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.     

The triple jet: influence of shear history on the stretching of polymer solutions

A kerosene-based aircraft safety fuel and aqueous solutions of poly (ethylene oxide) and polyacrylamide are examined using the “triple jet” system. This device allows the solution to be stretched as it flows from a capillary tube and the axial stress, strain and strain rate in the liquid are measured.The shear history of the solution is altered by placing cylindrical inserts in the capillary tube. This is shown to have a large effect on the extensional behaviour of aircraft safety fuel, a moderate effect on the extensional behaviour of poly (ethylene oxide) solution and little effect on the behaviour of polyacrylamide solution. The extensional viscosity of the aircraft fuel is raised by an order of magnitude when a long period of high shear is used; the effects last for periods of up to one second, though traditional methods suggest a relaxation time of the order of 10^?3 seconds. A liquid of shear viscosity 4 centipoise may have an extensional viscosity of over 100 poise.Plots of the extensional modulus of the jet as a function of distance along the jet emphasize the importance of shear history for the first two types of solution and suggest that the latter stages of the stretching process are elastic in character. Typical extensional moduli for the solutions tested are in the range 1.3–5.0 × 10⁴ dyn.cm^?2.The relevance of the interplay between shearing and stretching flow to the phenomena of lubrication and turbulence suppression is mentioned.     

Characterization of polyacrylamide gels as an elastic model for food gels

Serving as an elastic model system for food gels, characteristics of polyacrylamide (PAAm) gels were investigated using small amplitude and large deformation rheological tests. The PAAm gels displayed elastic or viscoelastic behavior depending on network crosslink density. For elastic PAAm gels, the rheological properties obeyed the theory of rubber elasticity; whereas for viscoelastic PAAm gels, shear modulus depended on temperature. The elastic PAAm gel fracture parameters did not change with deformation rate (0.2–5.5 s^–1), indicating insignificant viscous flow during deformation. Fracture stress was correlated with gel monomer concentration, whereas the fracture strain remained constant regardless of the monomer concentration. In addition, the stress was linearly proportioned with strain up to fracture, indicating that PAAm gels did not experience finite network chain extensibility during large deformation. Consequently, the fracture of PAAm gels did not result from the extensional limitation of network chains, nor did gel fracture result from the nonlinear force–distance relationship between polymer connections. Purportedly, the fracture of PAAm gels was caused by external force overcoming the gel cohesive forces, and low strength of PAAm gels compared to rubbers caused fracture prior to experiencing nonlinear stress-strain deformation.Paper No. FSR04-20 of the Journal Series of the North Carolina Agricultural Research Service, Raleigh, NC 27695-7643. The use of trade names does not imply endorsement by the North Carolina Agricultural Research Service of products named, nor criticisms of similar ones not mentioned.     

Rheomechanical and morphological study of compatibilized PP/EVOH blends

In order to find the relationships between processibility and properties of the polypropylene/ethylene vinyl alcohol copolymer (PP/EVOH) blends, their rheological behavior, in both shear and extensional flows, was studied and related with mechanical, morphological, and barrier properties of the materials. The nonlinear viscoelastic behavior in shear was also analyzed. The data showed that the rheological parameters (viscosity, loss modulus, storage modulus, extensional viscosity, and Trouton ratio) improved with the addition of low quantities of sodium ionomer copolymer used as compatibilizer. At the same time, the overall properties of the PP/EVOH blends improved as a result of the compatibilizer addition. The morphological analysis showed that the changes in the material properties were related with a more uniform distribution of EVOH particles in the PP matrix. The rheological data obtained allowed us to choose the optimal range for EVOH and ionomer contents, especially in terms of combining good processing characteristics with the good final properties.     

