Showing papers in "Rheologica Acta in 2010"

Structure and linear viscoelasticity of flexible polymer solutions: comparison of polyelectrolyte and neutral polymer solutions

Abstract: The current state of understanding for solution conformations of flexible polymers and their linear viscoelastic response is reviewed. Correlation length, tube diameter, and chain size of neutral polymers in good solvent, neutral polymers in θ-solvent, and polyelectrolyte solutions with no added salt are compared as these are the three universality classes for flexible polymers in solution. The 1956 Zimm model is used to describe the linear viscoelasticity of dilute solutions and of semidilute solutions inside their correlation volumes. The 1953 Rouse model is used for linear viscoelasticity of semidilute unentangled solutions and for entangled solutions on the scale of the entanglement strand. The 1971 de Gennes reptation model is used to describe linear viscoelastic response of entangled solutions. In each type of solution, the terminal dynamics, reflected in the terminal modulus, chain relaxation time, specific viscosity, and diffusion coefficient are reviewed with experiment and theory compared. Overall, the agreement between theory and experiment is remarkable, with a few unsettled issues remaining.

A double wall-ring geometry for interfacial shear rheometry

Abstract: The rheological properties of complex fluid interfaces are of prime importance in a number of technological and biological applications. Whereas several methods have been proposed to measure the surface rheological properties, it remains an intrinsically challenging problem due to the small forces and torques involved and due to the intricate coupling between interfacial and bulk flows. In the present work, a double wall-ring geometry to measure the viscoelastic properties of interfaces in shear flows is presented. The geometry can be used in combination with a modern rotational rheometer. A numerical analysis of the flow field as a function of the surface viscoelastic properties is presented to evaluate the non-linearities in the surface velocity profile at a low Boussinesq number. The sensitivity of the geometry, as well as its applicability, are demonstrated using some reference Newtonian and viscoelastic fluids. Oscillatory and steady shear measurements on these reference complex fluid interfaces demonstrate the intrinsic sensitivity, the accuracy, and the dynamic range of the geometry when used in combination with a sensitive rheometer.

Large amplitude oscillatory shear of pseudoplastic and elastoviscoplastic materials

Abstract: We explore the utility of strain-controlled large amplitude oscillatory shear (LAOS) deformation for identifying and characterizing apparent yield stress responses in elastoviscoplastic materials. Our approach emphasizes the visual representation of the LAOS stress response within the framework of Lissajous curves with strain, strain rate, and stress as the coordinate axes, in conjunction with quantitative analysis of the corresponding limit cycle behavior. This approach enables us to explore how the material properties characterizing the yielding response depend on both strain amplitude and frequency of deformation. Canonical constitutive models (including the purely viscous Carreau model and the elastic Bingham model) are used to illustrate the characteristic features of pseudoplastic and elastoplastic material responses under large amplitude oscillatory shear. A new parameter, the perfect plastic dissipation ratio, is introduced for uniquely identifying plastic behavior. Experimental results are presented for two complex fluids, a pseudoplastic shear-thinning xanthan gum solution and an elastoviscoplastic invert-emulsion drilling fluid. The LAOS test protocols and the associated material measures provide a rheological fingerprint of the yielding behavior of a complex fluid that can be compactly represented within the domain of a Pipkin diagram defined by the amplitude and timescale of deformation.

Viscoelastic properties of MR elastomers under harmonic loading

Abstract: This paper presents both experimental and modeling studies of viscoelastic properties of MR elastomers under harmonic loadings. Magnetorheological elastomer (MRE) samples were fabricated by mixing carbonyl iron power, silicone oil, and silicone rubber and cured under a magnetic field. Its steady-state and dynamic properties were measured by using a parallel-plate rheometer. Various sinusoidal loadings, with different strain amplitude and frequencies, were applied to study the stress responses. The stress–strain results demonstrated that MR elastomers behave as linear visocoelastic properties. Microstructures of MRE samples were observed with a scanning electron microscope. A four-parameter linear viscoelatic model was proposed to predict MRE performances. The four parameters under various working conditions (magnetic field, strain amplitude, and frequency) were identified with the MATLAB optimization algorithm. The comparisons between the experimental results and the model predictions demonstrate that the four-parameter viscoelastic model can predict MRE performances very well. In addition, dynamic properties of MRE performances were alternatively represented with equivalent stiffness and damping coefficients.

