ABSTRACT The dynamics of kinks (domain walls) in a linear chain system with frustration, in which... more ABSTRACT The dynamics of kinks (domain walls) in a linear chain system with frustration, in which incommensurate phases occur, is studied. In this both numerical and analytical techniques are used. The kinks, which can be interpreted as discommensurations in incommensurate phases, are found to be unstable, in a continuum approximation, but their lifetime may be long near the lock-in transition due to pinning effects.
A statistical approach is developed, based on a Monte Carlo method, in order to determine the sta... more A statistical approach is developed, based on a Monte Carlo method, in order to determine the statistical composition of a polyamide-6 sample composed of caprolactam (an AB-type monomer) and of a di-acid (A 2 type) or a triacid (A 3 type) as coupling agents. For this composition, the linear rheological behavior of these systems is predicted using a tube-based theory. This allows us to show that while coupling agents of type A 2 can be seen as flow improver, the effect of branching agents of type A 3 , depending on the synthesis recipe and the conversion level, can lead either to an increase or to a decrease of the viscosity. By adding specific amount of these agents, we also show that it is possible to obtain materials with the same zero-shear viscosity but with different shear thinning behavior. Furthermore, the polydispersity of linear samples of the same average number molecular weight, M n , is discussed in function of the amount of A 2 monomers they contain. Ranging from 2 to 1.5, this difference in polydispersity is expected to have a significant influence on the processing behavior of such materials.
Xenoposeidon proneneukos is a sauropod dinosaur from the Early Cretaceous Hastings Group of Engla... more Xenoposeidon proneneukos is a sauropod dinosaur from the Early Cretaceous Hastings Group of England. It is represented by a single partial dorsal vertebra, NHMUK PV R2095, which consists of the centrum and the base of a tall neural arch. Despite its fragmentary nature, it is recognisably distinct from all other sauropods, and is here diagnosed with five unique characters. One character previously considered unique is here recognised as shared with the rebbachisaurid diplodocoid Rebbachisaurus garasbae from the mid-Cretaceous of Morocco: an "M"-shaped arrangement of laminae on the lateral face of the neural arch. Following the more completely preserved Rebbachisaurus garasbae, these laminae are now interpreted as ACPL and lateral CPRL, which intersect anteriorly; and PCDL and CPOL, which intersect posteriorly. Similar arrangements are also seen in some other rebbachisaurid specimens (though not all, possibly due to serial variation), but never in non-rebbachisaurid sauropods. Xenoposeidon is therefore referred to Rebbachisauridae. Due to its inferred elevated parapophysis, the holotype vertebra is considered a midposterior dorsal despite its elongate centrum. Since Xenoposeidon is from the Berriasian-Valanginian (earliest Cretaceous) Ashdown Formation of the Wealden Supergroup of southern England, it is the earliest known rebbachisaurid by some 10 million years. Electronic 3D models were invaluable in determining Xenoposeidon's true affinities: descriptions of complex bones such as sauropod vertebrae should always provide them where possible.
Take-down policy If you believe that this document breaches copyright please contact us providing... more Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.
The aim of the present paper is to analyse the differences between tube-based models which are wi... more The aim of the present paper is to analyse the differences between tube-based models which are widely used for predicting the linear viscoelasticity of monodisperse linear polymers, in comparison to a large set of experimental data. The following models are examined: Milner–McLeish, Likhtman–McLeish, the Hierarchical model proposed by the group of Larson, the BoB model of Das and Read, and the TMA model proposed by the group of van Ruymbeke. This comparison allows us to highlight and discuss important questions related to the relaxation of entangled polymers, such as the importance of the contour-length fluctuations (CLF) process and how it affects the reptation mechanism, or the contribution of the constraint release (CR) process on the motion of the chains. In particular, it allows us to point out important approximations, inherent in some models, which result in an overestimation of the effect of CLF on the reptation time. On the contrary, by validating the TMA model against expe...
This study considers step-growth polymerizing systems of general type "Afi Bgi" whereby one or mo... more This study considers step-growth polymerizing systems of general type "Afi Bgi" whereby one or more of the reacting monomer species bear at least three reactive groups. The random polymerization process will lead to a population of polymer molecules in which the individual molecules may differ widely with respect to degree of polymerization and number of branch points. This study presents an algorithmic method to calculate the statistical distribution of weight over these two molecular properties. The method uses bivariate generating functions, recurrences, and integer arithmetic.
A framework for a consistent description of the flow-induced correlation effects within a linear ... more A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present model allows one to take into account all the major relaxation mechanisms. Special cases of the derived set of equations are shown to yield existing models and shed some light on the connection between them. Consequences of several assumptions widely used in the literature are analyzed within the developed framework.
