Showing papers in "Rheologica Acta in 2004"

Miniature universal testing platform: from extensional melt rheology to solid-state deformation behavior

Abstract: Described is a detachable fixture for a rotational rheometer, the Sentmanat Extensional Rheometer Universal Testing Platform, which incorporates dual wind-up drums to ensure a truly uniform extensional deformation during uniaxial extension experiments on polymers melts and elastomers. Although originally developed as an extensional rheometer, this highly versatile miniature test platform is capable of converting a conventional rotational rheometer host system into a single universal testing station able to characterize a host of physical properties on a variety of polymer melts and solid-state materials over a very wide range of temperatures and kinematic deformations and rates. Experimental results demonstrating these various testing capabilities are presented for a series of polymers of varying macrostructure and physical states.

Towards a rheological classification of flow induced crystallization experiments of polymer melts

Abstract: Departing from molecular based rheology and rubber theory, four different flow regimes are identified associated to (1) the equilibrium configuration of the chains, (2) orientation of the contour path, (3) stretching of the contour path, and (4) rotational isomerization and a deviation from the Gaussian configuration of the polymer chain under strong stretching conditions. The influence of the ordering of the polymer chains on the enhanced point nucleation, from which spherulites grow, and on fibrous nucleation, from which the shish-kebab structure develops, is discussed in terms of kinetic and thermodynamic processes. The transitions between the different flow regimes, and the associated physical processes governing the flow induced crystallization process, are defined by Deborah numbers based on the reptation and stretching time of the chain, respectively, as well as a critical chain stretch. An evaluation of flow induced crystallization experiments reported in the literature performed in shear, uniaxial and planar elongational flows quantitatively illustrates that the transition from an enhanced nucleation rate of spherulites towards the development of the shish-kebab structure correlates with the transition from the orientation of the chain segments to the rotational isomerization of the high molecular weight chains in the melt. For one particular case this correlation is quantified by coupling the wide angle X-ray diffraction and birefringence measurements of the crystallization process to numerical simulations of the chain stretch of the high molecular weight chains using the extended Pom-Pom model in a cross-slot flow.

Coalescence suppression in model immiscible polymer blends by nano-sized colloidal particles

Abstract: The effect of nanometer sized silica particles (R≈16 nm) on the flow-induced morphology of immiscible polymer blends is studied. Polydimethylsiloxane (PDMS) and polyisobutylene (PIB) are chosen as model components. A stable droplet/matrix microstructure is obtained for blends of 30% PIB in 70% PDMS or vice versa. Rheological measurements are used to show that the silica particles alter the sensitivity of the of dispersed phase/matrix microstructure to shear flow. Coalescence is suppressed or at least slowed down on a practical time scale, especially when PDMS is the matrix phase. The effect of mixing conditions, pre-shear rate and particle concentration on the blend morphology are studied. Cryo-SEM is used to observe the accumulation of the particles at the interface. Blends stabilized by solid particles could provide an interesting alternative to blends compatibilized by block-copolymers.

Viscoelastic properties of magnetorheological fluids

Abstract: We have studied the rheological properties of some magnetorheological fluids (MRF). MRF are known to exhibit original rheological properties when an external magnetic field is applied, useful in many applications such as clutches, damping devices, pumps, antiseismic protections, etc. While exploiting parameters such as magnetic field intensity, particle concentration and the viscosity of the suspending fluid, we highlighted the importance of each one of these parameters on rheology in the presence of a magnetic field. We made this study by conducting rheological experiments in dynamic mode at very low strain which facilitates the comprehension of the influence of the structure on MRF rheology. Our results confirmed the link between the magnetic forces which ensure the cohesion of the particles in aggregates, and the elastic modulus. Moreover, we found that the loss modulus varies with the frequency in a similar manner than the elastic modulus. The system, even with the smallest deformations, was thus not purely elastic but dissipates also much energy. Moreover, we demonstrated that this dissipation of energy was not due to the matrix viscosity. Actually, we attributed viscous losses to particle movements within aggregates.