Extensional rheology of a shear-thickening cornstarch and water suspension

Abstract: A filament-stretching rheometer is used to measure the extensional viscosity of a shear-thickening suspension of cornstarch in water. The experiments are performed at a concentration of 55 wt.%. The shear rheology of these suspensions demonstrates a strong shear-thickening behavior. The extensional rheology of the suspensions demonstrates a Newtonian response at low extension rates. At moderate strain rates, the fluid strain hardens. The speed of the strain hardening and the extensional viscosity achieved increase quickly with increasing extension rate. Above a critical extension rate, the extensional viscosity goes through a maximum and the fluid filaments fail through a brittle fracture at a constant tensile stress. The glassy response of the suspension is likely the result of jamming of particles or clusters of particles at these high extension rates. This same mechanism is responsible for the shear thickening of these suspensions. In capillary breakup extensional rheometry, measurement of these suspensions demonstrates a divergence in the extensional viscosity as the fluid stops draining after a modest strain is accumulated.

Viscoelasticity in inkjet printing

Abstract: We investigate the effects of viscoelasticity on drop generation in inkjet printing. In drop-on-demand printing, individual ink ‘drops’ are ejected from a nozzle by imposed pressure pulses. Upon exiting the nozzle, the shape of each ‘drop’ is that of a nearly spherical bead with a long thin trailing ligament. This ligament subsequently breaks up under the Rayleigh instability, typically into several small droplets (known as satellite drops). These satellite drops can create unwanted splash on the target substrate and a reduction in printing quality. Satellite drops can potentially be eliminated by adding polymer to the ink; elastic stresses can act to contract the trailing ligament into the main drop before capillary breakup occurs. However, elasticity can also reduce the drop velocity and can delay or even prevent the break-off of the drop from the ink reservoir within the nozzle. To achieve optimal drop shape and speed, non-Newtonian parameters such as the polymer concentration and molecular weight must be chosen correctly. We explore this parameter space via numerical simulations, using the Lagrangian–Eulerian finite-element method of Harlen et al. (J Non-Newtonian Fluid Mech 60:81–104, 1995). Results are compared with experimental observations taken from real printheads.

On secondary loops in LAOS via self-intersection of Lissajous–Bowditch curves

Abstract: When the shear stress measured in large amplitude oscillatory shear (LAOS) deformation is represented as a 2-D Lissajous–Bowditch curve, the corresponding trajectory can appear to self-intersect and form secondary loops. This self-intersection is a general consequence of a strongly nonlinear material response to the imposed oscillatory forcing and can be observed for various material systems and constitutive models. We derive the mathematical criteria for the formation of secondary loops, quantify the location of the apparent intersection, and furthermore suggest a qualitative physical understanding for the associated nonlinear material behavior. We show that when secondary loops appear in the viscous projection of the stress response (the 2-D plot of stress vs. strain rate), they are best interpreted by understanding the corresponding elastic response (the 2-D projection of stress vs. strain). The analysis shows clearly that sufficiently strong elastic nonlinearity is required to observe secondary loops on the conjugate viscous projection. Such a strong elastic nonlinearity physically corresponds to a nonlinear viscoelastic shear stress overshoot in which existing stress is unloaded more quickly than new deformation is accumulated. This general understanding of secondary loops in LAOS flows can be applied to various molecular configurations and microstructures such as polymer solutions, polymer melts, soft glassy materials, and other structured fluids.