Electro-hydrodynamic equations describing the behavior of a charged polymer jet are analyzed by a... more Electro-hydrodynamic equations describing the behavior of a charged polymer jet are analyzed by analytical methods and scaling approach. A FENE-P constitutive equation is employed to describe the viscoelastic properties of a conducting polymer liquid. Effects of the electric field, the flow rate, and the material parameters on the jet dynamics are investigated. Four different regimes are examined. In particular, a regime in which the electric current is linearly proportional to the electric field and independent on the flow rate and a regime in which the electric current is linearly proportional to the flow rate and independent on the electric field are identified. An operating window limiting the region of a stable cone-jet mode is also considered.
DOI to the publisher's website. • The final author version and the galley proof are versions of t... more DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:
ABSTRACT We present a modified version of the time-marching algorithm (TMA) [van Ruymbeke et al.,... more ABSTRACT We present a modified version of the time-marching algorithm (TMA) [van Ruymbeke et al., 2005, 2010] for predicting the linear viscoelasticity of monodisperse symmetric star polymer melts. Several new elements were added to the original TMA model. In particular, the remaining fraction of the initial tube segments is considered as a function of time, while taking into account the past relaxation history of each molecular segment. We validate the TMA model and, for the first time, compare it with the so-called BoB model [Das et al., 2006]. The predictions obtained with the two models are compared to a large set of experimental data, which cover a broad range of arm molecular weights (from 1.5 to 55 entanglements per arm) of different chemistries (polystyrene, polybutadiene, and polyisoprene). We indicate the significant differences between the two approaches, which mainly affect the choice of material parameters of the models. We then point out a systematic deviation of the TMA model in accurately predicting the intermediate regime of relatively short star chains, while the BoB model fails in correctly describing the plateau modulus of these short chains. From our point of view, both disparities have the same origin and, in the case of the TMA, can be solved by removing the high-frequency mode contribution to the contour length fluctuation of the primitive path. An excellent agreement between data and theory is then obtained for all molecular weights of the arms, which indicates the capability of the TMA to provide a quantitative prediction of the rheology of monodisperse star-shaped polymers. A very good agreement is also obtained with the BoB model, despite the expected discrepancy observed with short star chains. This proves the fact that current tube-based models are successful in quantitative predictions of linear rheology of monodisperse star-shaped polymers.
The rheology of systems containing rigid spheres suspended in both viscous and viscoelastic media... more The rheology of systems containing rigid spheres suspended in both viscous and viscoelastic media, studied by Stokesian dynamics simulations.
ABSTRACT In our previous publication, we presented a molecular model to describe the dynamics of ... more ABSTRACT In our previous publication, we presented a molecular model to describe the dynamics of the interfacial layer between a flowing polymer melt and a die wall. We showed that the ensemble-averaged behavior of polymer molecules adsorbed on the wall could be successfully described in terms of the so-called bond vector probability distribution function (BVPDF). The BVPDF couples the chain orientation and chain stretch on the level of single segment, and thus is an extension of the orientation distribution function of Doi and Edwards introduced for inextensible chains. In this paper, the developed formalism is extended to molecules in the polymer bulk. We show how the well-known Doi and Edwards theory (DE) for inextensible chains based on the orientation distribution function can be naturally extended to include chain stretch and (convective) constraint release (CCR). The final constitutive equation accounts for such mechanisms on polymer chains as reptation, retraction, convection, contour length fluctuations, and (convective) constraint release. It is valid for both linear and non-linear flow regimes. The proposed theory is quantitative, and contains the same input parameters as the original DE model. As an application of the full theory, a simple equation of motion for the stress tensor is derived. Despite the simplicity, its predictions are found to be in good agreement with available experimental data over a wide range of flow regimes and histories.
A general theory of thermoacoustics is derived for arbitrary stack pores. Previous theoretical tr... more A general theory of thermoacoustics is derived for arbitrary stack pores. Previous theoretical treatments of porous media are extended by considering arbitrarily shaped pores with the only restriction that the pore cross-sections vary slowly in the longitudinal direction. No boundary-layer approximation is necessary. Furthermore, the model allows temperature variations in the pore wall. By means of a systematic approach based on dimensional analysis and small parameter asymptotics, we derive a set of ordinary differential equations for the mean temperature and the acoustic pressure and velocity, where the equation for the mean temperature follows as a consistency condition of the assumed asymptotic expansion. The problem of determining the transverse variation is reduced to finding a Green's function for a modified Helmholtz equation and solving two additional integral equations. Similarly the derivation of streaming is reduced to finding a single Green's function for the Po...
