Free volume dependence of polymer viscosity

The Simha–Somcynsky (S–S) equation of state (eos) was used to compute the free volume parameter, h, from the pressure–volume–temperature (PVT) dependencies of eight molten polymers. The predicted by eos variation of h with T and P was confirmed by the positron annihilation lifetime spectroscopy; good agreement was found for h(P = constant) = h(T) as well as for h(T = constant) = h(P). Capillary shear viscosity (η) data of the same polymers (measured at three temperatures and six pressures up to 700 bars), were plotted as logη vs 1/h, the latter computed for T and P at which η was measured. In previous works, such a plot for solvents and silicone oils resulted in a “master curve” for the liquid, in a wide range of T and P. However, for molten polymers, no superposition of data onto a “master curve” could be found. The superposition could be obtained allowing the characteristic pressure reducing parameter, P*, to vary. The necessity for using a “rheological” characteristic pressure reducing parameter, P*_R = κP*, with κ = 1 to 2.1 indicates that the free volume parameter extracted from the thermodynamic equilibrium data may not fully describe the dynamic behavior. After eliminating possibility of other sources for the deviation, the most likely culprit seems to be the presence of structures in polymer melts at temperatures above the glass transition, T _g. For example, it was observed that for amorphous polymers at T ≅ 1.52T _g the factor κ = 1, and the deviation vanish.     

Piezo rotary and axial vibrator (PRAV) characterization of a fresh coating during its drying

Using a piezo rotary and axial vibrator (PRAV) the viscoelastic properties of a fresh Al₂O₃ coating that is deposited on a well-chosen plate can be measured simultaneously during drying. There are three types of vibrations available to be excited and detected in their resonance modes, by measuring resonance frequencies f _k and half-widths h _k, before and after coating as a function of time: axial vibration, bending vibration to get the evolving Young’s modulus and rotary vibration to follow the viscosity increase during drying of the thin coating. This information is contained in the complex frequency shifts Ω_k = 2Δf _k /f _k + iΔh _k /f _k of the three vibration modes caused by the coating on the plate. A derivation of the relationships, their validation on Newtonian liquids and experimental applications carried out using the PRAV are given in the paper.     

Squeeze flow between plane and spherical surfaces

Experiments are described in which a constant force F squeezed a fluid, either between two parallel circular plates, or between a plate and convex spherical lens. Newtonian fluids obeyed the relation of Stefan (1874) for plates, and the relation of Adams et al. (1994) for plate and lens. The non-Newtonian yield stress fluids Brylcreem, Laponite and Sephadex were squeezed between plates of various diameter D to attain a stationary separation h. Only for separations greater than h ^* (which depended on the fluid) did Brylcreem and Laponite obey the relation F/D ³ ∝ h ⁻¹ of Scott (1931) and give a yield stress in agreement with the vane method. For Sephadex the dependence of F/D ³ on h disagreed with Scott's relation, but varied as h ^−5/2 for h > 0.6 mm and h ^−3/2 for h < 0.6 mm. On rotating one plate in its plane the yield stress fluids at a fixed F suffered a marked decrease of h. This, and the existence of h ^*, are discussed in terms of the soft glassy material model of Sollich et al. (1997) and Sollich (1998). Brylcreem and Laponite were squeezed between a plate and lenses of various curvature and their yield stress obtained using the relation of Adams et al. (1994) was compared with measurements by plate-plate squeeze-flow and vane methods. Received: 12 April 2000 Accepted: 26 October 2000     