Differences between stress and strain control in the non-linear behavior of complex fluids

Abstract: Various techniques have been proposed to characterize the behavior in the non-linear regime. A new theoretical framework, as proposed recently by Ewoldt et al. (J Rheol 52(6):1427–1458, 2008), provides a quantitative analysis of Lissajous figures during large-amplitude oscillatory shear (LAOS). Intra- and intercycle non-linearities, strain stiffening and softening, and shear thinning and thickening are described and can be distinguished. The new LAOS framework from Ewoldt et al. has been extended to a sinusoidal stress input. Measurements on two different samples reveal significant different results for sinusoidal strain or sinusoidal stress input. For both sinusoidal inputs, the results have been verified by cyclic stress and strain loading tests. The sinusoidal input tests are analyzed as an oscillatory test by the rheometer software and firmware, whereas the cyclic loading tests are purely rotational tests. Since both types of testing give the same results, any instrumental artifacts can be excluded. This implies that complex fluids can behave differently whether periodic stress or strain input functions outside the linear visco-elastic range are applied. All tests in controlled strain and stress in rotational and oscillatory modes have been performed with the same rheometer based on an air bearing-supported electrically commutated synchronous motor.

Shear rheology of carbon nanotube suspensions

Abstract: The shear rheology of carbon nanotube suspensions is reviewed from the perspective of colloid and polymer science. In the semi-dilute to concentrated regimes, the nature of the equilibrium or quiescent state is often dominated by nanotube entanglement and strong attractive inter-particle interactions that favor the formation of a disordered network or gel. The strength of this network with respect to the applied stress dictates the development of mesoscale structural anisotropy, first through a global yield stress and then through a critical stress for homogenization. For concentrated suspensions, the nematic liquid-crystalline order anticipated for high-aspect-ratio rigid rods has been observed in a few select scenarios. The opportunity for deeper theoretical insight is emphasized and intuitive physical arguments are offered that might serve as a foundation for future study.

Capillary breakup extensional rheometry (CaBER) on semi-dilute and concentrated polyethyleneoxide (PEO) solutions

Abstract: Semi-dilute (\(c^\ast ce) solutions of PEO yield uniformly thinning, cylindrical filaments in capillary breakup extensional rheometry (CaBER) experiments. Up to c ≈ ce thinning can be characterized by a single elongational relaxation time λE. Comparison with the longest shear relaxation time, λS reveals that λE/λS decreases with increasing concentration or molecular weight according to (c[η]) − 4/3. This is attributed to the large deformation the solutions experience during filament thinning. A factorable integral model including a single relaxation time and a Soskey or Wagner damping function accounting for the large deformation in CaBER experiments is used to calculate λE/λS and provides good agreement with experimental results. Irrespective of concentration or molecular weight a beads-on-a-string structure occurs prior to filament breakup at a diameter ratio D/D0 ≈ 0.01. This instability is supposed to be closely related to a flow-induced phase separation.

Models for the deformation of a single ellipsoidal drop: a review

Abstract: Dilute polymer blends and immiscible liquid emulsions are characterized by a globular morphology. The dynamics of a single drop subjected to an imposed flow field has been considered to be a valuable model system to get information on dilute blends. This problem has been studied either theoretically by developing exact theories for small drop deformations or by developing simplified models often based on phenomenological assumptions. In this paper, a critical overview of the available models for the dynamics of a single drop is presented, discussing four different systems, namely the Newtonian system, where a single Newtonian drop is immersed in an infinite Newtonian matrix; the non-Newtonian system, where at least one of the components, the drop fluid or the matrix one, is non-Newtonian; the confined Newtonian system, where the matrix is confined and wall effects alter the drop dynamics; and the confined non-Newtonian system.