A molecular model is presented which allows the calculation of the stress relaxation function G f... more A molecular model is presented which allows the calculation of the stress relaxation function G for binary blends consisting of two monodisperse samples with arbitrary molecular weights. It extends the Doi-Edwards reptation theory (Doi M. and Edwards S. F., The Theory of Polymer Dynamics (Oxford Press, New York) 1986) to highly polydisperse melts by including constraint release (CR) and thermal fluctuations (CLF), yet making use of the same input parameters. The model reveals an explicit nonlinear dependence of CR frequency in the blend on the blend's molecular weight distribution (MWD). It provides an alternative way to quantify polydisperse systems compared to the widely used "double-reptation" theories. The results of the present model are in a good agreement with the experimental data given in Rubinstein M.
A framework for a consistent description of the correlation effects along polymer chains subject ... more A framework for a consistent description of the correlation effects along polymer chains subject to flow is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present description allows to take into account all the relevant relaxation mechanisms for slow flows. Special cases of the derived set of equations are shown to yield some existing models and shed some light on the connection between them.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014
h i g h l i g h t s • Nanoprecipitation of polymers in a bad solvent with surfactants was examine... more h i g h l i g h t s • Nanoprecipitation of polymers in a bad solvent with surfactants was examined. • We derived a kinetic model for diffusion limited coalescence. • Final nanoparticle size is independent of polymer molar mass of the polymer. • The final particle volume increases linearly with polymer concentration. • Experimental results are in good agreement with theoretical predictions.
DOI to the publisher's website. • The final author version and the galley proof are versions of t... more DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:
A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsor... more A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulkϩboundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.
ABSTRACT The dynamics of kinks (domain walls) in a linear chain system with frustration, in which... more ABSTRACT The dynamics of kinks (domain walls) in a linear chain system with frustration, in which incommensurate phases occur, is studied. In this both numerical and analytical techniques are used. The kinks, which can be interpreted as discommensurations in incommensurate phases, are found to be unstable, in a continuum approximation, but their lifetime may be long near the lock-in transition due to pinning effects.
A statistical approach is developed, based on a Monte Carlo method, in order to determine the sta... more A statistical approach is developed, based on a Monte Carlo method, in order to determine the statistical composition of a polyamide-6 sample composed of caprolactam (an AB-type monomer) and of a di-acid (A 2 type) or a triacid (A 3 type) as coupling agents. For this composition, the linear rheological behavior of these systems is predicted using a tube-based theory. This allows us to show that while coupling agents of type A 2 can be seen as flow improver, the effect of branching agents of type A 3 , depending on the synthesis recipe and the conversion level, can lead either to an increase or to a decrease of the viscosity. By adding specific amount of these agents, we also show that it is possible to obtain materials with the same zero-shear viscosity but with different shear thinning behavior. Furthermore, the polydispersity of linear samples of the same average number molecular weight, M n , is discussed in function of the amount of A 2 monomers they contain. Ranging from 2 to 1.5, this difference in polydispersity is expected to have a significant influence on the processing behavior of such materials.
Xenoposeidon proneneukos is a sauropod dinosaur from the Early Cretaceous Hastings Group of Engla... more Xenoposeidon proneneukos is a sauropod dinosaur from the Early Cretaceous Hastings Group of England. It is represented by a single partial dorsal vertebra, NHMUK PV R2095, which consists of the centrum and the base of a tall neural arch. Despite its fragmentary nature, it is recognisably distinct from all other sauropods, and is here diagnosed with five unique characters. One character previously considered unique is here recognised as shared with the rebbachisaurid diplodocoid Rebbachisaurus garasbae from the mid-Cretaceous of Morocco: an "M"-shaped arrangement of laminae on the lateral face of the neural arch. Following the more completely preserved Rebbachisaurus garasbae, these laminae are now interpreted as ACPL and lateral CPRL, which intersect anteriorly; and PCDL and CPOL, which intersect posteriorly. Similar arrangements are also seen in some other rebbachisaurid specimens (though not all, possibly due to serial variation), but never in non-rebbachisaurid sauropods. Xenoposeidon is therefore referred to Rebbachisauridae. Due to its inferred elevated parapophysis, the holotype vertebra is considered a midposterior dorsal despite its elongate centrum. Since Xenoposeidon is from the Berriasian-Valanginian (earliest Cretaceous) Ashdown Formation of the Wealden Supergroup of southern England, it is the earliest known rebbachisaurid by some 10 million years. Electronic 3D models were invaluable in determining Xenoposeidon's true affinities: descriptions of complex bones such as sauropod vertebrae should always provide them where possible.