Effect of droplet size on the rheological properties of highly-concentrated w/o emulsions

Abstract: Rheological properties of highly concentrated emulsions of the water-in-oil type were studied. Water phase (concentration approximately 91%) consists of a supersaturated aqueous solution of nitrate salts; water comprises less than 20% by mass. The average size of droplets, D, in the emulsions was varied. It was found that the emulsions are non-Newtonian liquids and flow curves measured in a sweep regime of shearing have clear low-shear-rate Newtonian domain. The complete flow curves are fitted by the Cross equation. The elastic modulus is practically constant in a very wide frequency range. Hence the viscoelastic relaxation processes might be expected at times >>100 s and in the short-term side of the curve at approximately 0.01 s. The elastic modulus (measured in oscillating testing and in elastic recovery as well) is proportional to D -2 while the Newtonian viscosity is proportional to D −1. The time effects were observed: it was found that the emulsions behave as rheopectic materials because prolonged shearing results in an increase of viscosity in the low shear rate domain of several orders of magnitude.

The weak shear kinetic phase diagram for nematic polymers

Abstract: We study the shear problem for nematic polymers as modeled by the molecular kinetic theory of Doi (1981), focusing on the anomalous slow flow regime. We provide the kinetic phase diagram of monodomain (MD) attractors and phase transitions vs normalized nematic concentration (N) and weak normalized shear rate (Peclet number, Pe). We then overlay all rheological features typically reported in experiments: alignment properties, normal stress differences and shear stress. These features play a critical role in the synthesis between theory and experiment for nematic polymers (Larson 1999; Doi and Edwards 1986). MD type is routinely used for rheological shear characterization: cf., flow-aligning 5CB (Mather et al. 1996a), tumbling PBT (Srinivasarao and Berry 1991), and 8CB (Mather et al. 1996b), evidence for a wagging regime (Mewis et al. 1997), out-of-plane kayaking modes (Larson and Ottinger 1991), and evidence for chaotic major director dynamics (Bandyopadhyay et al. 2000). MD transitions correlate with sign changes in normal stresses (Larson and Ottinger 1991; Magda et al. 1991; Kiss and Porter 1978, 1980). Furthermore, structure formation in shear devices appears to be correlated with monodomain precursor dynamics (Tan and Berry 2003; Forest et al. 2002a). In this paper we combine seminal kinetic theory results (Kuzuu and Doi 1983, 1984; Larson 1990; Larson and Ottinger 1991; Faraoni et al. 1999; Grosso et al. 2001), symmetry observations (Forest et al. 2002b), and mesoscopic results on the fate of orientational degeneracy in weak shear (Forest and Wang 2003; Forest et al. 2003a), together with our resolved numerical simulations, to provide the kinetic flow-phase diagram of Doi theory in the weak shear regime, 01 ; as the definitive benchmark for any mesoscopic or continuum model; and experimental data can be compared in order to determine accuracy and limitations of the Doi theory in weak shear.

Rheology and microstructure of heat-induced egg yolk gels

Abstract: The evolution of native egg yolk undergoing a thermal-induced sol-gel transition was studied by using temperature controlled small amplitude oscillatory shear measurements. The critical gel point was determined according to Winter’s criterion: 1) from the measurements of storage and loss moduli as a function of heating time at different frequencies, and 2) from the exponents of the power law mechanical spectra obtained after cure experiments performed up to a maximum temperature (60–90 °C) followed by a sudden decrease in temperature up to 20 °C. Differential Scanning Calorimetry (DSC) was performed in order to investigate thermal transitions in egg yolk. Microstructure of gels was evaluated by Transmission and Scanning Electron Microscopy. The results obtained were discussed in terms of the processes involved in protein gelation: change in the protein system, aggregation of partially denaturated protein molecules and association of aggregates. As a result, an elastic gel network was always obtained. The influence of frequency, heating rate, solids concentration and maximum temperature of processing, was analysed. Most of the transformations found during thermal processing were found to be basically irreversible, even at the sol state and gel point. However, some reversible phenomena were detected during constant temperature processing depending on the maximum temperature performed.