Suspensions of titania nanoparticle networks in nematic liquid crystals: rheology and microstructure

We study the influence of confinement on the rheology and structure of nematic liquid crystals (NLCs). NLCs get confined in networks of titania (TiO₂, primary particle size = 21 nm) nanoparticles in suspensions of TiO₂ and NLC, N-(4-methoxybenzylidene)-4-butylaniline (MBBA). Suspensions with TiO₂ nanoparticle volume fraction (?) of 0.006–0.017, form viscoelastic solids with low elastic modulus (G′) of 10¹ Pa–10² Pa and short relaxation times. Increase in TiO₂ nanoparticle ? leads to a rise in G′ with TiO₂ nanoparticles forming a percolating network at a critical volume fraction (? _c) = 0.023, and G′ of ~10³ Pa. TiO₂/MBBA NLC suspensions at and above ? _c = 0.023 show G′ ~ ω ^x?1 scaling, where ω is the angular frequency and the minimum in loss modulus (G′′) with ω. The effective noise temperature, x decreases and approaches 1 with the increase in the TiO₂ nanoparticle ? from 0.023–0.035, is indicative of an increase in the glassy dynamics. Through the polarized light microscopy and differential scanning calorimetry experiments, we propose that the progressive addition of TiO₂ nanoparticles introduces a quenched random disorder (QRD) in the NLC medium which disturbs the nematic order. This results in metastable TiO₂/MBBA NLC suspensions in which NLC domains get confined in the network of flocs of TiO₂ nanoparticles. We also show that the salient rheological signatures of soft glassy rheology develop only in the presence of NLC MBBA and are absent in the isotropic phase of MBBA.     

Rheology of polymer blends: linear model for viscoelastic emulsions

 Kerner's model for flow of composite elastic media is extended to an emulsion of viscoelastic phases with interfacial tension undergoing deformations of small amplitude. A privileged internal structure inside the suspended drops is discussed in terms of fluid circulation across the interface. It is shown that for usual drop radius and interfacial tension values of emulsions, the rheological behavior predicted by the model, with very simple expression for the complex shear modulus, is quantitatively similar to that predicted by Palierne's model. Predictions of the model are compared with experimental data obtained on a polystyrene/polyethylene blend sheared in a small-amplitude oscillatory mode. Received: 10 August 1998 Accepted: 18 December 1998     

Measurement method of complex viscoelastic material properties

A measurement technique of viscoelastic properties of polymers is proposed to investigate complex Poisson’s ratio as a function of frequency. The forced vibration responses for the samples under normal and shear deformation are measured with varying load masses. To obtain modulus of elasticity and shear modulus, the present method requires only knowledge of the load mass, geometrical characteristics of a sample, as well as both the amplitude ratio and phase lag of the forcing and response oscillations. The measured data were used to obtain the viscoelastic properties of the material based on a 2D numerical deformation model of the sample. The 2D model enabled us to exclude data correction by the empirical form factor used in 1D model. Standard composition (90% PDMS polymer + 10% catalyst) of silicone RTV rubber (Silastic^® S2) were used for preparing three samples for axial stress deformation and three samples for shear deformation. Comprehensive measurements of modulus of elasticity, shear modulus, loss factor, and both real and imaginary parts of Poisson’s ratio were determined for frequencies from 50 to 320 Hz in the linear deformation regime (at relative deformations 10^?6 to 10^?4) at temperature 25 °C. In order to improve measurement accuracy, an extrapolation of the obtained results to zero load mass was suggested. For this purpose measurements with several masses need to be done. An empirical requirement for the sample height-to-radius ratio to be more than 4 was found for stress measurements. Different combinations of the samples with different sizes for the shear and stress measurements exhibited similar results. The proposed method allows one to measure imaginary part of the Poisson’s ratio, which appeared to be about 0.04–0.06 for the material of the present study.     

Dynamic rheology of the immiscible blends of liquid crystalline polymers and flexible chain polymers

Immiscible blends containing liquid crystalline polymers (LCP) as dispersed phases show different dynamic rheological properties than those composed of flexible polymers. The widely used Palierne’s model was shown by many authors to be insufficient to describe the frequency dependence of dynamic modulus of such blends. A new model was presented to describe the dynamic rheology of the immiscible blend containing LCP as a dispersed phase. The flexible chain polymer matrix was assumed to be a linear viscoelastic material under small amplitude oscillatory shear flow, and the LCP was assumed to be an Ericksen’s transversely isotropic fluid. The Rapini-Papoular equation of anisotropic interfacial energy was used to account for the effect of nematic orientation on the interfacial tension. It was found that the orientation of the director and the anchoring energy greatly influenced the storage modulus at the “shoulder” regime. The overall dynamic modulus of the blend can be well described by the model with suitable choice of the orientation of the director and anchoring energy of LCP.     

