Rheological properties of polymer blends with sphere-in-sphere morphology

The linear viscoelastic behavior of polystyrene (PS) and poly(methylmethacrylate) (PMMA) blends with PS as the matrix and amounts of PMMA in the range 10–30 wt% was investigated. Transmission electron microscopy (TEM) revealed a complex morphology which was characterized by the existence of composite particles; the PMMA particles which are enclosed in the PS matrix themselves carry PS inclusions. In order to explain the G* data of these blends a model is presented which consists of a Palierne model for the composite particles and a Palierne model for the whole blend, taking into account composite and neat particles. Simulations show the principal relevance of the assumptions made. Moreover, it is shown that the measurements agree well with the model for the whole measured frequency region and that the fit parameters, the size of the composite particles and the concentration and size of interior particles are in reasonable agreement with data available from TEM. Received: 1 November 1998 Accepted: 5 April 1999     

Rheological behavior of compatibilized and non-compatibilized PA6/EPM blends

The rheological properties of PA-6/EPM polymer blends, non-compatibilized and compatibilized with grafted ethylene propylene rubber (EPM-g-MA), have been investigated. Linear and non-linear (relaxation both in shear and extension) experiments were realized. Stress relaxation experiments coupled with scanning electron microscopy (SEM) analysis showed the existence of one relaxation time and non-deformed droplets for the immiscible blend, and two relaxation times and deformed droplets for the compatibilized ones, the second relaxation being more pronounced for higher compatibilizer contents. These results clearly indicate that, despite the high viscosity and elasticity ratios, if high amounts of compatibilizer are added to the blend, interfacial slip is suppressed and a high-enough adhesion between the phases is achieved for the high-viscosity dispersed phase to be deformed. Paper presented at the 3rd Annual European Rheology Conference, April 27–29, 2006, Crete, Greece     

Rheological behavior of poly(methyl methacrylate)/polystyrene (PMMA/PS) blends with the addition of PMMA-<Emphasis Type="BoldItalic">ran</Emphasis>-PS

In this work, the dynamic behavior of poly(methyl methacrylate)/polystyrene blend to which P(S_0.5-ran-MMA_0.5) was added was studied. Several blend (ranging from 5 to 20 wt% of dispersed phase) and copolymer (up to 20 wt% with respect to dispersed phase) concentrations were studied. The rheological behavior of the blends was compared to Bousmina’s (Rheol Acta 38:73–83, 1999) and Palierne’s (Rheol Acta 29:204–214, 1990) generalized models. The relaxation spectra of the blends were also inferred, and the results were analyzed in light of the analysis of Jacobs et al. [J Rheol 43:1495–1509, 1999]. The relaxation spectra of the blends with smaller dispersed phase (below 10 wt%) and larger copolymer concentrations (above 0.4 wt%) showed the presence of four relaxation times, two corresponding to the blend phases, τ _F , corresponding to the relaxation of the shape of the dispersed phase of the blend and that can be attributed to the relaxation of Marangoni stresses tangential to the interface between the dispersed phase and matrix. The experimental values of and were used to infer the interfacial tension (Γ) and the interfacial complex shear modulus (β) for the different blends, Γ decreased with increasing copolymer concentration. β decreased with increasing blend dispersed phase concentration and decreasing copolymer concentration. The predictions of Palierne’s generalized model were found to corroborate the experimental data once the values of Γ and β, found analyzing the relaxation spectra, were used in the calculations. Bousmina’s model was found to corroborate the data only for larger dispersed phase concentration. Paper was presented at the 3rd Annual Rheology Conference, AERC 2006, April 27–29, 2006, Crete, Greece.     

Rheology and morphology of polystyrene/polypropylene blends with in situ compatibilization

Rheology and flow-induced morphology were studied in immiscible polypropylene (PP)/polystyrene (PS) blends with a droplet–matrix microstructure. Two reactive precursors, maleic anhydride grafted PP and amino terminated PS, were added during the melt-mixing process to form a graft copolymer. The effects of both the amount of compatibilizer and the shear history on the rheological and morphological behavior were investigated systematically. Small amplitude oscillatory experiments and scanning electron microscopy were used to study the phase morphology. Shear history has an important effect on the morphology of the uncompatibilized blends. The droplet size refines with increasing shear rate. The decrease of this effect with increasing degrees of in situ compatibilization is mapped out. The results are discussed in terms of interfacial tension and the interfacial coverage. It turns out that most of the conclusions that were previously obtained on physically compatibilized blends are also valid for chemically compatibilized ones.     