Estimation of the parameters of Herschel-Bulkley fluid under wall slip using a combination of capillary and squeeze flow viscometers

Abstract: The determination of the parameters of viscoplastic fluids subject to wall slip is a special challenge and accurate results are generally obtained only when a number of viscometers are utilized concomitantly. Here the characterization of the parameters of the Herschel-Bulkley fluid and its non-linear wall slip behavior is formulated as an inverse problem which utilizes the data emanating from capillary and squeeze flow rheometers. A finite element method of the squeeze flow problem is employed in conjunction with the analytical solution of the capillary data collected following Mooney’s procedure, which uses dies with differing surface to volume ratios. The uniqueness of the solution is recognized as a major problem which limits the accuracy of the solution, suggesting that the search methodology should be carefully selected.

Dynamic rheological analysis of the gelation behaviour of waxy crude oils

Abstract: In this work we have characterised the viscoelastic behaviour of paraffin crystals in three different complex crude oils, close to the gelation threshold and after curing the gels under quiescent isothermal conditions, by means of oscillatory shear measurements. An increase in gelation temperature is observed with increasing oil’s molecular weight. The interactions between wax crystals and the formation of the space-filling network of interlocking wax crystals are thus facilitated by the presence of paraffins with higher molecular weight. The apparent gelation time, obtained from isothermal curing experiments, decreases as the curing temperature was decreased, and it is highly temperature-dependent. The presence and the importance of the ageing of the wax were established under isothermal conditions. It must result from a coarsening of the crystallites presents in the oil and it is, more important, close to the gel point where its full development is very slow taking several days to occur. After ageing the gels, the connective domains or junction zones linking the crystal arrays fail when relatively small strains are applied to the system and the mechanical spectra of the gels reveal an imperfect elastic network, typical rheological characteristics of a particle gel. Despite the compositional differences among the samples, the similarity of their mechanical behaviour is quite remarkable indicating that in all cases the gel-like organisation of the waxy material results from the formation of identical structures in the different oils, which is related not only to the wax content but also to the presence of other material that may reduce the crystallinity of the structure. The low fractal dimensionality obtained indicates elongated substructures. These results, together with the very high elastic modulus obtained at low volume fractions of crystallised material, are indicative of network structures with high degree of porosity: a lattice of wax crystals with large spaces among them filled by the oil and non-precipitated material.

Shear flow behavior of confined magnetorheological fluids at low magnetic field strengths

Abstract: The non-linear properties of iron based magneto-rheological (MR) fluids are investigated at low magnetic field strengths (0–1.7 kA/m) and different gap thickness (0–500 μm) in a plate-plate configuration. Single-width chain models qualitatively predict the low-shear flow behavior when plotting the field-specific viscosity, ηF, as a function of the Mason number, Mn: a slope close to −1 is observed in log-log representations. Wall depletion effects are observed when the suspensions are sheared under the presence of low external magnetic fields applied and/or large gap distances. These results are correlated to frictional yield stress measurements and chain length distribution calculations in the presence of the external magnetic field. Finally, an equivalent slip layer thickness is calculated using the method of Yoshimura and Prud’homme.

Effect of vinyl acetate content and silicate loading on EVA nanocomposites under shear and extensional flow

Abstract: In this study, three EVAs (ethylene-vinyl acetate co-polymers) with different vinyl contents (VA) ranging from 9 wt% to 28 wt% (EVA9, EVA18 and EVA28) were melt blended with organo-clay to obtain polymer layered silicate nanocomposites. Filler intercalation and exfoliation were evidenced by X-ray diffraction. The melt state viscoelastic properties of EVA nanocomposites were studied to examine the influence of clay in altering the flow properties of these polymeric nanocomposites. The EVA18 and EVA28 nanocomposites exhibited remarkable difference in dynamic and steady shear properties compared to neat polymers. On the other hand, EVA9-5% nanocomposite did not exfoliate and exhibited rheological behaviour very similar to that of the neat polymer. Furthermore, the first normal stress difference was found to be dependent on the silicate loadings when measured at low shear stresses. The uniaxial extensional viscosity measurement indicated that the strain hardening was weaker in EVA nanocomposites compared to neat polymers. Environmental scanning electron (ESE)-microscopy elucidated a possible reason for reduced strain hardening in these systems.