Shear-thickening behavior of polymethylmethacrylate particles suspensions in glycerine–water mixtures

Abstract: The rheological behavior of polymethylmethacrylate (PMMA) particles suspensions in glycerine–water mixtures has been investigated by means of steady and dynamic rheometry in this work. The shear rheology of these suspensions demonstrates a strong shear thickening behavior. The variations of shear viscosity with the volume fraction and ratios of glycerine to water are discussed. The effect of volume fraction can be qualitatively explained using a clustering mechanism, which attributes the phenomena to the formation of temporary, hydrodynamic clusters. The influence of interactions between glycerine–water mixtures and PMMA particles on shear thickening is investigated by varying the ratio of glycerine to water. In addition, the reversible and thixotropic properties of suspensions of PMMA dispersed in glycerine–water (3:1) mixtures are also investigated, and the results demonstrate the excellent reversible and thixotropic properties of PMMA particle suspensions.

Investigating the transient response of a shear thickening fluid using the split Hopkinson pressure bar technique

Abstract: The split Hopkinson pressure bar (SHPB) technique is implemented to evaluate the transient response of a colloidal suspension exhibiting shear thickening at strain rates and timescales never before explored in a laboratory instrument. These suspensions are shown to exhibit a discontinuous transition from fluid-like (shear thinning) to solid-like (shear thickening) behavior when evaluated using rotational rheometry. The effect of loading rate on this transition time is studied for a particle volume fraction of 0.54 using the SHPB technique. It is shown that the time required for transition to occur decreases logarithmically with loading rate. From these results, we conclude that transition is not triggered by a characteristic shear rate, but rather a critical shear strain is required. Results from SHPB experiments performed up to Peclet numbers of order 107 are presented and discussed for 0.50, 0.52, and 0.54 particle volume fraction suspensions.

Non-linear viscoelasticity and temporal behavior of typical yield stress fluids: Carbopol, Xanthan and Ketchup

Abstract: The viscoelastic properties of yield stress fluids are difficult to measure outside the linear viscoelastic regime, in particular above their yield stress. These properties are investigated for several common yield stress fluids using inertio-elastic oscillations. From this coupling between the instrument’s inertia and the viscoelasticity of the materials, the complete simple shear rheology can be determined, including viscoelasticity under flow. Findings show that the tested materials have an almost constant elasticity below and above the yield stress, even for applied stresses several times larger than the yield stress. Moreover, the temporal behavior of the materials is unambiguously determined. Concentrated Xanthan is shown to be thixotropic, while Ketchup mainly shows retarded viscoelasticity. Carbopol does not show long-term temporal dependance but apparently exhibits fracturation.

Extensional rheology of concentrated emulsions as probed by capillary breakup elongational rheometry (CaBER)

Abstract: Elongational flow behavior of w/o emulsions has been investigated using a capillary breakup elongational rheometer (CaBER) equipped with an advanced image processing system allowing for precise assessment of the full filament shape. The transient neck diameter D(t), time evolution of the neck curvature κ(t), the region of deformation ldef and the filament lifetime tc are extracted in order to characterize non-uniform filament thinning. Effects of disperse volume fraction ϕ, droplet size dsv, and continuous phase viscosity ηc on the flow properties have been investigated. At a critical volume fraction ϕc, strong shear thinning, and an apparent shear yield stress τy,s occur and shear flow curves are well described by a Herschel–Bulkley model. In CaBER filaments exhibit sharp necking and tc as well as κmax = κ (t = tc) increase, whereas ldef decreases drastically with increasing ϕ. For ϕ < ϕc, D(t) data can be described by a power-law model based on a cylindrical filament approximation using the exponent n and consistency index k from shear experiments. For ϕ ≥ ϕc, D(t) data are fitted using a one-dimensional Herschel–Bulkley approach, but k and τy,s progressively deviate from shear results as ϕ increases. We attribute this to the failure of the cylindrical filament assumption. Filament lifetime is proportional to ηc at all ϕ. Above ϕc,κmax as well as tc/ηc scale linearly with τy,s. The Laplace pressure at the critical stretch ratio ec which is needed to induce capillary thinning can be identified as the elongational yield stress τy,e, if the experimental parameters are chosen such that the axial curvature of the filament profile can be neglected. This is a unique and robust method to determine this quantity for soft matter with τy < 1,000 Pa. For the emulsion series investigated here a ratio τy,e/τy,s = 2.8 ± 0.4 is found independent of ϕ. This result is captured by a generalized Herschel–Bulkley model including the third invariant of the strain-rate tensor proposed here for the first time, which implies that τy,e and τy,s are independent material parameters.