Effect of interfacial tension on linear viscoelastic behavior of immiscible polymer blends

When interfacial tension is increased from zero to infinity, the storage dynamic modulus predicted by Palierne's model varies in a nearly Gaussian fashion with almost equal asymptotic values at the limits of low and high interfacial tension. We report a simple physical discussion of such an effect. Received: 13 January 1999 Accepted: 22 March 1999     

Noether's theory of mechanical systems with unilateral constraints

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Rheological properties of network models with configuration-dependent creation and loss rates

A numerical stochastic approach allows the exact solution of the convection equation arising in network theories. We now want to show the flexibility and the limits of this approach by studying the rheological properties of different kinds of models.     

Manifestation of phase separation processes in oscillatory shear: droplet-matrix systems versus co-continuous morphologies

Phase separation processes in mixtures of poly-α-methylstyrene-co-acrylonitrile (PαMSAN) and poly-methylmethacrylate (PMMA) with lower critical solution temperature (LCST) behavior have been studied, focusing on the manifestation of the interface in oscillatory shear measurements. By using blends of different composition, systems with a droplet-matrix morphology or a co-continuous structure are generated during the phase separation process. The feasibility of probing this morphology development by rheological measurements has been investigated. The development of a disperse droplet phase leads to an increase in the elasticity of the blend at low frequency, showing up as a shoulder in the plot of storage modulus versus frequency. Here, the droplet growth is unaffected by the shear amplitude up to strains of 0.2; therefore the resulting dynamic data are suitable for quantitative analysis. In contrast, for blends in which phase separation leads to a co-continuous structure, the storage modulus shows a power law behavior at low frequency and its value decreases as time proceeds. For the latter systems, effects of the dynamic measurement on the morphology development have been observed, even for strain amplitudes as low as 0.01. To probe the kinetics of morphology evolution in droplet-matrix systems, measurements of the time dependence of the dynamic moduli at fixed frequency should be performed (for a whole series of frequencies). Only from such measurements, curves of the frequency dependence of the moduli at a well defined residence time can be constructed. From fitting these curves to the emulsion model of Palierne, the droplet diameter distribution at that particular stage in the phase separation and growth process can be obtained. It is not appropriate to use a simplified version of the Palierne model containing only the average droplet size, because a morphology with too broad a size distribution is generated. Received: 15 February 1999 Accepted: 20 May 1999     

Dynamics of finite element structural models with multiple unilateral constraints

Fast and accurate simulation of mechanical structures with complex geometry requires application of the finite element method. This leads frequently to models with a relatively large number of degrees of freedom, which may also possess non-linear properties. Things become more complicated for systems involving unilateral contact and friction. In classical structural dynamics approaches, such constraints are usually modeled by special contact elements. The characteristics of these elements must be selected in a delicate way, but even so the success of these methods cannot be guaranteed. This study presents a numerical methodology, which is suitable for determining dynamic response of large scale finite element models of mechanical systems with multiple unilateral constraints. The method developed is based on a proper combination of results from two classes of direct integration methodologies. The first one includes standard methods employed in determining dynamic response of structural models possessing smooth non-linearities. The second class of methods includes specialized methodologies that simulate the response of dynamical systems with unilateral constraints. The validity and effectiveness of the methodology developed is illustrated by numerical results.     

