The influence of epoxy resin on the morphological and rheological properties of PET/PA66 blend

Interfacial reactions have dominant effects on the morphological and rheological properties of compatibilized polymer blends. This work aims to investigate the effect of epoxy resin, as a coupling agent, on the interface properties and subsequent influences on the morphological and rheological properties of polyethylene terephthalate/polyamide66 (PET/PA66) blend. PET/PA66 70/30 blends with different amount of bisphenol A epoxy resin (0, 1, 3, and 5 wt.%) were prepared. SEM micrographs show reduction in droplet size with increasing epoxy resin concentration, confirming the reactive compatibilizing effect of the epoxy resin. Reactions at the interface of the PET-EP-PA66 blend are confirmed by FTIR spectra. Shear viscosity results demonstrates that adding epoxy resin could suppress the interfacial slip at the blend interphase. Obtained results from storage modulus (G′) curves show the presence of one plateau for the blends at low frequency region; nevertheless, relaxation spectra indicate the presence of two more relaxation mechanisms than precursors which are related to the shape relaxation of droplets and the interface relaxation. The presence of the interface relaxation time in the blend without epoxy resin can prove the presence of reactions between two condensation polymers; however, adding the epoxy resin results in reducing both relaxation time and interfacial tension and increasing interfacial shear modulus. These observations indicate that the epoxy resin has been successful to boost the reactions at the interface between two polymers. Fitting the obtained experimental data using Palierne model indicates that the general Palierne model could describe rheological properties of the blends very well.     

Polypropylene-polyethylene blends

Summary Die swell behaviour and morphology of melt blends of isotactic polypropylene (PP) and high density polyethylene for pure polymers and blends with 25, 50 and 75 weight % PP are described in the present study. A light interference contrast microscopy technique was used for the morphological characterization of melt blends and extrudate samples of the blends obtained with an Instron capillary rheometer. The results indicate that the domains from blends where the dispersed phase has higher viscosity than the continuous phase remain as continuous domains in the extrudate whereas domain destruction takes place when blends where the continuous phase has the higher viscosity are extruded.The die swell behaviour as well as the fiber forming properties of extrudates of melts having unstable domains extruded at high shear stresses resemble the behaviour of homopolymers, whereas samples with stable domains are significantly different, die swell increases with temperature at constant shear stress and stable fibers cannot be obtained after necking.With 10 figures and 1 table     

Transient shear and elongational behavior of blends of PET with a LCP

Blends of polyethylene terephthalate (PET) with a liquid crystalline polymer (LCP) and a compatibilizer were produced by twin screw extrusion and injection molding. Transesterification and compatibilization studies were made in a torque rheometer. The morphology of the injection-molded plaques was studied by scanning electron microscopy. The blends shear growth function was measured in a cone and plate rheometer. The elongational growth function was measured in a modified rotational rheometer. Transesterification was observed in the PET/LCP/compatibilizer 95/5/0 blend. The injection-molded plaques displayed the usual “skin-core” morphology. All the blends were highly shear-thinning, even at low shear rates; thus, a zero-shear viscosity could not be calculated. The compatibilized blend had the highest shear viscosity of all the blends, confirming the strong PET/LCP interphase and the effectiveness of the compatibilizing agent. On the other hand, the 90/10/0 blend had the lowest shear viscosity. All the blends showed strain softening behavior, similar to the PET. The 90/10/0 blend had the highest elongational growth function, while the 95/5/0 had the lowest. The compatibilized blend had an intermediate behavior between both blends.     

Rheology of polymer blends

Rheological properties of blends of amorphous and crystalline polymers were studied for a broad range of compositions and temperatures. It was established that below the melting pointT _m the viscoelastic properties of blends of crystalline polymers are similar to those of polymers filled with mineral fillers. In both cases these properties are influenced by the existence, in such systems, of a temporary structural network formed by mineral or polymeric particles and its subsequent breakdown under the action of shear stresses. It was found that an anomalous decrease in the melt viscosity of the main component on addition of a small amount of a second polymer depended on deformation conditions. The comparison of data on viscoelastic properties and thermodynamic interaction between the components in the melt, estimated from the parameter ₂₃ of a new Flory theory, shows that the sharp drop of viscosity takes place in the region of microphase separation due to the appearance of an excess free volume in the interphase region. Calculation of the relaxation spectra for various blends also revealed marked changes when various amounts of a second component were added to the main polymer.     