Extracting extensional properties through excess pressure drop estimation in axisymmetric contraction and expansion flows for constant shear viscosity,extension strain-hardening fluids

In this study, hyperbolic contraction–expansion flow (HCF) devices have been investigated with the specific aim of devising new experimental measuring systems for extensional rheological properties. To this end, a hyperbolic contraction–expansion configuration has been designed to minimize the influence of shear in the flow. Experiments have been conducted using well-characterized model fluids, alongside simulations using a viscoelastic White–Metzner/FENE-CR model and finite element/finite volume analysis. Here, the application of appropriate rheological models to reproduce quantitative pressure drop predictions for constant shear viscosity fluids has been investigated, in order to extract the relevant extensional properties for the various test fluids in question. Accordingly, experimental evaluation of the hyperbolic contraction–expansion configuration has shown rising corrected pressure drops with increasing elastic behaviour (De=0～16), evidence which has been corroborated through numerical prediction. Moreover, theoretical to predicted solution correspondence has been established between extensional viscosity and first normal stress difference. This leads to a practical means to measure extensional viscosity for elastic fluids, obtained through the derived pressure drop data in these HCF devices.     

Simulation of the linear rheological behavior of silica-filled,star-shaped SBR compounds

The rheological behavior of star-shaped SSBR/silica 60 phr compounds with different filler surface areas was experimentally studied and simulated using constitutive modeling. Rheological behavior was characterized in small amplitude oscillatory shear (SAOS) and stress relaxation after a small step shear. Unfilled SBR and SBR filled with four different silica grades with BET surface areas of 55, 135, 160, and 195 m²/g were used. A clear trend in rheological behavior was observed with surface area. A frequency sweep in the SAOS regime indicated an increase in dynamic properties with surface area. Additionally, linear stress relaxation tests at a strain level of 0.05 showed an increase in relaxation modulus with surface area and the presence of a plateau in the relaxation modulus at large times in compounds containing silica with high surface areas. The Leonov and Simhambhatla-Leonov models, modified to incorporate multimode particle network relaxation, were successfully used to simulate the frequency dependence of the storage modulus and the time evolution of the linear relaxation modulus for all samples. However, simulations of the frequency dependence of the loss modulus showed poor results in comparison with experimental data for the filled compounds.     

The distinction of viscoelastic phases from entangled wormlike micelles and of densely packed multilamellar vesicles on the basis of rheological measurements

It is shown in this work how two viscoelastic surfactant systems that are both shear thinning but differ in their morphology can be distinguished on the basis of rheological measurements. The measurements were carried out on the novel surfactant system cetyltrimethylammonium 2-hydroxy-1-naphthoate. The phases in this system are produced by mixing cetyltrimethylammonium hydroxide and 2-hydroxy-1-naphthoic acid. With increasing counterion surfactant ratio X, the system has two viscoelastic regions that are separated by a two-phase region. It is shown by cryo-transmission electron microscopy and by small angle neutron scattering that the first viscoelastic region which exists between X=0.5 and X=0.75 contains wormlike micelles, while the second viscoelastic region that exists between X=0.9 and X=1.4 contains multilamellar vesicles. Both phases look alike, are highly viscoelastic, have similar storage modulus values, and are shear thinning. The phases and the properties of the phases for the studied system are very similar as the phases for the system CTA-3-hydroxy-2-naphthoate that has been studied before (see Hassan et al. Langmuir, 12:4350–4357, 1996; Horbaschek et al. J Colloid Interface Sci, 206:439–456, 1998). The two viscoelastic phases show the same shear-thinning behavior, but differ in other rheological results. The phases can most easily be distinguished with the help of normal stress measurements. The wormlike viscoelastic solutions show large normal stresses that give rise to a large Weissenberg effect while the vesicle phases show no Weissenberg effect.     