Rheological predictions of a transversely isotropic fluid model with extensible microstructure

A continuum extensible director theory was formulated to describe the isothermal, incompressible flow of uniaxial rodlike semiflexible liquid crystalline polymers. The model is strictly restricted to material that flow-align in shear, and that, in the absence of flow, are sufficiently far from the nematic-isotropic phase transition. The microstructure of the continuum is described by a variable length director, but the extensibility is finite. The model is an extension of the TIF (Transversely Isotropic Fluid) model of Ericksen (1960). The thermodynamic restrictions on the model parameters are found using the non-negative definiteness of the entropy production. The rheological material functions predicted by the model are calculated for steady simple shear and steady uniaxial extensional flows. In the rigid rod limit the model predictions agree with those of the TIF model, and for the finite extensibility case the model predictions are in agreement with those associated with flexible isotropic polymers: strong non-Newtonian shear viscosity, positive first normal stress differences, recoverable shear of order one, negative second normal stress differences, and a maximum in the steady uniaxial extensional viscosity.     

Temperature dependence of the interfacial tension of PS/PMMA, PS/PE, and PMMA/PE blends

The effect of temperature on the interfacial tension for PS/PMMA, PS/PE, and PMMA/PE was measured using the imbedded fiber retraction method. Interfacial tensions for PS/PMMA, PS/PE, and PMMA/PE were measured over temperature ranges of 160–250 °C, 140–220 °C, and 140–220 °C, respectively. The interfacial tension was found to follow a dependence of 3.6–0.013 T dyn/cm, 7.6–0.051 T dyn/cm and 11.8–0.017 T dyn/cm for PS/PMMA, PS/PE, and PMMA/PE, respectively. Comparison of the data with the mean field theory of Helfand and Sapse were made; however, a simple linear fit to the data described the temperature dependence in the experimental window as well as the predictions of the mean field theory. Received: 6 July 1999 Accepted: 23 March 2000     

Quantitative rheological evaluation of phase inversion in two-phase polymer blends with cocontinuous morphology

 The present work is focused on the rheological properties of two-phase polymer blends in the phase inversion region. A large number of PS/PMMA- and PSAN/PMMA-blends has been investigated in order to establish a rheological criterion which allows the quantitative determination of the phase inversion concentration φ_PI by rheological means. Three rheological criteria based on the viscous and elastic blend properties such as maximum of dynamic viscosity η′, slope of G′, and maximum of G′ at a constant evaluation frequency have been tested. By correlating the rheological results to data from quantitative morphological analysis we could prove that the chosen rheological criteria are differently suitable for the determination of φ_PI. It has turned out that the G′ criterion is the most robust and most suitable one yielding an excellent correlation with morphological data. Based on these findings we propose a new simple equation for the prediction of φ_PI-values. Received: 14 March 2001 Accepted: 15 May 2001     

Grafting of polyamide 6 on a styrene–acrylonitrile maleic anhydride terpolymer: melt rheology at the critical gel state

In this work, we studied the melt rheology of multigraft copolymers with a styrene–acrylonitrile maleic anhydride (SANMA) terpolymer backbone and randomly grafted polyamide 6 (PA 6) chains. The multi-grafted chains were formed by interfacial reactions between the maleic anhydride groups of SANMA and the amino end groups of PA 6 during melt blending. Because of the phase separation of SANMA and PA 6, the grafted SANMA backbones formed nearly circular domains which were embedded in the PA 6 melt with a diameter in the order of 20 to 40 nm. The linear viscoelastic behaviour of PA 6/SANMA blends at a sufficiently large SANMA concentration displayed the characteristics of the critical gel state, i.e. the power relations G′ ∝ G′′ ∝ ω ^0.5. In elongation, the PA 6/SANMA blend at the critical gel state showed a non-linear strain hardening behaviour already at a very small Hencky strain. In contrast to neat PA 6, the elasticity of the PA 6/SANMA blends was strongly pronounced, which was demonstrated by recovery experiments. Rheotens tests agreed with the linear viscoelastic shear oscillations and the measurements using the elongational rheometer RME. Increasing the SANMA concentration led to a larger melt strength and a reduced drawability. The occurrence of the critical gel state can be interpreted by the cooperative motion of molecules which develops between the grafted PA 6 chains of neighbouring micelle-like SANMA domains.     

