• Title/Summary/Keyword: polymer kinetic theory

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Micro and macro in the dynamics of dilute polymer solutions: Convergence of theory with experiment

  • Prakash, J. Ravi
    • Korea-Australia Rheology Journal
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    • v.21 no.4
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    • pp.245-268
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    • 2009
  • Recent developments in dilute polymer solution rheology are reviewed, and placed within the context of the general goals of predicting the complex flow of complex fluids. In particular, the interplay between the use of polymer kinetic theory and continuum mechanics to advance the microscopic and the macroscopic description, respectively, of dilute polymer solution rheology is delineated. The insight that can be gained into the origins of the high Weissenberg number problem through an analysis of the configurational changes undergone by a single molecule at various locations in the flow domain is discussed in the context of flow around a cylinder confined between flat plates. The significant role played by hydrodynamic interactions as the source of much of the richness of the observed rheological behaviour of dilute polymer solutions is highlighted, and the methods by which this phenomenon can be incorporated into a macroscopic description through the use of closure approximations and multi scale simulations is discussed.

Bifunctional Perfluoroaryl Boranes as Cationic Initiators for Isobutylene Polymerization

  • Piers Warren E.;Chase Preston A.;Henderson Lee, D.;Sciarone Timo;Collins Scott;Chai, Jianfang;Parvez Masood
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.150-151
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    • 2006
  • Perfluoroaryl boranes are widely employed as co-catalysts in olefin polymerization processes. Perfluoroaryl diboranes, possessing borane centers in close proximity, are a subclass of this family of compounds that are in theory capable of chelating neutral and anionic bases. The resulting anions are exceptionally weakly coordinating. We have prepared examples of such compounds and studied their coordination behavior with neutral Lewis bases that have the capability to bridge Lewis acid sites in an effort to delineate the kinetic and thermodynamic factors that influence bonding mode. When protic Lewis bases such as alcohols or water are reacted with diboranes, strong Bronsted acids capable of initiating cationic polymerizations under unusual conditions result.

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Shear Stress Effect on Isothermal Crystallization Behavior of Semicrystalline Polymer (고분자수지의 등온 결정화거동에 미치는 전단응력의 영향)

  • 박헌진
    • The Korean Journal of Rheology
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    • v.9 no.4
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    • pp.174-182
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    • 1997
  • 결정성 고분자수지는 가공조건에 의해 결정되는 미세구조의 변화에 따라 최종물성 이 현저히 달라지므로 최종 성형품의 물성을 극대화하기 위해서는 성형가공 중에 필연적으 로 부가되는 열이력 뿐만 아니라 전단이력이 결정화 거동에 미치는 영향을 규명하고 가공조 건의 최적화를 통하여 미세구조를 적절히 제어하는 것이 요구된다. 따라서 본 연구에서 in-situ 상태로 전단유도 결정화거동을 조사할수 있는 rheo-kinetic 실험 방법을 개발하고 결정화 거동에 미치는 열이력과 전단이력의 영향을 규명하고자 하였다. 이를 위해 비교적 결정화 속도가 빠른 폴리 부틸렌 테레프탈레이트 수지를 대상으로 냉각조건, 전단부가시간, 전단속도등을 다양하게 변화시키면서 plate-plate 레오미터로 시간에 따른 전단응력의 변화 를 조사하는 rheo-kinetic 연구를 수행하였다. 아울러 실험 중에 액체 질소로 급냉하여 얻은 시료를 대상으로 등온 및 비등온의 열분석 실험을 수행하고 JMA식과 Hoffman-Lauritzentlr 을 사용하여 분석한 다음, 그 결과를 rheo-kinetic 해석결과와 비교함으로써 결정화 거동에 미치는 전단응력의 영향을 규명하였다. 일정전단속동하에서 수행한 rheo-kinetic 실험결과, 시간에 따른 저난응력의 증가와 용융열이 증가하는 경향이 매우 유사한 거동을 보이므로 전 단응력의 증가는 결정화가 일어남에 기인한 결과임을 확인할수 있었으며 고분자수지가 전단 이력을 받게 되면 분자배향의 결과로 결정화 유도시간이 짧아지고 결정화속도가 증가할 뿐 만 아니라 보다 더 높은 온도에서 결정화가 일어나게 됨을 알수 있었다. 또 결정화 반가기 시간과 Hoffman-Lauritzen 식의 매개변수들이 전단속도, 전단부가시간, 결정화 온도 등의 이력에 무관하게 전단응력에 따라 선형적으로 변하고 있으므로 전단유도 결정화거동은 수지 에 부가되는 전단응력에 직접적인 영향을 받음을 알수 있었다. 이상과같은 전단유도 결정화 거동에 관한 결과를 가공공정상의 열전달 현상과 결합하여 해서하면 성형품 내부의모폴로지 의 예측이 가능하므로 성형품 물성의 극대화 방안의 수립에 이용될수 있을것으로 사료된다.

