Jjm Han Slot

Theory of microphase separation in multiple segment-type statistical multiblock copolymers with arbitrary block molecular weight distributions

A Landau free energy is derived for the weak segregation regime (WSR) of melts belonging to a very general class of statistical multiblock copolymers, referred to as “multiple segment-type statistical multiblock copolymers.” Copolymer chains in this class consist of sequences of up to M⩾2 chemically different types of segments, organized into sequences of blocks of varying lengths (molecular weights). The possible sequences of blocks that are encountered in the copolymer chains, as far as their type is concerned, are described by a first-order Markov process, while the block molecular weight distributions of these M types of blocks are completely arbitrary. The number of blocks per chain is assumed to be large. This class of copolymers is sufficiently general to encompass all industrial relevant bulk statistical multiblock copolymers, such as all known thermoplastic elastomers. The particular free energy considered is just one realization of an even more general Landau free energy which is applicable to the WSR of melts of all conceivable copolymers, including homopolymers and all possible blends. The derivation of this Landau free energy is given in Appendix A.

Dynamics of an electrically charged polymer jet

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.

Structure and rheology of branched polyamide 6 polymers from their reaction recipe

The structure and rheology of randomly branched polyamide melts, in particular that of branched polyamide 6, are predicted on the basis of their initial reaction recipe. To this end, a Monte Carlo approach has been developed in order to build different molecular architectures from the initial reactant monomers at the appropriate conversion level. This approach allows us to analyze the composition of these melts in terms of topological architecture and molecular weight of the various polymer species present. Subsequently, the linear rheology of each sample is predicted within the tube model framework [van Ruymbeke et al., Macromol. 2006], based on the position/seniority of the different branches in these polymer species, by averaging over a limited number of representative segments. This approach allows us to discuss the role the different polymer architectures play in the overall viscoelastic response, the importance of the different initial monomers to adequately tune the composition (and thus the rheology) of these branched systems and the necessity of reaching a high conversion level in order to obtain a large zero-shear viscosity. We also extend this approach by applying a bimodal distribution to describe the solid state polycondensation of these products. The predictions are in good agreement with experiments. This method may be applied to any branched polymer product that is synthesized via a melt condensation type reaction and can be used as a tool to test and screen in detail the flow properties of materials without prior synthesis.

A simple constitutive model for a polymer flow near a polymer-grafted wall

A simple constitutive model is proposed to describe a polymer flow near a polymer-grafted wall. The model is based on a generalization of the Rolie-Poly equation [A. E. Likhtman and R. S. Graham, J. Non-Newton. Fluid Mech. 114, 1–12 (2003)] to a “bulk+wall” system combined with a microscopic picture of the relaxation of the tethered chains. Different grafting regimes are considered, varying from nonoverlapping to strongly interacting tethered chains. Despite its simplicity, the model allows one to reproduce all the generic features of the flow. Different scaling regimes are predicted, in accord with earlier studies, and the transition between them is quantified. Special attention is paid to a careful comparison to available experimental data: a reasonable agreement is demonstrated and possible shortcomings of the model are discussed.

Composition and rheology of polyamide-6 obtained by using bi- and tri-functional coupling agents

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 (A2 type) or a triacid (A3 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 A2 can be seen as flow improver, the effect of branching agents of type A3, 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, Mn, is discussed in function of the amount of A2 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.