Take-down policy If you believe that this document breaches copyright please contact us providing... more Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.
The aim of the present paper is to analyse the differences between tube-based models which are wi... more The aim of the present paper is to analyse the differences between tube-based models which are widely used for predicting the linear viscoelasticity of monodisperse linear polymers, in comparison to a large set of experimental data. The following models are examined: Milner–McLeish, Likhtman–McLeish, the Hierarchical model proposed by the group of Larson, the BoB model of Das and Read, and the TMA model proposed by the group of van Ruymbeke. This comparison allows us to highlight and discuss important questions related to the relaxation of entangled polymers, such as the importance of the contour-length fluctuations (CLF) process and how it affects the reptation mechanism, or the contribution of the constraint release (CR) process on the motion of the chains. In particular, it allows us to point out important approximations, inherent in some models, which result in an overestimation of the effect of CLF on the reptation time. On the contrary, by validating the TMA model against expe...
This study considers step-growth polymerizing systems of general type "Afi Bgi" whereby one or mo... more This study considers step-growth polymerizing systems of general type "Afi Bgi" whereby one or more of the reacting monomer species bear at least three reactive groups. The random polymerization process will lead to a population of polymer molecules in which the individual molecules may differ widely with respect to degree of polymerization and number of branch points. This study presents an algorithmic method to calculate the statistical distribution of weight over these two molecular properties. The method uses bivariate generating functions, recurrences, and integer arithmetic.
A framework for a consistent description of the flow-induced correlation effects within a linear ... more A framework for a consistent description of the flow-induced correlation effects within a linear polymer chain in a melt is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present model allows one to take into account all the major relaxation mechanisms. Special cases of the derived set of equations are shown to yield existing models and shed some light on the connection between them. Consequences of several assumptions widely used in the literature are analyzed within the developed framework.
Electro-hydrodynamic equations describing the behavior of a charged polymer jet are analyzed by a... more Electro-hydrodynamic equations describing the behavior of a charged polymer jet are analyzed by analytical methods and scaling approach. A FENE-P constitutive equation is employed to describe the viscoelastic properties of a conducting polymer liquid. Effects of the electric field, the flow rate, and the material parameters on the jet dynamics are investigated. Four different regimes are examined. In particular, a regime in which the electric current is linearly proportional to the electric field and independent on the flow rate and a regime in which the electric current is linearly proportional to the flow rate and independent on the electric field are identified. An operating window limiting the region of a stable cone-jet mode is also considered.
DOI to the publisher's website. • The final author version and the galley proof are versions of t... more DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:
ABSTRACT We present a modified version of the time-marching algorithm (TMA) [van Ruymbeke et al.,... more ABSTRACT We present a modified version of the time-marching algorithm (TMA) [van Ruymbeke et al., 2005, 2010] for predicting the linear viscoelasticity of monodisperse symmetric star polymer melts. Several new elements were added to the original TMA model. In particular, the remaining fraction of the initial tube segments is considered as a function of time, while taking into account the past relaxation history of each molecular segment. We validate the TMA model and, for the first time, compare it with the so-called BoB model [Das et al., 2006]. The predictions obtained with the two models are compared to a large set of experimental data, which cover a broad range of arm molecular weights (from 1.5 to 55 entanglements per arm) of different chemistries (polystyrene, polybutadiene, and polyisoprene). We indicate the significant differences between the two approaches, which mainly affect the choice of material parameters of the models. We then point out a systematic deviation of the TMA model in accurately predicting the intermediate regime of relatively short star chains, while the BoB model fails in correctly describing the plateau modulus of these short chains. From our point of view, both disparities have the same origin and, in the case of the TMA, can be solved by removing the high-frequency mode contribution to the contour length fluctuation of the primitive path. An excellent agreement between data and theory is then obtained for all molecular weights of the arms, which indicates the capability of the TMA to provide a quantitative prediction of the rheology of monodisperse star-shaped polymers. A very good agreement is also obtained with the BoB model, despite the expected discrepancy observed with short star chains. This proves the fact that current tube-based models are successful in quantitative predictions of linear rheology of monodisperse star-shaped polymers.
The rheology of systems containing rigid spheres suspended in both viscous and viscoelastic media... more The rheology of systems containing rigid spheres suspended in both viscous and viscoelastic media, studied by Stokesian dynamics simulations.
