• Title/Summary/Keyword: polymer melts

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Constitutive equations for polymer mole and rubbers: Lessons from the $20^{th}$ century

  • Wagner, Manfred H.
    • Korea-Australia Rheology Journal
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    • v.11 no.4
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    • pp.293-304
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    • 1999
  • Refinements of classical theories for entangled or crosslinked polymeric systems have led to incommensurable models for rubber networks and polymer melts, contrary to experimental evidence, which suggests a great deal of similarity. Uniaxial elongation and compression data of linear and branched polymer melts as well as of crosslinked rubbers were analyzed with respect to their nonlinear strain measure. This was found to be the result of two contributions: (1) affine orientation of network strands, and (2) isotropic strand extension. Network strand extension is caused by an increasing restriction of lateral movement of polymer chains due to deformation, and is modelled by a molecular stress function which in the tube concept of Doi and Edwards is the inverse of the relative tube diameter. Up to moderate strains, $f^2$ is found to be linear in the average stretch for melts as well as for rubbers, which corresponds to a constant tube volume. At large strains, rubbers show maximum extensibility, while melts show maximum molecular tension. This maximum value of the molecular stress function governs the ultimate magnitude of the strain-hardening effect of linear and long-chain branched polymer melts in extensional flows.

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Modelling nonlinear polymer rheology is still challenging

  • Marrucci Giuseppe;Ianniruberto Giovanni
    • Korea-Australia Rheology Journal
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    • v.17 no.3
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    • pp.111-116
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    • 2005
  • The new tube model with variable diameter (Marrucci and Ianniruberto, 2004), recently introduced to interpret new elongational data of polymer melts, is here extended to encompass arbitrary flows, specifically shear flows. The predicted results compare well with existing data of entangled polymer melts. Challenges still remain when the comparison is extended to recent elongational data on entangled solutions by Sridhar.

Nonlinear rheology of linear polymer melts: Modeling chain stretch by interchain tube pressure and Rouse time

  • Wagner, Manfred H.;Rolon-Garrido, Victor H.
    • Korea-Australia Rheology Journal
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    • v.21 no.4
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    • pp.203-211
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    • 2009
  • In flows with deformation rates larger than the inverse Rouse time of the polymer chain, chains are stretched and their confining tubes become increasingly anisotropic. The pressures exerted by a polymer chain on the walls of an anisotropic confinement are anisotropic and limit chain stretch. In the Molecular Stress Function (MSF) model, chain stretch is balanced by an interchain pressure term, which is inverse proportional to the $3^{rd}$ power of the tube diameter and is characterized by a tube diameter relaxation time. We show that the tube diameter relaxation time is equal to 3 times the Rouse time in the limit of small chain stretch. At larger deformations, we argue that chain stretch is balanced by two restoring tensions with weights of 1/3 in the longitudinal direction of the tube (due to a linear spring force) and 2/3 in the lateral direction (due to the nonlinear interchain pressure), both of which are characterized by the Rouse time. This approach is shown to be in quantitative agreement with transient and steady-state elongational viscosity data of two monodisperse polystyrene melts without using any nonlinear parameter, i.e. solely based on the linear-viscoelastic characterization of the melts. The same approach is extended to model experimental data of four styrene-butadiene random copolymer melts in shear flow. Thus for monodisperse linear polymer melts, for the first time a constitutive equation is presented which allows quantitative modeling of nonlinear extension and shear rheology on the basis of linear-viscoelastic data alone.

Structure-property relations for polymer melts: comparison of linear low-density polyethylene and isotactic polypropylene

  • Drozdov, A.D.;Al-Mulla, A.;Gupta, R.K.
    • Advances in materials Research
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    • v.1 no.4
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    • pp.245-268
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    • 2012
  • Results of isothermal torsional oscillation tests are reported on melts of linear low density polyethylene and isotactic polypropylene. Prior to rheological tests, specimens were annealed at various temperatures ranging from $T_a$ = 180 to $310^{\circ}C$ for various amounts of time (from 30 to 120 min). Thermal treatment induced degradation of the melts and caused pronounced decreases in their molecular weights. With reference to the concept of transient networks, constitutive equations are developed for the viscoelastic response of polymer melts. A melt is treated as an equivalent network of strands bridged by junctions (entanglements and physical cross-links). The time-dependent response of the network is modelled as separation of active strands from and merging of dangling strands with temporary nodes. The stress-strain relations involve three adjustable parameters (the instantaneous shear modulus, the average activation energy for detachment of active strands, and the standard deviation of activation energies) that are determined by matching the dependencies of storage and loss moduli on frequency of oscillations. Good agreement is demonstrated between the experimental data and the results of numerical simulation. The study focuses on the effect of molecular weight of polymer melts on the material constants in the constitutive equations.