Flow instability for binary blends of linear polyethylene and long-chain branched polyethylene

The rheological properties and flow instability are studied for binary blends composed of a long-chain branched polyethylene and a linear polyethylene. It is found that the blends containing a linear-polyethylene with high shear viscosity exhibit higher oscillatory moduli, drawdown force, and strain-hardening behavior. The blends showing the anomalous rheological phenomena show sharkskin failure in low shear rate region as compared with a pure linear polyethylene. Moreover, the blends exhibit severe gross melt fracture at low output rate. Enhanced strain-hardening in elongational viscosity and large entrance angle at a die entry will be responsible for the severe gross melt fracture for the blends.     

Dynamics and rheology of the morphology of immiscible polymer blends – on modeling and simulation

 The material properties of heterogeneous polymer blends are crucially influenced by their morphology, i.e., by the spatial structure of the blend components and by the specific configuration of the interfaces separating the phases. Hence, in order to understand the behavior of experimentally obtained morphologies, one is interested in modeling the relevant dynamics of the morphology subject to external flow. Thus one can study, e.g., through the interfacial stress tensor the rheological properties due to the interfaces. The balance equations used for that purpose are based on a Cahn-Hilliard equation for the local concentration, the continuity equation, and a modified Navier-Stokes equation for the local velocity. The essential material and processing parameters such as surface tension, viscosity and volume fraction of both polymers, and imposed shear rate are taken into consideration as model coefficients. By regarding hydrodynamic interaction, which is proved to be important in case of immiscible blends, the interfacial relaxation is described properly. Simulations in both three and two dimensions agree at least qualitatively with experimental results concerning droplet deformation, droplet coalescence, and interfacial rheological properties of the blend. Received: 25 September 2000 Accepted: 24 April 2001     

Rheological properties of carbon black-filled blends of liquid-crystalline copolyester with thermoplastic polysulfone

Rheological properties of a two-phase polymeric blend containing LCCPE of poly(ethylene terephthalate) and p-hydroxybenzoic acid and thermoplastic polysulfone with varying concentrations of polymeric components and particulate filler have been studied. The theological behavior of such blends at different temperatures is governed by variation of the degree of ordering of LC-CPE macromolecules associated with the phase transition in the CPE at 260°C. Experimental results are discussed on the basis of concepts of compatibility of polymeric components in the melt or, if the system is incompatible, of the degree of interphase interaction between the components, as well as the impact of the filler and of the shear straining conditions on structurization in the system and compatibility. The filler exerts a compatibilizing effect on blend components, while the shear stress encourages the phase separation in the system. An extremal variation of viscosity of the LC-CPE/carbon black, silica and talk blends with the filler concentration on both at the flow in a uniform shear stress field and at the capillary flow has been found. Normalization of the filler concentration with respect to its specific surface yields a unified concentration dependence of the relative viscosity of LC-CPE filled with solid particles of various natures and specific surfaces.     

Slip at the interface between immiscible polymer melts I: method to measure slip

Slip at the interface between immiscible polymer melts remains poorly understood. A method that relies solely on rheological measurements to obtain the interfacial slip velocity uses the slip-induced deviation in the flow variables. To use the method, accurate estimates of the flow variables under the assumption of no-slip are necessary. Although such estimates can be easily derived under some cases, in general, this is not straightforward. Therefore, methods to determine the interfacial slip velocity without using estimates for the flow variables under no-slip conditions are desirable. In this work, we focus on investigations of slip at the interface between two immiscible polymer melts undergoing two-phase coaxial flow. To enable such investigations, we have adapted the Mooney method, usually used to investigate wall slip, to investigate polymer/polymer interfacial slip. Using this method, we have measured the slip velocity at the interface between polypropylene and polystyrene as a function of the interfacial stress. To determine the validity of the modified Mooney method, we also determine the slip velocity using the slip-induced deviation in the flow variables. To enable this determination, we use polypropylene and polystyrene with almost identical shear rate-dependent viscosities over a range of shear rates. The slip velocity obtained from the modified Mooney method displayed excellent agreement with that determined using the deviation from no-slip. In agreement with prior work, the dependence of the slip velocity on the interfacial stress is a power-law. Our investigation spans a sufficiently wide range of interfacial stress to enable the direct observation of two power-law regimes and also the transition between the two regimes. We also find that the power-law exponent of approximately 3 at low stresses decreases to approximately 2 at high stresses.     