The effect of particle size and migration on the formation of flow-induced structures in viscoelastic suspensions

Abstract: Flow-induced structures in suspensions containing spheres in viscoelastic suspending media were investigated by microscopy and rheo-optical methods. Suspensions of monodisperse polystyrene spheres with diameters ranging from 1.2 to 2.8 μm and dispersed in aqueous solutions of hydroxypropylcellulose were studied in simple shear flows. Optical microscopy observations as well as small-angle light-scattering (SALS) experiments were performed using a parallel plate geometry. In agreement with previous work, necklaces of particles aligned in the flow direction were observed when shearing faster then a critical shear rate, which was found to be independent of particle size. In contrast to earlier work, however, the role of particle migration was found to be of prime importance. Particles were shown to migrate toward the plates where the particles assembled and aligned in strings running in the flow direction. For the smallest particles (1 μm diameter), the formation of particle doublets or short strings along the vorticity direction was observed at low shear rates, which flipped to an orientation into the flow direction and grew into longer strings at higher shear rates. SALS experiments were used to quantify the degree of alignment and its dependence on particle size, shear rate, and gap. For the system under investigation, the degree of alignment was found to increase with increasing shear rate and particle size and with decreasing gap. The present results suggest that, depending on the details of the suspending medium and the size and nature of the suspended particles, the formation of aligned structures is affected by the relative magnitude of the colloidal and hydrodynamic forces and the kinetics of string formation versus the kinetics of migration.

Interfacially active particles in droplet/matrix blends of model immiscible homopolymers: Particles can increase or decrease drop size

Abstract: Particles have been shown to adsorb at the interface between immiscible homopolymer melts and to affect the morphology of blends of those homopolymers. We examined the effect of such interfacially active particles on the morphology of droplet/matrix blends of model immiscible homopolymers. Experiments were conducted on blends of polydimethylsiloxane and 1,4-polyisoprene blended in either a 20:80 or 80:20 weight ratio. The effects of three different particle types, fluoropolymer particles, iron particles, and iron oxyhydroxide particles, all at a loading of 0.5 vol.%, were examined by rheology and by direct flow visualization. Particles were found to significantly affect the strain recovery behavior of polymer blends, increasing or decreasing the ultimate recovery, slowing down or accelerating the recovery kinetics, and changing the dependence of these parameters on the applied stress prior to cessation of shear. These rheological observations were found to correlate reasonably well with particle-induced changes in drop size. The particles can both increase as well as decrease the drop size, depending on the particle type, as well as on which phase is continuous. The cases in which particles cause a decrease in drop size are analogous to the particle stabilization of “Pickering emulsions” well-known from the literature on oil/water systems. We hypothesize that cases in which particles increase drop size are analogous to the “bridging–dewetting” mechanism known in the aqueous foam literature.

Rheological representation of fractional order viscoelastic material models

Abstract: We develop rheological representations, i.e., discrete spectrum models, for the fractional derivative viscoelastic element (fractional dashpot or springpot). Our representations are generalized Maxwell models or series of Kelvin-Voigt units, which, however, maintain the number of parameters of the corresponding fractional order model. Accordingly, the number of parameters of the rheological representation is independent of the number of rheological units. We prove that the representations converge to the corresponding fractional model in the limit as the number of units tends to infinity. The representations extend to compound fractional derivative models such as the fractional Maxwell model, fractional Kelvin-Voigt model, and fractional standard linear solid. Computational experiments show that the rheological representations are accurate approximations of the fractional order models even for a small number of units.