Quantitative analysis of melt elongational behavior of LLDPE/LDPE blends

Abstract: Shear and elongational data of blends of linear (LLDPE) and branched (LDPE) polyethylene are reported. Blends show thermo-rheological complex behavior. Also, in unidirectional shear or elongational flow, the linear-viscoelastic deformation regime of the blends is significantly reduced, and the terminal relaxation times of the blends are shifted in the direction of the LDPE homopolymer. Quantitative analysis of elongational viscosity data by use of the Molecular Stress Function (MSF) model reveals that the strain hardening behavior of LLDPE/LDPE blends is completely determined by the LDPE component. While the linear-viscoelastic response changes with blend composition, the nonlinear strain measure is independent of blend composition for blends with LDPE contents between 100% (homopolymer) and 20%. Even for blends containing only 5 or 10% of LDPE, the LDPE strain measure gives a good qualitative description of the strain hardening observed. We argue that this complex behavior of LLDPE/LDPE blends can be understood by assuming the existence of two phases in the blends: (a) one phase composed of highly branched low molecular weight (MW) chains from both the LLDPE minority phase and the low MW part of LDPE and (b) one phase composed of the high MW (more linear) part of LLDPE and the higher MW part of LDPE. Composition of the phases is both temperature and deformation dependent.

The flow-phase diagram of Doi-Hess theory for sheared nematic polymers II: finite shear rates

Abstract: The purpose of this paper is to extend the rheological predictions of the Doi-Hess kinetic theory for sheared nematic polymers from the anomalous weak shear regime (Forest et al. 2004a) to arbitrary shear rates, and to associate salient rheological and optical properties with the solution space of kinetic theory. Using numerical bifurcation software (AUTO), we provide the phase diagram of all stable monodomain orientational probability distribution functions (PDFs) and their phase transitions (bifurcations) vs nematic concentration (N) and normalized shear rate (Peclet number, Pe) for Pe≥1. Shear stresses, normal stress differences, the peak direction of the orientational distribution, and birefringence order parameters are calculated and illustrated for each type of PDF attractor: steady flow-aligning, both in and out of the flow deformation plane and along the vorticity axis; unsteady limit cycles, where the peak orientation direction rotates in-plane or around the vorticity axis or in bi-stable orbits tilted between them; and chaotic attractors first observed in kinetic simulations by Grosso et al. (2001). We pay particular attention to correlations between rheological features and the variety of monodomain phase transitions. Together with the weak flow regime, these results provide a nearly complete picture of the rheological consequences of the Doi-Hess kinetic theory for sheared monodomains of rigid, extreme aspect ratio, nematic rods or platelets.

Rheology of particle suspensions in viscoelastic media. Wood flour-polypropylene melt

Abstract: The dynamic mechanical behavior of suspensions of wood flour in polypropylene (PP) melts was investigated at varying filler concentrations. The main observed features were related to the viscoelastic nature of the polymer and to the filler aggregation, where the process of formation and destruction of particle clusters is governed by the polymer chain dynamics. The effect of the wood flour particles at low and large deformations was analyzed. The sample containing a wood flour concentration of 50% (by weight) showed a solid like behavior at low frequencies and was identified as the sample closer to a liquid-solid transition (LST). The values of the Newtonian viscosity obtained from sinusoidal oscillations at low frequencies were related to the concentration of filler in the suspensions. Moreover, a filler concentration scaling was found, that allows to obtain a master curve using the neat polymer as the reference and from which it is possible to calculate the dynamic mechanical behavior of all the suspensions. Apparently, for this system, the relaxation mechanisms of the neat polymer are not changed by the presence of the filler. However, the corresponding relaxation times are increased as a function of the filler concentration.