Small and large strain rheology of wheat gluten

 The rheological properties of wheat gluten were studied under both small and large deformation and compared with those of the parent flours. The limiting strain of linear viscoelastic behaviour of gluten doughs, 3 × 10⁻², was an order of magnitude larger than that of the flour doughs, 10⁻³. The role of starch in the lower limiting strain of flour doughs was indicated by the exponential decrease in the limiting strain of gluten-starch mixtures with greater quantities of starch. Large strain measurements showed gluten doughs possessed greater shear and elongational viscosities than flour doughs and these differences were greatest at lower shear and elongation rates (0.01 and 0.1 s⁻¹). The larger viscosities of flour and gluten doughs at the low strain rates help to stabilise and prevent the collapse of gas bubbles during bread fermentation and baking. Increasing starch levels in gluten-starch mixtures, at either constant or optimal water levels, lowered the elongational viscosity. Dynamic measurements were, however, more sensitive to the level of water added to the gluten-starch mixtures. The storage modulus decreased with increasing starch levels when constant water levels were used to prepare the mixtures, but when optimal water levels were used the storage modulus increased. Gluten and starch are major contributors to the large and small strain rheological properties of flour doughs; however, gluten-starch mixtures were unable to duplicate exactly the rheological properties of flour doughs, indicating that other flour components such as pentosans, lipids and water soluble proteins also influence dough rheology. Received: 20 March 2001 Accepted: 11 July 2001     

Surface rheology

This review article approaches the subject of surface rheology from a phenomenological point of view. Operational definitions are given for the four surface rheological parameters: modulus and viscosity in either dilation or shear. Results of recent measurements are discussed. Observed non-Newtonian or viscoelastic behaviour has in some cases been interpreted in terms of known relaxation processes. The surface rheological behaviour affects the flow of bulk liquid near the surface; coupling occurs through the tangential stress boundary condition.     

Application of scaling transformation to characterizing complex rheological behaviors and fractal derivative modeling

It has been long observed that cumbersome parameters are required for the traditional viscoelastic models to describe complex rheological behaviors. Inspired by the relationship between normal and anomalous diffusions, this paper tentatively employs t ^α to replace t, called as the scaling transformation, in the traditional creep compliance and relaxation modulus. With this methodology, the relaxation modulus is found to agree with the well-known Kohlrausch-Williams-Watts (KWW) stretched exponential function. The fitting results confirm that the proposed models accurately characterize rheological behaviors only with one more parameter α. Moreover, it is noted that the present formulations are directly related to the fractal derivative viscoelastic models and the index α is actually the order of the fractal derivative.     

Rheology of oil-in-water emulsions

The effect of interfacial tension on the steady-flow and dynamic viscoelastic behavior of emulsions are studied experimentally. At very low inter-facial tensions and low volume fractions, the viscosity decreases with increasing shear rate and becomes constant at high shear rates. The high-shear-rate Newtonian viscosity is not affected by interfacial tension, but the transition from pseudoplastic to Newtonian flow shifts to lower shear rates as the interfacial tension decreases. At an interfacial tension of 5 × 10^–3 Nm^–1, the viscosity decreases, passes through a minimum, and then increases as the shear rate is increased. The dilatant behavior may be attributed to elastic responses of interfaces during collision of drops. At high volume fractions, the emulsions show remarkable elasticity resulting from the interfacial energy associated with deformation of liquid films. The modulus and viscosity are proportional to interfacial tension and inversely proportional to drop size.     