Rheology of pulp suspensions using ultrasonic Doppler velocimetry

Abstract: Conventional rheometry coupled with local velocity measurements (ultrasonic Doppler velocimetry) are used to study the flow behaviour of various commercial pulp fibre suspensions at fibre mass concentrations ranging from 1 to 5 wt.%. Experimental data obtained using a stress-controlled rheometer by implementing a vane in large cup geometry exhibits apparent yield stress values which are lower than those predicted before mainly due to existence of apparent slip. Pulp suspensions exhibit shear-thinning behaviour up to a high shear rate value after which Newtonian behaviour prevails. Local velocity measurements prove the existence of significant wall slippage at the vane surface. The velocimetry technique is also used to study the influence of pH and lignin content on the flow behaviour of pulp suspensions. The Herschel–Bulkley constitutive equation is used to fit the local steady-state velocity profiles and to predict the steady-state flow curves obtained by conventional rheometry. Consistency between the various sets of data is found for all suspensions studied, including apparent yield stress, apparent wall slip and complete flow curves.

Measurement technique and data analysis of extensional viscosity for polymer melts by Sentmanat extensional rheometer (SER)

Abstract: Transient extensional viscosity of low-density polyethylene was measured by Sentmanat extensional rheometer in combination with MCR301 rheometer (Anton Paar) at different temperatures. Issues related to the experimental procedure, namely fixing the sample and controlling the temperature, as well as correction for true sample dimensions in calculation of extensional viscosity of polymer melts, were discussed. The molecular stress function model was used to describe the experimental data. The results were in accordance with other test methods and theoretical description when the measurements were done without using the sample fixing clamps, careful temperature control was followed, and the experimental data were corrected for sample dimensions affected by thermal expansion and pre-stretching at the beginning of the test.

A smoothed particle hydrodynamics-based fluid model with a spatially dependent viscosity: application to flow of a suspension with a non-Newtonian fluid matrix

Abstract: A smoothed particle hydrodynamics ap- proach is utilized to model a non-Newtonian fluid with a spatially varying viscosity. In the limit of constant viscosity, this approach recovers an earlier model for Newtonian fluids of Espanol and Revenga (Phys Rev E 67:026705, 2003). Results are compared with numerical solutions of the general Navier-Strokes equation using the "regularized" Bingham model of Papanastasiou (J Rheol 31:385-404, 1987) that has a shear-rate- dependent viscosity. As an application of this model, the effect of having a non-Newtonian fluid matrix, with a shear-rate-dependent viscosity in a moderately dense suspension, is examined. Simulation results are then compared with experiments on mono-size silica spheres in a shear-thinning fluid and for sand in a calcium carbonate paste. Excellent agreement is found between simulation and experiment. These results indicate that measurements of the shear viscosity of simple shear- rate-dependent non-Newtonian fluids may be used in simulation to predict the viscosity of concentrated sus- pensions having the same matrix fluid.

Viscoelastic properties of ultra-high viscosity alginates

Abstract: Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHVN, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHVT, containing 22% M and 78% G). The viscoelastic behavior of the aqueous solutions of these alginates was determined in shear flow in terms of the shear stress σ 21, the first normal stress difference N 1, and the shear viscosity η in isotonic NaCl solutions (0.154 mol/L) at T = 298 K in dependence of the shear rate $\dot{\gamma}$ for solutions of varying concentrations and molar masses (3–10 × 105 g/mol, homologous series was prepared by ultrasonic degradation). Data obtained in small-amplitude oscillatory shear (SAOS) experiments obey the Cox–Merz rule. For comparison, a commercial alginate with intermediate chemical composition was additionally characterized. Particulate substances which are omnipresent in most alginates influenced the determination of the material functions at low shear rates. We have calculated structure–property relationships for the prediction of the viscosity yield, e.g., η–M w–c– $\dot{\gamma}$ for the Newtonian and non-Newtonian region. For the highest molar masses and concentrations, the elasticity yield in terms of N 1 could be determined. In addition, the extensional flow behavior of the alginates was measured using capillary breakup extensional rheometry. The results demonstrate that even samples with the same average molar mass but different molar mass distributions can be differentiated in contrast to shear flow or SAOS experiments.

