• Title/Summary/Keyword: Non-fickian

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Evaluation of Moisture Sorption Characteristics in Polymer Material (고분자 소재에서 흡습 특성의 평가)

  • Park, Hee-Jin
    • Transactions of the Korean Society of Mechanical Engineers A
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    • v.36 no.11
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    • pp.1297-1303
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    • 2012
  • In this paper, the standard procedures for measuring the moisture sorption properties of thin polymeric materials such as polyethylene terephthalate (PET) by using the thermo-gravimetric method to characterize the moisture diffusion in the polymer are presented, and the sorption properties are quantified. The moisture diffusivity and solubility are characterized to investigate the effect of temperature and humidity on the moisture sorption properties according to the Arrhenius equation. The validation of the obtained sorption properties using thermogravimetry is discussed with the measured permeability based on Fickian diffusion. The nonlinear behavior of the concentration dependent moisture diffusion is investigated experimentally, and the nonlinearity is characterized numerically for the case of having an interface with an inorganic material such as a metal. The Fickian/Non-Fickian model based on the obtained moisture sorption properties is compared and discussed.

Generalized coupled non-Fickian/non-Fourierian diffusion-thermoelasticity analysis subjected to shock loading using analytical method

  • Hosseini, Seyed Amin;Abolbashari, Mohammad Hossein;Hosseini, Seyed Mahmoud
    • Structural Engineering and Mechanics
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    • v.60 no.3
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    • pp.529-545
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    • 2016
  • In this article, the generalized coupled non-Fickian diffusion-thermoelasticity analysis is carried out using an analytical method. The transient behaviors of field variables, including mass concentration, temperature and displacement are studied in a strip, which is subjected to shock loading. The governing equations are derived using generalized coupled non-Fickian diffusion-thermoelasticity theory, which is based on Lord-Shulman theory of coupled thermoelasticity. The governing equations are transferred to the frequency domain using Laplace transform technique and then the field variables are obtained in analytical forms using the presented method. The field variables are eventually determined in time domain by employing the Talbot technique. The dynamic behaviors of mass concentration, temperature and displacement are studied in details. It is concluded that the presented analytical method has a high capability for simulating the wave propagation with finite speed in mass concentration field as well as for tracking thermoelastic waves. Furthermore, the obtained results are more realistic than that of others.

The Uptake of Solvent in Polymeric Thin Membranes By a Relaxation-Sorption Coupled Mechanism

  • Song, Kyu-Min;Hong, Won-Hi
    • Proceedings of the Membrane Society of Korea Conference
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    • 1995.10a
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    • pp.43-44
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    • 1995
  • The diffusion behavior of liquid into polymer has been described by Fick's law, but the departure from Fickian diffusion is frequently found. In this study, 'noble' expressions for the rates of relaxation and sorption are introduced to eliminate these limitations. The ralaxation-sorption coupled mechanism model are based on the possibility of contacting liquid molecule and the active site which has the numerical concept of free volume. The concept has an analogy of reaction rate expressed by the possibility of collision with molecules and used in adsorption and reactive extraction etc. The new model simulated by Rungc-Kutta method for initial-value problem and Fickian diffusion is caompared with experimental data. The results show that the ralaxation-sorption coupled mechanism is able to account well for Fickian and non-Fickian sorption behavior including sigmoid and two-stage. In addition, this model has a chance of expansion to multi-component sorption with ease.

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The application of model equations to Non-Fickian diffusion observed in Fluoropolymers

  • Lee, Sangwha
    • Proceedings of the Membrane Society of Korea Conference
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    • 1996.04a
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    • pp.34-35
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    • 1996
  • The diffusional behavior of many non-solvents in glassy or semicrystalline polymers cannot be adequately described by a concentration-dependent form of Fick's law, especially when mass transfer is coupled with structural changes. Many mathematical models have been devised to interprete non-Fickian diffusion dominated by relaxation kinetics. In formulation of non-Fickian diffusion mathematics, therefore, the most important factor to consider is how relaxation effects can influence the governing constitutive equation and boundary conditions. That is, relaxation parameters can be accommodated by variable boundary conditions or a modified continuity equation, or both, depending on specific systems and conditions (Frish, 1980). Accoring to Astarita and Nicolais (1983), the model equations can be broadly categorized as continuous or discontinuous. Continuous model equations encompass phenomena where the structural change takes place gradually over the whole volume of the polymer sample (Crank, 1953; Long and Richman, 1961; Berens and Hopfenberg, 1978). On the other hand, discontinuous model equations deal with the phenomena where the morphological change appears to be abrupt (Li, 1984). Four mathematical models with different relaxation parameters were applied to fit the anomalous sorption data observed in fluoropolymers (PVDF, ECTFE). The fitted result for PVDF-benzene sorption data is shown in Fig. 1.