Dependence of linear viscoelastic critical strain and stress values on extent of gelation for a thermally activated gelling system

A large body of literature is focused on the accurate determination of a gel point for systems undergoing a sol-gel phase transition. Investigation into the limiting strain and stress for linear viscoelastic behaviour at various stages of a phase transition such as gelation is a subject that is rarely commented on. The small amplitude oscillatory rheological behaviour of a biopolymer cross-linker system through a thermally activated sol-gel transition is presented. Mechanical spectra were interpreted through application of the gelation criteria of Chambon and Winter (Winter and Chambon 1986; Chambon and Winter 1987), where the (so-called gel strength) parameter S, and relaxation exponent, n are obtained. A detailed study of the limit of linear viscoelasticity yields important trends in critical stress (σ°_c) and critical strain (γ°_c) limits highlighting the possible experimental difficulties associated with mechanical measurements obtained in close proximity to the gel point. Received: 17 March 2000 Accepted: 2 October 2000     

Molecular theory for moderately concentrated polymer solutions in shear flow

A molecular theory for the rheological properties of moderately concentrated polymer solutions is developed on the basis of a model of interacting dumbbells. The interaction is treated in a mean field approximation, leading to an effective one-particle potential and a Gaussian stationary distribution function. Various rheological functions such as birefringence, shear viscosity and first normal-stress coefficient for simple shear flow and the Trouton viscosity for simple extensional flow are calculated. Good qualitative agreement with experimental observations is found, especially at intermediate flow rates. It is predicted, for example, that the birefringence increases approximately linearly with shear rate at intermediate shear rates and that the concentration dependence of the gradient varies asc ^1/2. The typical non-Newtonian behaviour is obtained for the shear viscosity. For small concentrations the onset of shear rate dependence decreases asc ^–1/2. At intermediate shear rates an apparent power law is obtained with an exponent between – 0.5 and – 1.0, decreasing with concentration.     

Rheology and structural changes of plasticized zeins in the molten state

Zeins, storage proteins from maize, are suitable for making biobased thermoplastic materials. The rheological behavior of a commercial zein plasticized with 20 w% glycerol was studied in the molten state by steady-state flow experiments in extrusion conditions and oscillatory rheometry. For low residence times, a shear-thinning viscoelastic behavior was observed, with G″ exceeding G′. After 300 s at 130 °C, the complex viscosity |η ^?|?=?7?×?10³ ω ^?0.46 was found to be similar to that of thermoplastic polymer melts used in fused deposition modeling. However, the ratio between the exponents of the power laws describing G′(ω) and G″(ω) did not meet the typical value of 2 for entangled polymer melts. Moreover, for longer residence times, the viscosity increased and a gelation phenomenon was observed with a crossing over of G′(ω) and G″(ω). Gel times ranged from 6000 s at 120 °C to 1700 s at 150 °C. The evolution of the macromolecular structure assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and high-performance size exclusion chromatography suggested that this gelation phenomenon involves various types of covalent and non-covalent cross-links. Disulfide bonds played a significant role in gelation kinetics despite a very low cysteine residue content in the protein primary structure (about 1 mol%). These results suggested that plasticized zeins initially behave like a low-viscosity non-entangled polymer melt, before cross-linking progressively led to a continuous network.     

Surface tension driven jet break up of strain-hardening polymer solutions

Experimental studies attempting to ascertain the influence of viscoelasticity on the atomization of polymer solution are often hindered by the inability to decouple the effect of shear thinning from the effect of extensional hardening. Here, the influence of viscoelasticity on the jet break up of a series of non-shear-thinning viscoelastic fluids is quantified. Previous characterization using an opposed-nozzle rheometer identified the critical extensional rates for strain hardening of these model fluids. The strain hardening fluids exhibit a beads-on-string structure with reduction or elimination of satellite drops. Capillary instabilities grow on the filaments connecting the spheres and eventually break the filaments up into a string of very small drops about one order of magnitude smaller than the satellite drops formed by a Newtonian fluid with the same shear viscosity, surface tension, and density. These results confirm that strain hardening is the key rheological property in jet break up and that the critical extensional rate of a fluid is pertinent in determining the final characteristics of break up. Results suggest that the opposed-nozzle rheometer does probe extensional behavior in the range of extensional rates that are relevant to jet break up, providing a tool to roughly predict jet break up.