Control of the sharkskin instability in the extrusion of polymer melts using induced temperature gradients

Abstract: The extrusion of polymer melts is often rate limited by the onset of an elastic surface instability known as sharkskin. Appearance of these surface distortions is generally unacceptable for commercial applications. The desire to forestall the onset of sharkskin to higher output rates has motivated a considerable amount of research to characterize the nature of the instability. In this manuscript, we will present a series of detailed experiments using a custom fabricated extruder and die. By incorporating thermal breaks and precise localized temperature control of the die and barrel, predetermined temperature gradients could be induced across the extrudate. Polymers are typically very poor thermal conductors, and therefore the effects of heating or cooling from a boundary can be designed to only affect the properties of the extrudate very close to the die wall. We will present data correlating the amplitude and frequency of the sharkskin instability to the bulk and die surface temperature as well as the shear rates. The result is a quantitative processing map that characterizes the instability and demonstrates that by modifying the rheology of the polymeric fluid very near the die exit corner, it is possible to suppress or control the sharkskin instability through isolated die heating or cooling. By reformulating our data into Weissenberg and Deborah numbers using the relaxation time evaluated at the wall temperature, we demonstrate that the sharkskin surface instability is dependent only on flow kinematics and viscometric properties of the fluid very near the die wall, a result of the stress singularity present at the die exit, and independent of bulk fluid properties. This technique could conceivably increase the profitability of extrusion processes and be extended to develop precisely-controlled sharkskin for designing specific functionality into extruded surfaces.

Stick-slip flow of high density polyethylene in a transparent slit die investigated by laser Doppler velocimetry

Abstract: The oscillating flow instability of a molten linear high-density polyethylene is carefully studied using a single screw extruder equipped with a transparent slit die. Experiments are performed using laser Doppler velocimetry in order to obtain the local velocities field across the entire die width. At low flow rate, the extrusion is stable and steady state velocity profiles are obtained. During the instability, the velocity oscillates between two steady state limits, suggesting a periodic stick-slip transition mechanism. At high flow rate, the flow is mainly characterized by a pronounced wall slip. We show that wall slip occurs all along the die land. An investigation of the slip flow conditions shows that wall slip is not homogeneous in a cross section of the slit die, and that pure plug flow occurs only for very high flow rates. A numerical computation of the profile assuming wall slip boundary conditions is done to obtain the true local wall slip velocity. It confirms that slip velocities are of the same order of magnitude as those measured with a capillary rheometer.

Non Linear Rheology for Long Chain Branching characterization, comparison of two methodologies : Fourier Transform Rheology and Relaxation.

Abstract: In this study we compare three rheological ways for Long Chain Branching (LCB) characterization of a broad variety of linear and branched polyethylene compounds. One method is based on dynamical spectrometry in the linear domain and uses the van Gurp Palmen plot. The two other methods are both based on non linear rheology (Fourier Transform Rheology (FTR) and chain orientation/relaxation experiments). FTR consists in the Fourier analysis of the shear stress signal due to large oscillatory shear strains. In the present work we focus on the third and the fifth harmonics of the shear stress response. Chain orientation/relaxation experiment consists in the analysis of the polymer relaxation after a large step strain obtained by squeeze flow. In this method, relaxation is measured by dynamical spectrometry and is characterized by two relaxation times related to LCB. All methods distinguish clearly the group of linear polyethylene from the group of branched polyethylene. However, FTR and Chain orientation/relaxation experiments show a better sensitivity than the van Gurp Palmen plot. Non linear experiments seem suitable to distinguish long branched polyethylene between themselves.

Rheology and structure of precipitated silica and poly(dimethyl siloxane) system

Abstract: The reinforcing capability of precipitated silica in poly(dimethyl siloxane: PDMS) was characterized by means of bound rubber formation, solvent swelling, yield stress, rheological and dynamic properties. Volume concentration of precipitated silica in PDMS was varied from 0 to 0.16. The homogeneity of the compounds after mixing was confirmed by studying a uniformity of dispersion of silica particles in PDMS via SEM morphology of vulcanizates. Bound rubber measurements of the compounds and solvent swelling studies of vulcanizates showed that the precipitated silica exhibited much stronger interaction with PDMS than that of typical carbon black with rubbers but less than that of fumed silica with PDMS. At high volume concentrations of silica (0.128 and 0.160), a yield behavior was evident from the storage modulus measurements. The network formation due to an interaction between the precipitated silica and PDMS was visualized via dynamic property measurements.