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Application of Diffusion Models to Anomalous Sorption in Fluoropolymer-aromatic Solvent Systems (불소고분자-방향족 용매계의 비이상적 흡수에 대한 확산 모델식의 적용)

  • 이상화
    • Membrane Journal
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    • v.10 no.3
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    • pp.139-147
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    • 2000
  • Non-Fickian (or anomalous) diffusion was observed in transient sorption of aromatic solvents(such as benzene, toluene, and chlorobenzene) in fluoropolymers (such as ETFE, ECTFE and PVDF). In this study, five other transient sorption models (Crank, Long & Richman, Berens & Hopfenberg, Neogi, Li) based on Fick's law were employed to fit the anomalous sorption data for aromatic solvents. The adjustable parameters were determined by least square analysis of the measured and predicted fractional uptake. For ETFE sorption data slightly deviating from Fickian behavior, all the models exhibited satisfactory results in fitting the anomalous sorption data. In particular, Neogj model predicted intrinsic diffusivity (0.4~0.8$\times$10$^{-5}$ $\textrm{cm}^2$/day) and equilibrium diffusivity (0.13~0.31$\times$10$^{-4}$ $\textrm{cm}^2$/day) as well as relaxation kinetics related to non-Fickain diffusion. For a typical sigmoidal sorption behavior in PVDF, only Crank's model could give the reasonable evaluation on transport properties. The ratio of intial diffusivity (D$_{i}$) to final equilibrium diffusivity (D$_{\infty}$) was ranged from 80 to 200. For the final stage of uptake In ECTFE with drastic acceleration, all the models exhibited significant deviations from the sorption data. New diffusion models based on thermodynamics and continuum mechanics should be employed to get valuable information on transport properties as well as relaxation kinetics coupled with non-Fickian diffusion.

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An explicit solution of residence time distribution for analyzing one-dimensional solute transport in streams (하천에서 1차원 오염물질 거동 해석을 위한 정체시간분포의 양해적 해석해)

  • Byunguk Kim;Siyoon Kwon;Il Won Seo
    • Proceedings of the Korea Water Resources Association Conference
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    • 2023.05a
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    • pp.518-518
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    • 2023
  • 자연하천에서 오염물질의 혼합 거동은 비균일한 지형학적 요인으로 인해 매우 복잡한 특성을 나타낸다. 일반적으로 오염물질 거동 모델링에서는 수체에서의 혼합을 Fick의 법칙에 따라 유속에 의한 이송과 난류에 의한 확산으로 계산하고, 국부적인 정체현상 등에 의한 non-Fickian 혼합을 야기하는 하천의 특성을 기하학적 지형 형상으로 구현하여 실제 현상에 근접한 혼합 거동을 재현한다. 하지만 계산의 효율성을 위하여 모델링의 차원을 낮추는 경우, 하천의 지형을 경계조건으로 고려할 수 없게 된다. 특히, 1차원 모델링의 경우 하천의 비균일성을 무시하고 1개의 유선으로 간주하며, 이 경우 non-Fickian 물질이동 해석을 위한 추가적인 현상학적 해석이 필요하다. 지난 50년간, non-Fickian 물질이동 해석을 위한 다양한 현상학적 모형이 제시되어 왔다. 하천을 흐름영역과 정체영역으로 구분하고 두 개의 영역 사이의 물질교환 속도를 모델링하거나, Random walk 개념으로 물질이 이동하는 경우와 이동하지 않는 경우를 확률론적으로 모델링하거나, 물질이 정체되었을 때 다시 빠져나오는 시간을 모델링하는 경우가 그 예이다. 본 연구에서는 선행연구에서 제시한 음함수 형태의 현상학적 모형을 기반으로, 수치적 반복계산 없이 상류 경계에서 임의의 형태의 농도곡선(shape-free breakthrough curve)을 갖는 오염물질운(cloud)이 일정 거리를 유하하며 발생하는 변화를 예측할 수 있는 해를 제시한다. 본 연구의 방법론은 추적법(routing procedure)을 활용한 Fickian 혼합 해석, 전달함수(transfer function) 형태의 정체시간분포 해석, 그리고 라플라스 도메인에서의 해석해 유도를 포함한다. 본 연구에서 제시된 해는 2020년 경상북도 김천시에 위치한 감천의 4.5 km 구간에서 수행한 추적자 실험의 현장 자료를 통해 정확도를 검증하여 타당성을 입증하였다.