Stress relaxation behavior of co-continuous PS/PMMA blends after step shear strain

Stress relaxation probing on the immiscible blends is an attractive route to reveal the time-dependent morphology–viscoelasticity correlations under/after flow. However, a comprehensive understanding on the stress relaxation of co-continuous blends, especially after subjected to a shear strain, is still lacking. In this work, the stress relaxation behavior of co-continuous polystyrene/poly(methyl methacrylate) (50/50) blends with different annealing times, strain levels, and temperatures was examined under step shear strain and was correlated with the development of their morphologies. It was found that co-continuous blends display a fast relaxation process which corresponded to the relaxation of bulk polymer and a second slower relaxation process due to the recovery of co-continuous morphology. The stress relaxation rates of co-continuous blends tend to decrease due to the coarsening of instable co-continuous structure during annealing. Furthermore, the stress relaxation of the co-continuous blends is strongly affected by the change of viscosity and interfacial tension caused by the temperature. The contribution of morphological coarsening, viscosity, and interfacial tension variation on the stress relaxation behavior of co-continuous blends was discussed based on the Lee–Park model and time–temperature superposition principle, respectively.     

Rheological behavior of filled propylene/ethylene copolymers

A new family of propylene-ethylene copolymers developed by The Dow Chemical Company has narrow molecular weight distributions for industrial polymers and broad chemical composition distributions. This molecular architecture makes possible high filler loadings while maintaining good processability. To provide a fundamental understanding of the lower than expected viscosity, a study of the shear rheological behavior of two series of composites was performed. The composites consist of stearate-coated calcium carbonate particles suspended in a propylene-ethylene copolymer. The matrix in one series was a new copolymer, and in the other series, it was a traditional metallocene copolymer. For both systems, the viscosity increases dramatically with increasing filler loading; however, the viscosity is lower in the case of the composites of the new copolymer. The stearate coating on the calcium carbonate particles decreases the adhesion of the polymer to the filler surface, allowing particle-matrix interfacial slip. A high temperature atomic force microscopy study has indicated the existence of ethylene-enriched zones in the matrix immediately surrounding the particles in the new copolymer. We hypothesize that these high ethylene content chains around the particle surface enhance particle-matrix interfacial slip resulting in the lower composite viscosity.     

Isothermal elongational behavior of liquid-crystalline polymers and LCPs based blends

The rheological behavior of two flexible thermoplastics, Nylon-6 (Ny) and bisphenol-A polysulfone (PSu), and two wholly aromatic liquid crystalline polymers, Vectra-A900 (VA) and Vectra-B950 (VB), as well as that of Ny/VB and PSu/VA blends with 10% LCP, has been investigated by the use of capillary viscometers equipped with cylindrical dies having different length-to-diameter ratios. The elongational viscosity of all materials was calculated, from the results of isothermal measurements carried out at 290°C, by means of the Cogswell's analysis, based on the estimation of the pressure drop due to the converging flow at the die inlet. The behavior in elongational flow was compared with the rheological behavior in shear flow conditions. It was found that the elongational viscosities of VA and VB are very large and account for a fairly marked pressure drop at the die entrance, due to the orientation of the LCP domains taking place in the converging flow zone. For these materials, the ratio of the elongational viscosity to the Newtonian shear viscosity is up to two orders of magnitude higher than the value expected on the basis of the Trouton rule. For the flexible resins, the Trouton ratio is 3 and ca. 3–10, are common values for high molar mass linear polymers. The addition of 10% LCP into the flexible resins strongly increases their elongational viscosity and makes the blends resemble neat LCPs in their extensional flow behavior. In shear flow, on the contrary, the addition of LCP was shown to induce a marked reduction of the melt viscosity, even when, as for the Ny/VB blend, the LCP is more viscous than the matrix.     

Direct numerical simulation of surfactant-stabilized emulsions

A 3D lattice Boltzmann model for two-phase flow with amphiphilic surfactant was used to investigate the evolution of emulsion morphology and shear stress in starting shear flow. The interfacial contributions were analyzed for low and high volume fractions and varying surfactant activity. A transient viscoelastic contribution to the emulsion rheology under constant strain rate conditions was attributed to the interfacial stress. For droplet volume fractions below 0.3 and an average capillary number of about 0.25, highly elliptical droplets formed. Consistent with affine deformation models, gradual elongation of the droplets increased the shear stress at early times and reduced it at later times. Lower interfacial tension with increased surfactant activity counterbalanced the effect of increased interfacial area, and the net shear stress did not change significantly. For higher volume fractions, co-continuous phases with a complex topology were formed. The surfactant decreased the interfacial shear stress due mainly to advection of surfactant to higher curvature areas. Our results are in qualitative agreement with experimental data for polymer blends in terms of transient interfacial stresses and limited enhancement of the emulsion viscosity at larger volume fractions where the phases are co-continuous.     

