern in thickness direction. furthermore by applying free volume theory the predicted residual stress at the center showed about 50% of the values without free volume theory for constrained quenched case.

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A Study on the Prediction of Thermally-Induced Residual Stress and Birefringence in Quenched Polystyrene Plate Including Free Volume Theory (자유 체적이론을 고려한 급냉 폴리스티렌판에 발생하는 잔류응력과 복굴절 형성에 관한 연구)

  • Kim, Jong-Sun;Yoon, Kyung-Hwan
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.27 no.1
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    • pp.77-87
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    • 2003
  • The residual stress and birefringence in injection-molded plastic parts can be divided into the flow-induced residual stress and birefringence produced in flowing stage, the thermally-induced residual stress and birefringence produced in cooling stage. However, the physics involved in the generation of the thermally-induced residual stress and birefringence still remains to be understood. Because polymer experiences viscoelastic history near the glass-transition temperature it is hard to model the entire process. Volume relaxation phenomenon was included to predict the final thermally-induced residual stress and birefringence in quenched plastic parts more accurately. The present study focused on comparing the predicted values far thermally-induced residual stress and birefringence with and without volume relaxation behavior (or free volume theory) under free and constrained quenching conditions. As a result, tile residual stress remained as a tensile stress at the center and as a compressible stress near the surface for the free quenching cases. In contract the residual stress remained as a compressible stress at the center and as a tensile stress near the surface fur the constrained quenching cases. The residual birefringence remained as minus values at the center and as plus values near the surface for the free quenching cases. Interestingly the residual birefringence showed minus values in entire zone for the constrained quenching cases. In the prediction of birefringence only the case including free volume theory showed the correct result for the distribution of birefringence in thickness direction.

A VOLUME OF FLUID METHOD FOR FREE SURFACE FLOWS AROUND SHIP HULLS (선체주위 자유수면 유동 해석을 위한 VOF법 연구)

  • Park, I.R.
    • Journal of computational fluids engineering
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    • v.20 no.1
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    • pp.57-64
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    • 2015
  • This paper describes a volume of fluid(VOF) method, mRHRIC for the simulation of free surface flows around ship hulls and provides its validation against benchmark test cases. The VOF method is developed on the basis of RHRIC method developed by Park et al. that uses high resolution differencing schemes to algebraically preserve both the sharpness of interface and the boundedness of volume fraction. A finite volume method is used to solve the governing equations, while the realizable ${\kappa}-{\varepsilon}$ model is used for turbulence closure. The present numerical results of the resistance performance tests for DTMB5415 and KCS hull forms show a good agreement with available experimental data and those of other free surface methods.

FREE SURFACE FLOW COMPUTATION USING MOMENT-OF-FLUID AND STABILIZED FINITE ELEMENT METHOD (Moment-Of-Fluid (MOF) 방법과 Stabilized Finite Element 방법을 이용한 자유표면유동계산)

  • Ahn, H.T.
    • 한국전산유체공학회:학술대회논문집
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    • 2009.11a
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    • pp.228-230
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    • 2009
  • The moment-of-fluid (MOF) method is a new volume-tracking method that accurately treats evolving material interfaces. Based on the moment data (volume and centroid) for each material, the material interfaces are reconstructed with second-order spatial accuracy in a strictly conservative manner. The MOF method is coupled with a stabilized finite element incompressible Navier-Stokes solver for two fluids, namely water and air. The effectiveness of the MOF method is demonstrated with a free-surface dam-break problem.

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