Capillary rheometry for polymer melts revisited

Abstract: Capillary rheometry provides an efficient access to high shear rate flow properties relevant for processing. An automated gas driven capillary rheometer developed at BASF enables accurate measurements at imposed wall shear stress, thus supplementing instruments operating at imposed flow rate. A simplified treatment of dissipative heating based on the assumption of a radially flat temperature profile is outlined and justified by means of finite element simulations. The combined treatment of dissipation and pressure dependent viscosity yields relations to treat throttling experiments at imposed flow rate. Throttle pressure coefficients from a long die and an orifice agree for LDPE but significantly differ for PαMSAN. The effect is explained on the basis of identical pressure coefficients for shear and elongational flows, with regard to a constant stress, however. The effect of melt compressibility is negligible in practical capillary rheometry if the temperature and pressure coefficients of the melt density are by an order of magnitude smaller than those of the viscosity. Gas pressure driven instruments allow an effective determination of wall slip velocities from Mooney plots. This is of advantage for the investigation of the mechanism of additives or processing aids. Furthermore, imposed pressure experiments are pertinent to investigate the spurt effect of HDPE and to demonstrate that two different slip processes contribute to the apparent flow curve above spurt.

Large-deformation properties of wheat dough in uni- and biaxial extension. Part II. Gluten dough

Abstract: Rheological and fracture properties of optimally mixed flour doughs from three wheat cultivars which perform differently in cereal products were studied in uniaxial and biaxial extension. Doughs were also tested in small angle sinusoidal oscillation. In accordance with previously published results the linear region was found to be very small. The rheological properties at small deformations hardly depended on the cultivar. A higher water content of the dough resulted in a lower value for the storage modulus and a slightly higher value for tan δ. For both uniaxial and biaxial extension a more than proportional increase in stress was found with increasing strain, a phenomenon called strain hardening. In uniaxial extension (i) stresses at a certain strain were higher and (ii) the stress was less dependent on the strain rate than in biaxial extension. This indicates that in elongational flow orientational effects are of large importance for the mechanical properties of flour dough. This conclusion is consistent with published data on birefringence of stretched gluten. Fracture stress and strain increased with increasing deformation rate. The observed time-dependency of fracture properties can best be explained by inefficient transport of energy to the crack tip. Presumably, this is caused by energy dissipation due to inhomogeneous deformation because of friction between structural elements, e.g. between dispersed particles and the network. Differences in the rheological properties at large deformations between the cultivars were observed with respect to (i) stress, (ii) strain hardening, (iii) strain rate dependency of the stress, (iv) fracture properties and (v) the stress difference between uniaxial and biaxial extension.

The rheology of two-dimensional foams

Abstract: We survey simulations of two-dimensional flowing foam inspired by recent illuminating experiments. We also describe the viscous froth model, an effective tool for such simulations, which accurately represents the detailed structure of the foam and includes a linear drag force.

Rheological analysis of the structural properties effecting the percutaneous absorption and stability in pharmaceutical organogels

Abstract: This study presents the organogels of glyceryl monostearate emulsifiers and coconut oil as an alternative for developing the traditional organogels. We investigated how the emulsifier type affects the semisolid consistency and the drug release. In these aspects we compared glyceryl monostearate organogels (GMSO) to commercially available references, while studying the effect of the individual constituents on the structural and functional properties. Rheology provided indirect information on the structure, relevant from an application point of view. We observed that glyceryl monostearate as an organogelator results in a network with elastic nature and moderate crosslink energy. The products had low viscosity and low yield value which means practically an easily spreadable pharmaceutical dosage form with soft consistency. Modelling the percutaneous absorption in vitro, we observed that the diffusion of the piroxicam incorporated was significantly affected by the thermodynamical potency of piroxicam, which was favoured by the emulsifier. The glyceryl monostearate enhanced the partition of the suspended drug, resulting in higher drug release.