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Dynamic characteristics of a CSTR with MMA polymerization

  • Ahn, Jong-Pil;Rhee, Hyun-Ku
    • 제어로봇시스템학회:학술대회논문집
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    • 1992.10b
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    • pp.100-105
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    • 1992
  • A mathematical model is developed for a CSTR in which free radical solution polymerization of methyl methacrylate(MMA) takes place. It turns out that five ordinary differential equations are to be treated simultaneously in order to predict the reactor performance. Although the reaction proceeds under the conditions of relatively low temperature and pressure, the system shows very complex bifurcation features due to the diffusion limitation (gel effect) and the temperature dependence of the kinetic parameters and physical properties. The effects of various system parameters on the reactor performance as well as on the polymer properties are investigated by using the bifurcation analysis. The application of the singularity theory enables us to divide the parameter space into several different regions, in each of which the system takes a unique steady state structure. Under certain circumstances, complex dynamic features such as HB points and limit cycles are observed and these should be taken into consideration in the reactor design.

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Chemically Modified Electrodes and Their Applications to Electrocatalysis-Poly-MePMP+BF4-/Ferri-ferrocyanide/Ascorbic Acid System (기능성 전극의 전기촉매로의 응용-Poly-MePMP+BF4-/Ferri-Ferri-ferrocyanide/Ascorbic Acid계)

  • Chang, Dong-Hun;Oh, Seung-Mo
    • Applied Chemistry for Engineering
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    • v.3 no.1
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    • pp.138-147
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    • 1992
  • Chemically-modified electrodes were fabricated and their electrocatalytic behaviors have been investigated. As a modifying layer, poly-[1-methyl-3-(pyrrol-1-ylmethyl) pyridinium] was electropolymerized onto Pt electrodes under constant current. The thickness of the polymer film was controlled by means of total charge consumed during the electropolymerization. SEM was used to measure the thickness. There was a linear relationship between the passed charge and the film thickness. Ferro/ferricyanide, used as an electron mediator in this study, was rapidly ion-exchanged into the polymer layer with its concentration of 1.2~1.3M. It was found that electrooxidation of ascorbic acid is catalyzed by incorporated ferri/ferrocyanide couple. Kinetic parameters for electrooxidation were determined by RDE experiments. The results indicate that the present system corresponds to ER+S case based on the Saveant theory. Improving methods have been proposed to be R+S case which is ideal for electrocatalysis.

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Geometrically nonlinear thermo-mechanical analysis of graphene-reinforced moving polymer nanoplates

  • Esmaeilzadeh, Mostafa;Golmakani, Mohammad Esmaeil;Kadkhodayan, Mehran;Amoozgar, Mohammadreza;Bodaghi, Mahdi
    • Advances in nano research
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    • v.10 no.2
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    • pp.151-163
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    • 2021
  • The main target of this study is to investigate nonlinear transient responses of moving polymer nano-size plates fortified by means of Graphene Platelets (GPLs) and resting on a Winkler-Pasternak foundation under a transverse pressure force and a temperature variation. Two graphene spreading forms dispersed through the plate thickness are studied, and the Halpin-Tsai micro-mechanics model is used to obtain the effective Young's modulus. Furthermore, the rule of mixture is employed to calculate the effective mass density and Poisson's ratio. In accordance with the first order shear deformation and von Karman theory for nonlinear systems, the kinematic equations are derived, and then nonlocal strain gradient scheme is used to reflect the effects of nonlocal and strain gradient parameters on small-size objects. Afterwards, a combined approach, kinetic dynamic relaxation method accompanied by Newmark technique, is hired for solving the time-varying equation sets, and Fortran program is developed to generate the numerical results. The accuracy of the current model is verified by comparative studies with available results in the literature. Finally, a parametric study is carried out to explore the effects of GPL's weight fractions and dispersion patterns, edge conditions, softening and hardening factors, the temperature change, the velocity of moving nanoplate and elastic foundation stiffness on the dynamic response of the structure. The result illustrates that the effects of nonlocality and strain gradient parameters are more remarkable in the higher magnitudes of the nanoplate speed.