Conservation laws and symmetries of systems with unilateral constraints in phase space

By introducing the generalized quasi-symmetry of the infinitestinal transformation for transformation groupG _r , this paper studies the conservation laws and symmetries of dynamical systems with unilateral constraints in phase space. Noether's theorem and Noether's inverse theorem for mechanical systems with unilateral constraints in phase space are obtained and two kinds of equivalent forms of generalized Killing equations which are used to determine the generators of the infinitestinmal group transformation are given. The project sponsored by the National Natural Science Foundation and the Doctoral Programme Foundation of Institution of Higher Education of China.     

Evolution of drop size distribution of polymer blends under shear flow by optical sectioning

In this work, we present a methodology to investigate the evolution of drop size distribution, due to coalescence, in liquid-liquid suspensions under simple shear flow. Our approach is based on 3D motorised sample scanning by optical sectioning and offline analysis of the acquired images. The application of such automated procedures allows the detection of a large number of drops, as required to minimise sampling errors and to obtain reliable results according to statistical methods from the literature. Three-dimensional reconstruction of the locations of the drops within the sample allows to evaluate possible wall and sedimentation effects. The proposed methodology is tested on polymer blends of polybutene and silicon oil, and a good reproducibility is found.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Rheology of polymer blends with matrix-phase viscoelasticity and a narrow droplet size distribution

A Hamiltonian framework of non-equilibrium thermodynamics is adopted to construct a set of dynamical continuum equations for a polymer blend with matrix viscoelasticity and a narrow droplet size distribution that is assumed to obey a Weibull distribution function. The microstructure of the matrix is described in terms of a conformation tensor. The variable droplet distribution is described in terms of two thermodynamic variables: the droplet shape tensor and the number density of representative droplets. A Hamiltonian functional in terms of the thermodynamic variables is introduced and a set of time evolution equations for the system variables is derived. Sample calculations for homogenous flows and constant droplet distribution are compared with data of a PIB/PDMS blend and a HPC/PDMS blend with high viscoelastic contrast. For the PIB/PDMS blend, satisfactory predictions of the flow curves are obtained. Sample calculations for a blend with variable droplet distribution are performed and the effect of flow on the rheology, droplet morphology, and on the droplet distribution are discussed. It is found that deformation can increase or decrease the dispersity of the droplet morphology for the flows investigated herein.     

Rheological properties of suspensions of TiO2 particles in polymer solutions. 1. Shear viscosity

This paper presents results on the rheological behaviour of suspensions of two kinds of TiO₂ particles in two different polymer solutions. The particles differ in their hydrophilic or hydrophobic properties. The dispersing media are a solution of high molecular weight polyisobutylene in decalin and a solution of a low molecular weight polybutene in decalin. The concentrations of polymer are adjusted in order to get the same zero shear viscosity. The shear viscosity measurements display an apparent yield stress in some cases. The existence and the values of the yield stress depend on the volume fraction of solid particles and on the type of particles. The evolution of the intrinsic viscosity and of the maximum packing fraction vs the shear rate is interpreted in terms of evolution of the size and of the shape of aggregates of particles under shear. The effect of temperature on the development of the yield stress is also discussed. The results are completed by microscopic observations.     

New Conservation Laws of Energy and C-D Inequalities in Continua with Microstructure

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A parameter investigation of shear-induced coalescence in semidilute PIB–PDMS polymer blends: effects of shear rate, shear stress volume fraction, and viscosity

In this work, drop coalescence of polymer blends under shear flow in a parallel flow apparatus was investigated by optical sectioning microscopy. In each experiment, shear rate was set at values low enough to avoid any break-up phenomena. The time evolution of the drop size distribution was determined by motorized sample scanning and iterative acquisition of stacks of images along sample depth. Drop size and location in the acquired images was found by automated image analysis techniques. A systematic experimental campaign to investigate the effects of shear rate (in the range 0.1–0.5 s⁻¹), volume fraction (2.5–10%), and viscosity of the two phases (3–63 Pa s) at different viscosity ratio (0.1–2.3) was carried out. By comparing data from different experiments, it was found that at any strain value, the average drop size decreases monotonically with the shear stress, calculated as the product of shear rate and matrix viscosity. Furthermore, the coalescence rate slowed down with increasing viscosity ratio. Overall, these results provide an extensive set of data, which can be used as a benchmark for modeling shear-induced coalescence in polymer blends.Paper presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005.