ABSTRACT In our previous publication, we presented a molecular model to describe the dynamics of ... more ABSTRACT In our previous publication, we presented a molecular model to describe the dynamics of the interfacial layer between a flowing polymer melt and a die wall. We showed that the ensemble-averaged behavior of polymer molecules adsorbed on the wall could be successfully described in terms of the so-called bond vector probability distribution function (BVPDF). The BVPDF couples the chain orientation and chain stretch on the level of single segment, and thus is an extension of the orientation distribution function of Doi and Edwards introduced for inextensible chains. In this paper, the developed formalism is extended to molecules in the polymer bulk. We show how the well-known Doi and Edwards theory (DE) for inextensible chains based on the orientation distribution function can be naturally extended to include chain stretch and (convective) constraint release (CCR). The final constitutive equation accounts for such mechanisms on polymer chains as reptation, retraction, convection, contour length fluctuations, and (convective) constraint release. It is valid for both linear and non-linear flow regimes. The proposed theory is quantitative, and contains the same input parameters as the original DE model. As an application of the full theory, a simple equation of motion for the stress tensor is derived. Despite the simplicity, its predictions are found to be in good agreement with available experimental data over a wide range of flow regimes and histories.
A general theory of thermoacoustics is derived for arbitrary stack pores. Previous theoretical tr... more A general theory of thermoacoustics is derived for arbitrary stack pores. Previous theoretical treatments of porous media are extended by considering arbitrarily shaped pores with the only restriction that the pore cross-sections vary slowly in the longitudinal direction. No boundary-layer approximation is necessary. Furthermore, the model allows temperature variations in the pore wall. By means of a systematic approach based on dimensional analysis and small parameter asymptotics, we derive a set of ordinary differential equations for the mean temperature and the acoustic pressure and velocity, where the equation for the mean temperature follows as a consistency condition of the assumed asymptotic expansion. The problem of determining the transverse variation is reduced to finding a Green's function for a modified Helmholtz equation and solving two additional integral equations. Similarly the derivation of streaming is reduced to finding a single Green's function for the Po...
A molecular model is presented which allows the calculation of the stress relaxation function G f... more A molecular model is presented which allows the calculation of the stress relaxation function G for binary blends consisting of two monodisperse samples with arbitrary molecular weights. It extends the Doi-Edwards reptation theory (Doi M. and Edwards S. F., The Theory of Polymer Dynamics (Oxford Press, New York) 1986) to highly polydisperse melts by including constraint release (CR) and thermal fluctuations (CLF), yet making use of the same input parameters. The model reveals an explicit nonlinear dependence of CR frequency in the blend on the blend's molecular weight distribution (MWD). It provides an alternative way to quantify polydisperse systems compared to the widely used "double-reptation" theories. The results of the present model are in a good agreement with the experimental data given in Rubinstein M.
A framework for a consistent description of the correlation effects along polymer chains subject ... more A framework for a consistent description of the correlation effects along polymer chains subject to flow is proposed. The formalism shows how correlations between chain segments in the flow can be incorporated into a hierarchy of distribution functions for tangent vectors. The present description allows to take into account all the relevant relaxation mechanisms for slow flows. Special cases of the derived set of equations are shown to yield some existing models and shed some light on the connection between them.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2014
h i g h l i g h t s • Nanoprecipitation of polymers in a bad solvent with surfactants was examine... more h i g h l i g h t s • Nanoprecipitation of polymers in a bad solvent with surfactants was examined. • We derived a kinetic model for diffusion limited coalescence. • Final nanoparticle size is independent of polymer molar mass of the polymer. • The final particle volume increases linearly with polymer concentration. • Experimental results are in good agreement with theoretical predictions.
DOI to the publisher's website. • The final author version and the galley proof are versions of t... more DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the "Taverne" license above, please follow below link for the End User Agreement:
A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsor... more A molecular model is proposed which predicts wall slip by disentanglement of polymer chains adsorbed on a wall from those in the polymer bulk. The dynamics of the near-wall boundary layer is found to be governed by a nonlinear equation of motion, which accounts for such mechanisms on surface chains as convection, retraction, constraint release, and thermal fluctuations. This equation is valid over a wide range of grafting regimes, including those in which interactions between neighboring adsorbed molecules become essential. It is not closed since the dynamics of adsorbed chains is shown to be coupled to that of polymer chains in the bulk via constraint release. The constitutive equations for the layer and bulk, together with continuity of stress and velocity, are found to form a closed system of equations which governs the dynamics of the whole "bulkϩboundary layer" ensemble. Its solution provides a stick-slip law in terms of the molecular parameters and extruder geometry. The model is quantitative and contains only those parameters that can be measured directly, or extracted from independent rheological measurements. The model predictions show a good agreement with available experimental data.
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