Molecular orientation in injection molding: experiments and analysis

Abstract: Modeling and simulation of the injection molding process of thermoplastic polymers has remarkably improved over the last decade. One of the most challenging scientific objectives is currently the reliable prediction of molecular orientation simulations of the molding process. Indeed, although pressure and velocity distribution can be satisfactorily described by viscous models, the viscoelastic nature of the polymer needs to be accounted for in the description of molecular orientation evolution. In this work, an amorphous PS was injection molded into a line gate rectangular cavity. Molding tests are carefully characterized and all information needed for further analysis is provided. The molds contained special dies that could accept various sized gates. In particular two gates were used whose thicknesses were 1.5 mm and 0.5 mm, respectively. Birefringence distribution (which for PS is essentially the orientation distribution) along the thickness direction was measured by using the wedge method at different positions in the moldings, and inside the gates. Data regarding the amount of frozen-in molecular strain were gathered by measuring the thermal shrinkage at different positions along the flowpath. Molding tests were simulated by means of a software developed at the University of Salerno, and a simple viscoelastic model was used to describe the evolution of molecular orientation due to the effect of kinematics obtained using a viscous approach. Simulation results describe the main features of experimental data collected from the molded samples; in particular, the effect of the packing flow is clear in both the data and simulations. In addition, the importance of the effect of pressure on relaxation time is discussed.

Break-up of a Newtonian drop in a viscoelastic matrix under simple shear flow

Abstract: The effect of matrix elasticity on the break-up of an isolated Newtonian drop under step shear flow is herein presented. Constant-viscosity, elastic polymer solutions (Boger fluids) were used as matrix phase. Newtonian silicon oils were used as drop phase. Three viscosity ratios were explored (drop/matrix), i.e. 2, 0.6 and 0.04. Following the theoretical analysis of Greco [Greco F (2002) J Non-Newtonian Fluid Mech 107:111–131], the role of elasticity on drop fluid dynamics was quantified according to the value of the parameter p=τ/τem, where τ is a constitutive relaxation time of the matrix fluid and τem is the emulsion time. Different fluids were prepared in order to have p ranging from 0.1 to 10. At all the viscosity ratios explored, break-up was hindered by matrix elasticity. The start-up transient of drop deformation, at high, but sub-critical capillary numbers, showed an overshoot, during which the drop enhanced its orientation toward the flow direction. Both phenomena increase if the p parameter increases. Finally, the non-dimensional pinch-off length and break-up time were also found to increase with p.

Modeling flow induced crystallization in film casting of polypropylene

Abstract: Data from iPP film casting experiments served as a basis to model the effect of flow on polymer crystallization kinetics. These data describe the temperature, width, velocity and crystallinity distributions along the drawing direction under conditions permitting crystallization along the draw length. In order to model the effect of flow on crystallization kinetics, a modification of a previously defined quiescent kinetic model was adopted. This modification consisted in using a higher melting temperature than in the original quiescent model. The reason for the modification was to account for an increase of crystallization temperature due to entropy decrease of the flowing melt. This entropy decrease was calculated from the molecular orientation on the basis of rubber elasticity theory applied to the entangled and elongated melt. The evolution of molecular orientation (elongation) during the film casting experiments was calculated using a non-linear dumbbell model which considers the relaxation time, obtained from normal stress difference and viscosity functions, to be a function of the deformation rate. The comparison between experimental distributions and model based crystallinity distributions was satisfactory.

Mechanism of gross melt fracture elimination in the extrusion of polyethylenes in the presence of boron nitride

Abstract: The mechanism by which the addition of a small amount of boron nitride into a polyethylene eliminates gross melt fracture is elucidated Simple elongational viscosity measurements at high rates revealed that the presence of boron nitride decreases the extensional viscosity of polyethylenes The extensional rates at which these effects are present were found to be about the same with those at which gross melt fracture is obtained (calculated from Cogswell’s analysis) Thus, it can be argued that the well dispersed boron nitride particles decrease extensional stresses that are responsible for gross melt fracture and/or their presence dissipate the release of energy resulting from isolated rupture or slip planes within the melt originating at the entrance to the capillary

Comparative rheological studies of polyamide-6 and its low loaded nanocomposite based on layered silicates