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Non-Fickian Diffusion of Organic Solvents in Fluoropolymeys (불소고분자내 유기용매의 비-픽 확산)

  • 이상화
    • Polymer(Korea)
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    • v.28 no.1
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    • pp.24-34
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    • 2004
  • Transient sorption experiments were conducted among several combinations of fluoropolymers and various organic solvents. Fully fluorinated polymer tended to exhibit ideal sorption behavior, while partially fluorinated polymers showed anomalous sorption behaviors with a drastic acceleration at the final stage of uptake. Minimization of least-squares of the measured and predicted fractional uptake, which indicated the increasing degree of deviation from Fickian diffusion, gave values of 3.0${\times}$10$\^$-4/, 1.75${\times}$10$\^$-3/, 8.68${\times}$10/sup-3/, 1.75${\times}$10$\^$-2/, respectively, for perfluoroalkoxy copolymer, poly(ethylene-co-tetrafluoroethylene), poly(vinylidene fluoride), poly(ethylene-co-chlorotrifluoroethylene). From stress-strain tests, it was confirmed that non-Fickian diffusion is closely related to the significant variation of mechanical properties (such as modulus and tensile strength) of swollen polymer. Anomalous sorption behavior stemmed from non-Fickian diffusion caused by nonlinear disruption of polar inter-segmental bonds due to solvent-induced plasticization. Thus, it is imperative to investigate the diffusion behavior of swelling solvents in partially fluorinated polymers, especially for the application to barrier materials or perm-selective membranes.

pH-Sensitive Dynamic Swelling Behavior of Glucose-containing Anionic Hydrogels (글루코스를 함유한 음이온 하이드로젤의 pH 감응성 동적 팽윤거동)

  • Kim, Bumsang
    • Korean Chemical Engineering Research
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    • v.43 no.2
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    • pp.299-304
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    • 2005
  • There have been many efforts to use anionic hydrogels as oral protein delivery carriers due to their pH-responsive swelling behavior. The dynamic swelling behavior of poly(methacrylic acid-co-methacryloxyethyl glucoside) [P(MAA-co-MEG)] hydrogels was investigated to determine the mechanism of water transport through these anionic hydrogels. The exponential relation $M_t/M_{\infty}=kt^n$ was used to calculate the exponent, n, describing the Fickian or non-Fickian behavior of swelling polymer networks. The mechanism of water transport through these gels was significantly affected by the pH of the swelling medium. The mechanism of water transport became more relaxation-controlled in the swelling medium of pH 7.0 that was higher than the $pK_a$ of the gels. Experimental results of time-dependent swelling behavior of the gels were analyzed with several mathematical models. Using ATR-FTIR spectroscopy, the effect of ionization of the carboxylic acid groups in the polymer networks on the water transport mechanism was investigated.

Adsorption and Release Characteristics of Sulindac on Chitosan-based Molecularly Imprinted Functional Polymer Films (키토산 기반 분자 각인 고분자 필름의 슐린닥 흡착 및 방출 특성)

  • Yoon, Yeon-Hum;Yoon, Soon-Do;Nah, Jae Woon;Shim, Wang Geun
    • Applied Chemistry for Engineering
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    • v.30 no.2
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    • pp.233-240
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    • 2019
  • Molecular recognition technology has attracted considerable attention for improving the selectivity of a specific molecule by imprinting it on a polymer matrix. In this study, adsorption and release characteristics of chitosan based drug delivery films imprinted with sulindac (SLD) were investigated in terms of the plasticizer, temperature and pH and the results were also interpreted by the related mathematical models. The adsorption characteristics of target molecules on SLD-imprinted polymer films were better explained by the Freundlich and Sips equation than that of the Langmuir equation. The binding site energy distribution function was also useful for understanding the adsorption relationship between target molecules and polymer films. The drug release of SLD-imprinted polymer films followed the Fickian diffusion mechanism, whereas the drug release using artificial skin followed the non-Fickian diffusion behavior.