High-pressure rheology of polymer melts containing supercritical carbon dioxide

  • Lee Sang-Myung;Han Jae-Ro;Kim Kyung-Yl;Ahn Young-Joon;Lee Jae-Wook
    • Korea-Australia Rheology Journal
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    • v.18 no.2
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    • pp.83-90
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    • 2006
  • Supercritical carbon dioxide ($scCO_2$) has advantages of being incorporated in polymer with high solubility and of being recovered easily by depressurizing. $scCO_2$ reduces the viscosity of polymer melt and it is expected to be use as a plasticizing agent. In this work, we studied on the effect of $scCO_2$ on the rheological properties of polymer melts during extrusion process. Slit die attached to twin screw extruder was used to measure the viscosity of polymer melts plasticized by supercritical $CO_2$. A gas injection system was devised to accurately meter the supercritical $CO_2$ into the extruder barrel. Measurements of pressure drop within the die, confirmed the presence of a one phase mixture and a fully developed flow during the measurements. The viscosity measurement of polypropylene was performed at experimental conditions of various temperatures, pressures and $CO_2$ concentrations. We observed that melt viscosity of polymer was dramatically reduced by $CO_2$ addition.

Viscosity of polymer melts reduced jointly by filler addition and LCP fibrillation

  • He, Jiasong
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.132-132
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    • 2006
  • Filler loading (fiber or particulate) usually increases the melt viscosity of polymers. In contrast, the addition of these fillers and fibrillation of thermotropic liquid crystalline polymer (LCP) jointly decreased the viscosity of polymer melts to lower than those of pure component polymers, filler-loaded or LCP-blended ones; and even decreased the viscosity with increasing filler loading. Termed as rheological hybrid effect, this phenomenon correlated well with the LCP fibrillation in these ternary systems. Research taking fillers of various shapes and sizes showed that the filler addition promoted the LCP fibrillation, depending upon thermodynamic and dynamic factors involved.

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Polymer Materials Design for Good Processability of Polymer Processing

  • Koyama, Kiyohito
    • Proceedings of the Polymer Society of Korea Conference
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    • 2006.10a
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    • pp.135-136
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    • 2006
  • The shear flow properties have been reported in many cases by manufactures and fabricators. Only this characteristic is sometimes insufficient for the processings to provide a complete picture of the relationship between the processability and the flow behavior when underwent free-surface processes in which the shape and thickness of the extrudate are determined by the rheological properties of the melt, the die dimensions etc. In this paper the methodology of control of elongational flow is discussed in terms of relaxation time control of the polymer melts.

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A comparative analysis of sheeting die geometries using numerical simulations

  • Igali, Dastan;Wei, Dongming;Zhang, Dichuan;Perveen, Asma
    • Advances in Computational Design
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    • v.5 no.2
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    • pp.111-125
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    • 2020
  • The flow behavior of polymer melts within a slit die is an important consideration when designing a die geometry. The quality of the extruded polymer product can be determined through an evaluation of the flow homogeneity, wall shear rate and pressure drop across the central height of the die. However, mathematical formulations cannot fully determine the behavior of the flow due to the complex nature of fluid dynamics and the nonlinear physical properties of the polymer melts. This paper examines two slit die geometries in terms of outlet velocity uniformity, shear rate uniformity at the walls and pressure drop by using the licensed computational fluid dynamics package, Ansys POLYFLOW, based on the finite element method. The Carreau-Yasuda viscosity model was used for the rheological properties of the polypropylene. Comparative analysis of the simulation results will conclude that the modified die design performs better in all three aspects providing uniform exit velocity, uniform wall shear rates, and lower pressure drop.