Anomalous shear banding: multidimensional dynamics under fluctuating slip conditions

Abstract: The strain-controlled flow of a wormlike micellar solution in cylindrical Couette geometries with smooth and rough glass inner walls is investigated using 2D 1H NMR velocimetry. We find anomalous shear banding in which fluctuating slip dynamics in combination with surfactant properties lead to a non-lever rule behaviour where the interface position remains constant while the high and low shear rates change. Velocities in the flow direction are imaged in the flow-gradient/vorticity plane. The spatiotemporal resolution achieved reveals fluctuations in flow structure along the vorticity axis and instability of the high shear band.

Extensional rheology of dilute polymer solutions in oscillatory cross-slot flow: the transient behaviour of birefringent strands

Abstract: Birefringent strands are key to understanding polymeric non-Newtonian flows, especially in extension. Utilising microfluidic extensional flow oscillatory rheometry coupled with microvelocimetry (μ-PIV), we report experiments on the genesis, steady state and decay of such strands, together with rheological consequences. For closely monodisperse atactic polystyrene, we report massive effects of the polymer on flow even at low concentrations. The often observed startup “overshoot” in stress and birefringence is observed at unprecedented dilution and discussed in terms of the local strain rate. Strand decay shows pronounced hysteresis. These factors are most important in modelling real flows such as cyclic and capillary entrance flows. Even with the closely monodisperse and well-characterised samples used, residual polydispersity plays a vital role in flow behaviour.

Novel bitumen/isocyanate-based reactive polymer formulations for the paving industry

Abstract: Reactive modification is lately gaining acceptance as a successful way to give added value to bitumen, a crude oil refining by-product. In order to study the effect of both bitumen type and processing method, isocyanate-based reactive modification was carried out with four types of bitumen from different sources, by following two different procedures (“water-free” and “water-involved” processing). The polymer used (MDI–PPG) was synthesized from the reaction of 4,4′-diphenylmethane diisocyanate with a low molecular weight polypropylene glycol. The results obtained demonstrate that the addition of small quantities of this reactive polymer to bitumen endows the resulting modified binder with an improved performance at high in-service temperatures. Interestingly, two different modification pathways have been identified: the first one, which occurs during mixing, is the result of chemical reactions between -NCO groups of the reactive polymer with functional groups containing active hydrogen atoms (mainly, –OH), such as those typically present in the most polar bitumen fractions; the second one has been proved to be a consequence of series reactions involving water. Both pathways, but mainly the latter, lead to bituminous paving materials showing a more complex microstructure, with the consequent change in their rheological response. Finally, very different degrees of modification, depending on the colloidal features of the as-received bitumen, were observed.

A magnetic-dipoles-based micro–macro constitutive model for MRFs subjected to shear deformation

Abstract: A micro–macro description for the constitutive behavior of magnetorheological fluids (MRFs) under shear deformation is formulated based on a more exact magnetic-dipolar model and a statistical approach. The conventional Bingham’s model of viscoplasticity and the dual-viscosity model for MRFs can be obtained from the proposed model as the special cases. This model can take into account the effect of each of the main influencing factors, such as the intensity of magnetic induction, the size, and the volume fraction of particles, shear strain and shear strain rate, saturated magnetization, on the yield shear stress of MRFs. The satisfactory agreement with the experimental results demonstrates the validity of the proposed model. The effect of light weight coating on the sedimentation velocity of the suspended particles is also investigated. This model can evaluate comprehensively the overall property of an MRF and the effects of different main influencing factors; therefore, it may also be of help for the initial design and optimization of high-performance MRFs.