Dynamic characterization of a CNT reinforced hybrid uniform and non-uniform composite plates

  • Lakshmipathi, Jakkamputi;Vasudevan, Rajamohan
    • Steel and Composite Structures
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    • v.30 no.1
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    • pp.31-46
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    • 2019
  • In the present study, the various dynamic properties of MWCNT embedded fiber reinforced polymer uniform and tapered composite (MWCNT-FRP) plates are investigated. Various configurations of a tapered composite plate with ply-drop off and uniform composite plate have been considered for the development of the finite element formulation and experimental investigations. First order shear deformation theory (FSDT) has been used to derive the kinetic and potential energy equations of the hybrid composite plates by including the effect of rotary inertia, shear deformation and non-uniformity in thickness of the plate. The governing equations of motion of FRP composite plates without and with MWCNT reinforcement are derived by considering a nine- node rectangular element with five degrees of freedom (DOF) at each node. The effectiveness of the developed finite element formulation has been demonstrated by comparing the natural frequencies and damping ratio of FRP composite plates without and with MWCNT reinforcement obtained experimentally. Various parametric studies are also performed to study the effect of CNT volume fraction and CNT aspect ratio of the composite plate on the natural frequencies of different configurations of CNT reinforced hybrid composite plates. Further the forced vibration analysis is performed to compare the dynamic response of the various configurations of MWCNT-GFRP composite plate with GFRP composite plate under harmonic excitations. It was observed that the fundamental natural frequency and damping ratio of the GFRP composite plate increase approximately 8% and 37% respectively with 0.5wt% reinforcement of MWCNT under CFCF boundary condition. The natural frequencies of MWCNT-GFRP hybrid composite plates tend to decrease with the increase of MWCNT volume fraction beyond 2% due to agglomeration of CNT's. It is also observed that the aspect ratio of the CNT has negligible effect on the improvement of dynamics properties due to randomly orientation of CNT's.

Seismic response of NFRP reinforced RC frame with shape memory alloy components

  • Varkani, Mohamad Motalebi;Bidgoli, Mahmood Rabani;Mazaheri, Hamid
    • Advances in nano research
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    • v.13 no.3
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    • pp.285-295
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    • 2022
  • Creation of plastic deformation under seismic loads, is one of the most serious subjects in RC structures with steel bars which reduces the life threatening risks and increases dissipation of energy. Shape memory alloy (SMA) is one of the best choice for the relocating plastic hinges. In a challenge to study the seismic response of concrete moment resisting frame (MRF), this article investigates numerically a new type of concrete frames with nano fiber reinforced polymer (NFRP) and shape memory alloy (SMA) hinges, simultaneously. The NFRP layer is containing carbon nanofibers with agglomeration based on Mori-Tanaka model. The tangential shear deformation (TASDT) is applied for modelling of the structure and the continuity boundary conditions are used for coupling of the motion equations. In SMA connections between beam and columns, since there is phase transformation, hence, the motion equations of the structure are coupled with kinetic equations of phase transformation. The Hernandez-Lagoudas theory is applied for demonstrating of pseudoelastic characteristics of SMA. The corresponding motion equations are solved by differential cubature (DC) and Newmark methods in order to obtain the peak ground acceleration (PGA) and residual drift ratio for MRF-2%. The main impact of this paper is to present the influences of the volume percent and agglomeration of nanofibers, thickness and length of the concrete frame, SMA material and NFRP layer on the PGA and drift ratio. The numerical results revealed that the with increasing the volume percent of nanofibers, the PGA is enhanced and the residual drift ratio is reduced. It is also worth to mention that PGA of concrete frame with NFRP layer containing 2% nanofibers is approximately equal to the concrete frame with steel bars.