Strain recovery of model immiscible blends without compatibilizer

Strain recovery after the cessation of shear was studied in model immiscible blends composed of polyisobutylene drops (10–30% by weight) in a polydimethylsiloxane matrix. Blends of viscosity ratio (viscosity of the drops relative to the matrix viscosity) ranging from 0.3 to 1.7 were studied. Most of the strain recovery was attributable to interfacial tension, and could be well-described by just two parameters: the ultimate recovery and a single retardation time. Both these parameters were found to increase with the capillary number of the drops prior to cessation of shear. For blends that had reached steady shear conditions, the ultimate recovery decreased with increasing viscosity ratio, whereas the retardation time increased with increasing viscosity ratio. The retardation time was well-predicted, but the ultimate recovery was over-predicted by a linear viscoelastic model developed previously by Vinckier et al. (Rheol Acta 38:65–72, 1999).     

Effect of melt viscosity of polypropylene on fibrillation of thermotropic liquid crystalline polymer in in situ composite film

 Various grades of polypropylene were melt blended with a thermotropic liquid crystalline polymer, a block copolymer of p-hydroxy benzoic acid and ethylene terephthalate (60/40 mole ratio). The blends were extruded as cast films at different values of draw ratio (slit width/film thickness). Fibrillation of TLCP dispersed phase with high fiber aspect ratio (length/width) was obtained with the matrix of low melt flow rate, i.e., high viscosity and with increasing film drawing. Melt viscosities of pure components and blends measured using capillary rheometer were found to decrease with increasing shear rate and temperature. Viscosity ratios (dispersed phase to matrix phase) of the systems being investigated at 255 °C at the shear rate ranged from 10² to 10⁴ s⁻¹, were found to lie between 0.04 and 0.15. The addition of a few percent of elastomeric compatibilizers; a tri-block copolymer SEBS, EPDM rubber and maleated-EPDM, was found to affect the melt viscosity of the blend and hence the morphology. Among these three compatibilizers, SEBS was found to provide the best fibrillation. Received: 10 January 2000/Accepted: 24 January 2000     

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     

Enhanced melt strength and stretching of linear low-density polyethylene extruded under strong slip conditions

The influence of extrusion under strong slip conditions on the extensional properties of linear low-density polyethylene was studied in this work. The material was extruded at two different temperatures under strong slip and no slip conditions, and was subsequently subjected to uniaxial elongational flow by means of a Rheotens device. Strong slip was evident through the elimination of sharkskin distortions and the stick-slip instability, as well as by the electrification of the extrudates. The extrudate swell was smaller in the presence of slip when comparing with no slip conditions at constant apparent shear rate, but it was found to be a unique function of the shear stress if comparison was performed at constant stress. The draw ratio and melt strength of the filaments obtained under slip conditions were larger compared to those without slip. In addition, draw resonance was postponed to higher draw ratios during the extrusion with strong slip at constant apparent shear rate. It is suggested that slip of the polymer at the die wall decreases the shear stress in the bulk, and therefore, restricts the disentanglement and orientation of macromolecules during flow, which subsequently produces the increase in draw ratio and melt strength during stretching.     

Specific rheology – morphology relationships for some blends containing LCPs

For the blend melts of isotropic polysulfone (PSF) and LC polyester (PES), differing in viscosity more than 10 times, the flow curves with maxima were observed in cone and plate geometry. The low shear rate branch is located near the PSF flow curve, and the high shear rate branch is close to the PES flow curve. At high strains, the formation of the ring-like morphology of the blend sample, accompanied by appearance of maximum on flow curve, was registered. The scaling analysis of the reasons for the ring morphology formation was based on stretching of the large, low-viscous LC droplet, embedded to the high-viscous polymer matrix, in a homogeneous shear field. It was shown that, if the critical Taylor radius is not exceeded, the droplet may form the closed torus. Under strong flows, the PSF melt manifests the “spurt effect”, consisting of a drastic increase of the shear rate when the critical value of the shear stress is reached. The pattern of the blend flow curves with maxima may be explained by a vanishing PSF input to the total shear stress, inherent for blends, while the PES melt continues to be in a liquid state and, consequently, is responsible for the blend viscosity at the high shear rates. The presence of regular heterogeneities in the blend in the form of LC rings may initiate the rupture of the entanglements network of the matrix PSF (close to LC rings) under strong shear flows. The appearance of the low-viscous “cracks” at the critical shear stress will diminish the contribution of the PSF to the blends rheological response. Received: 20 April 1999 Accepted: 28 January 2000     