Lubricated compression and X-ray microtomography to analyse the rheology of a fibre-reinforced mortar

Abstract: In this work, the microstructure and the rheology of a glass-fibre-reinforced fresh mortar were studied. Various fibre contents and aspect ratios and two types of fibrous reinforcement, i.e. slender fibre bundles and fibres, were tested. The microstructure was analysed by using X-ray microtomography. It is shown that the non-deformed mortar is a porous granular suspension, the porous microstructure of which is not influenced by the presence of fibres, which in turn display a 2D planar random fibre orientation. The rheology was investigated by subjecting samples to constant axial strain rate and lubricated compression. The roles of the actual strain, the mortar resting time, the fibre content and aspect ratio on recorded stress levels are emphasised. Besides, for the investigated strain rate and material parameters, the mortar flow is quasi-incompressible and does not affect significantly the porous microstructure nor the fibrous one. Lastly, the stress increase which is induced by the addition of fibre bundles is similar to that predicted by Newtonian models of semi-dilute fibre suspensions.

Simulation of the rheological properties of suspensions of oblate spheroidal particles in a Newtonian fluid

Abstract: A simulation algorithm was developed to predict the rheological properties of oblate spheroidal suspensions. The motion of each particle is described by Jeffery’s solution, which is then modified by the interactions between the particles. The interactions are considered to be short range and are described by results from lubrication theory and by approximating locally the spheroid surface by an equivalent spherical surface. The simulation is first tested on a sphere suspension, results are compared with known experimental and numerical data, and good agreement is found. Results are then presented for suspensions of oblate spheroids of two mean aspect ratios of 0.3 and 0.2. Results for the relative viscosity η r, normal stress differences N 1 and N 2 are reported and compared with the few available results on oblate particle suspensions in a hydrodynamic regime. Evolution of the orientation of the particles is also observed, and a clear alignment with the flow is found to occur after a transient period. A change of sign of N 1 from negative to positive as the particle concentration is increased is observed. This phenomenon is more significant as the particle aspect ratio increases. It is believed to arise from a change in the suspension microstructure as the particle alignment increases.

The rheology of polymer solution elastic strands in extensional flow

Abstract: We apply micro-oscillatory cross-slot extensional flow to a semi-dilute poly(ethylene oxide) solution. Micro-particle image velocimetry (μPIV) is used to probe the real local flow field. Extreme flow perturbation is observed, where birefringent strands of extended polymer originate from the stagnation point. This coincides with a large increase in the extensional viscosity. The combination of stagnation point flow and μPIV enables us to investigate directly the stress and strain rates in the strand and so determine the true extensional viscosity of the localised strand alone. The Trouton ratio in the strand is found to be ~4000, amongst the highest values of Trouton ratio ever reported. Consideration of the flow in the exit channels surrounding the highly elastic strand suggests a maximum limit for the pressure drop across the device and the apparent extensional viscosity. This has implications for the understanding of high Deborah number extensional thinning reported in other stagnation point flow situations.

Synthesis and electrorheological properties of polar molecule-dominated TiO 2 particles with high yield stress

Abstract: Two types of amorphous TiO2 particles with different particle sizes were synthesized by a simple sol–gel method and were characterized by X-ray diffraction analysis, field emission scanning electron microscopy, and Fourier transform infrared spectrometry. The electrorheological (ER) results show that the TiO2/silicone oil suspensions exhibited a remarkable ER effect. The static shear stress can be up to 130 kPa (shear rate 0.2 s − 1) under the DC electric field of 4 kV/mm at room temperature. The polar molecules present on the particles’ surface play a decisive role for the observed giant ER effect, which arises from the alignment of polar molecules in the gap between neighboring particles.