Abstract: We study some rheological properties for polyamide-6 (PA-6) and a low concentrated clay nanocomposite melt based on polyamide-6 and montmorillonite. Simple shear experiments, carried out for both the neat system and nanocomposite at two different temperatures, include start up shear flows, stress relaxation after cessation of steady flow and oscillatory shear. The dynamic data for the neat PA-6 matrix differ markedly from that of the nanocomposite system, even if it has very low nanofiller concentration. Thermal stability of the PA-6 matrix imposed many restrictions on rheological studies of our systems. Therefore an experimental window was established via rheological and thermal characterization of the materials, wherein the polymer matrix was confirmed to be thermally stable. The relaxation spectra for both polymer systems were determined from linear dynamic experiments using the Pade’-Laplace procedure. A rough estimation of nanocomposite volume fraction at percolation allowed us to attribute the occurrence of extra (relative to the neat polymer) Maxwell modes observed for the nanocomposite to the formation of a particulate network above the percolation threshold.

Rheooptical study of the early stages of flow enhanced crystallization in isotactic polypropylene

Abstract: The effect of a shear flow on the early stages and the kinetics of isothermal crystallization of an isotactic polypropylene has been studied experimentally. In the shear rate region where crystallization proceeds through point-like precursors, the magnitude of the shear rate, the shearing time as well as the instant in time at which the deformation starts have all been varied, in combination with rheooptical measurements. These include depolarized light intensity and birefringence. In agreement with previous work, above a critical shear rate and a critical shearing time, the crystallization kinetics are enhanced. Somewhat surprisingly, below a characteristic time, t0,max, the kinetics are not affected by the instant in time at which flow is applied or stops. As long as flow takes place before this critical dwell time, only the shearing time and primarily the magnitude of the shear rate seem to matter. When flow is started only after t0,max, its effect to accelerate crystallization kinetics becomes less efficient. The range over which the different parameters have an effect have been compared to the rheological relaxation times and to the measurements of global chain extension. To investigate the effects of flow on the early stages in more detail, time resolved Small-Angle Light Scattering experiments were used to detect changes in the density and orientation fluctuations. Measurements explicitly compare the effect of temperature and shear flow on the kinetics and the intensity of the density fluctuations.

The influence of matrix viscoelasticity on the rheology of polymer blends

Abstract: We examine the effects of matrix phase viscoelasticity on the rheological modeling of polymer blends with a droplet morphology. Two contravariant, second-rank tensor variables are adopted along with the translational momentum density of the fluid to account for viscoelasticity of the matrix phase and the ellipsoidal droplet shapes. The first microstructural variable is a conformation tensor describing the average extension and orientation of the molecules in the matrix phase. The other microstructural variable is a configuration tensor to account for the average shape and orientation of constant-volume droplets. A Hamiltonian framework of non-equilibrium thermodynamics is then adopted to derive a set of continuum equations for the system variables. This set of equations accounts for local conformational changes of the matrix molecules due to droplet deformation and vice versa. The model is intended for dilute blends of both oblate and prolate droplets, and droplet breakup and coalescence are not taken into account. Only the matrix phase is considered as viscoelastic; i.e., the droplets are assumed to be Newtonian. The model equations are solved for various types of homogeneous deformations, and microstructure/rheology relationships are discussed for transient and steady-state conditions. A comparison with other constrained-volume rheological models and experimental data is made as well.

The rheology of recycled EVA/LDPE modified bitumen

Abstract: This paper describes linear viscoelasticity, at low and intermediate temperatures, and the flow behaviour, at high temperatures, of polymer modified bitumen (PMB) containing 5 and 9 wt% recycled EVA/LDPE. The relationship between flow behaviour and microstructure of the modified bitumen was also considered, by comparison of experiments carried out in capillary and rotational rheometers and photomicrographs taken using a microscopy system whilst the sample was being sheared. Blends of 60/70 penetration grade bitumen and waste plastic (EVA/LDPE) were processed in an open mixer using a four blade propeller. Rheological tests, differential scanning calorimetry (DSC) and microscopy showed that the bitumen performance was improved by adding the recycled polymer. As a consequence, the use of recycled EVA/LDPE in PMBs can be considered a suitable and interesting alternative from both an environmental and economical point of view. The experimental results also show that pure bitumen has shear-thinning characteristics. The blending of polymer into the bitumen modifies the melt processing characteristics of the blend, whilst the viscoelastic properties of the semi-solid composite are enhanced.