Rheology and morphology of starch/synthetic polymer blends

Corn starch and maleic anhydride functionalized synthetic polymers were melt blended in a Haake twin-screw extruder. The amount of starch in the blends was 60 and 70% by weight. The synthetic polymer used was either styrene maleic anhydride (SMA) or ethylene propylene maleic anhydride copolymer (EPMA). The blends did not exhibit normal thermoplastic behavior; and hence, rheological data was obtained by extrusion feeding the material through a slit die or cylindrical tube viscometer. The starch/SMA blends were extruded through a slit viscometer with a 45% half entry angle, while the starch/EPMA blends were extruded through a cylindrical tube viscometer with a half entry angle of 37.5°. For the blends, data could be obtained at low to moderate shear rates (10< _app<200s^–1). At higher shear rates, blends exhibited slip and/or degradation of starch. The viscosity of the blends exhibited shear-thinning properties. Regrinding and re-extruding through the viscometer a second time showed a significant reduction in shear viscosity for starch/SMA blends. Gel permeation chromatography data indicated that starch macromolecules degraded upon successive extrusion. Extensional viscosity, as estimated from entrance pressure drop method for starch/EPMA blends showed stretch thinning properties. Regrinding and re-extruding showed that the samples were more sensitive to changes in extensional viscosity as observed from the Trouton ratio versus extension rate plot. Optical microscopy showed the presence of starch granules after melt blending, the size of which was related to the torque (or stress) generated during extrusion. The higher the torque, the smaller the size of the starch granules. Successive extrusion runs reduced the number of unmelted granules.Nomenclature A,B Constants associated with power law fluids (Pa s^{m or n}) - e Entrance correction - H Height of slit die (m) - m, n Flow behavior index in shear and extension flow respectively - P _s Shear component of the entrance pressure drop (Pa) - P _e Extensional component of the entrance pressure drop (Pa) - Q volumetric flow rate (m³S^–1) - R _o radius of barrel exit (m) - R ₁ radius of cylindrical die (m) - T _r Trouton ratio - w width of slit die (m) - pressure gradient (Pam^–1) - half die entry angle - P _en Entrance Pressure Drop (Pa) - apparent extension rate (s^–1) - apparent shear rate (s^–1) - _w wall shear stress (Pa) - first normal stress difference in uniaxial extension (Pa)     

Wall slip and melt fracture of poly(lactides)

The wall slip and melt fracture behaviour of several commercial polylactides (PLAs) as well as their rheological properties under shear and extensional have been investigated. The PLAs have had weight-average molecular weights in the range of 10⁴–10⁵ g/mol and studied in the temperature range of 160–200°C. The solution properties and linear viscoelastic behaviour of melts indicate linear microstructure behaviour. PLAs with molecular weights greater than a certain value were found to slip, with the slip velocity to increase with decrease of molecular weight. The capillary data were found to agree well with linear viscoelastic envelope once correction for slip effects was applied. The onset of melt fracture for the high molecular weight PLAs was found to occur at about 0.2 to 0.3 MPa, depending on the geometrical characteristics of the dies and independent of temperature. Addition of 0.5 wt.% of a polycaprolactone (PCL) into the PLA that exhibits melt fracture was found to be effective in eliminating and delaying the onset of melt fracture to higher shear rates. This is due to significant interfacial slip that occurs in the presence of PCL.     

Rheology and morphology of multilayer reactive polymers: effect of interfacial area in interdiffusion/reaction phenomena

The rheological behavior of multilayered reactive polymers was investigated. Dynamic mechanical experiments were performed to probe the effect of the interfacial area on the rheological behavior of a multilayered structure as compared to that of a droplet-type morphology. Polyamide (PA6)/polyethylene grafted with glycidyl methacrylate was used as a model system, and in the molten state, such a system generated a reaction between amine, carboxylic, and epoxy groups. Multilayer structures containing various amounts of both interfacial area and volume fractions of the two components were studied. Relationships between viscoelastic material functions and compositions were used to analyze the effects of bulk and reactive functions in the polyolefin phase at the interface with PA. The contribution of the interface/interphase effect was investigated along with the increase in the number of layers, and the results showed that the variation in dynamic modulus of the multilayer system was a result of both diffusion and chemical reaction. Specific experiments were carried out to separate the thermodynamic effects from the kinetic ones, and the results were rationalized by comparing the obtained data with theoretical models. Finally, the effect of the interface/interphase triggered between the neighboring layers was quantified at a specific welding time and shear rate.