Edge fracture in cone-plate and parallel plate flows

Edge fracture is an instability of cone-plate and parallel plate flows of viscoelastic liquids and suspensions, characterised by the formation of a `crack' or indentation at a critical shear rate on the free surface of the liquid. A study is undertaken of the theoretical, experimental and computational aspects of edge fracture. The Tanner-Keentok theory of edge fracture in second-order liquids is re-examined and is approximately extended to cover the Criminale-Ericksen-Filbey (CEF) model. The second-order theory shows that the stress distribution on the semi-circular crack is not constant, requiring an average to be taken of the stress; this affects the proportionality constant, K in the edge fracture equation −N _2c = KΓ/a, where N _2c is the critical second normal stress difference, Γ is the surface tension coefficient and a is the fracture diameter. When the minimum stress is used, K = 2/3 as found by Tanner and Keentok (1983). Consideration is given to the sources of experimental error, including secondary flow and slip (wall effect). The effect of inertia on edge fracture is derived. A video camera was used to record the inception and development of edge fracture in four viscoelastic liquids and two suspensions. The recorded image was then measured to obtain the fracture diameter. The edge fracture phenomenon was examined to find its dependence on the physical dimensions of the flow (i.e. parallel plate gap or cone angle), on the surface tension coefficient, on the critical shear rate and on the critical second normal stress difference. The critical second normal stress difference was found to depend on the surface tension coefficient and the fracture diameter, as shown by the theory of Tanner and Keentok (1983); however, the experimental data were best fitted by the equation −N _2c = 1.095Γ/a. It was found that edge fracture in viscoelastic liquids depends on the Reynolds number, which is in good agreement with the inertial theory of edge fracture. Edge fracture in lubricating grease and toothpaste is broadly consistent with the CEF model of edge fracture. A finite volume method program was used to simulate the flow of a viscoelastic liquid, obeying the modified Phan-Thien-Tanner model, to obtain the velocity and stress distribution in parallel plate flow in three dimensions. Stress concentrations of the second normal stress difference (N ₂) were found in the plane of the crack; the velocity distribution shows a secondary flow tending to aid crack formation if N ₂ is negative, and a secondary flow tending to suppress crack formation if N ₂ is positive. Received: 4 January 1999 Accepted: 19 May 1999     

Linear viscoelastic behavior of perfluorooctyl sulfonate micelles: effects of counter-ions

Linear viscoelastic behavior was investigated for aqueous solutions of perfluorooctyl sulfonate (C₈F₁₇SO⁻ ₃; abbreviated as FOS) micelles having a mixture of tetraethylammonium (N⁺(C₂H₅)₄; TEA) and lithium (Li⁺) ions as the counter-ions. The solutions had the same FOS concentration (0.1 mol l⁻¹) and various Li⁺ fractions in the counter-ions, φ_Li = 0−0.6, and the FOS micelles in these solutions formed threads which further organized into dendritic networks. At T ≤ 15 °C, the terminal relaxation time τ and the viscosity η, governed by thermal scission of the networks, increased with increasing φ_Li up to 0.55. A further increase of φ_Li resulted in decreases of τ and η and in broadening of the relaxation mode distribution. These rheological changes are discussed in relation to the role of TEA ions in thermal scission: Previous NMR studies revealed that only a fraction of TEA ions were tightly bound to the FOS micellar surfaces and these bound ions stabilized the thread/network structures. The concentration of non-bound TEA ions, C_TEA ^*, decreased and finally vanished on increasing φ_Li up to φ_Li ^* ≅ 0.6, and the concentration of the bound TEA ions significantly decreased on a further increase of φ_Li. The non-bound TEA ions appeared to catalyze the thermal scission of the FOS threads, and the observed increases of τ and η for φ_Li < 0.55 were attributed to the decrease of C_TEA ^*. On the other hand, the decreases of τ and η as well as the broadening of the mode distribution, found for φ_Li > 0.55 (where C_TEA ^* ≅ 0), were related to destabilization of the FOS threads/networks due to a shortage of the bound TEA ions and to the existence of concentrated Li⁺ ions. Viscoelastic data of pure FOSTEA and FOSTEA/FOSLi/TEACl solutions lent support to these arguments for the role of TEA ions in the relaxation of FOSTEA/FOSLi solutions. Received: 12 October 1999/Accepted: 1 November 1999     

Yield stress of structured fluids measured by squeeze flow

Various structured fluids were placed between the parallel circular plates of a squeeze-flow rheometer and squeezed by a force F until the fluid thickness h was stationary. Fluid thickness down to a few microns could be measured. Most fluids showed two kinds of dependence of f on h according to an experimentally-determined thickness h ^*. If h > h ^* then F varied in proportion to h ⁻¹ as predicted by Scott (1931) for a fluid with a shear yield stress τ₀. The magnitude of τ₀ from squeeze-flow data in this region was compared with the yield stress measured by the vane method. For some fluids τ₀ measured by squeeze flow was less than the vane yield stress, suggesting that the yield stress of fluid in contact with the plates was less than the bulk yield stress. If h < h ^* then F varied approximately as h ^−5/2 and the squeeze-flow data in this region analysed with Scott's relationship gave a yield stress which increased as the fluid thickness decreased. This previously unreported effect may result from unconnected regions of large yield stress in the fluid of size similar to h ^* which are not sensed by the vane and which become effective in squeeze flow only when h < h ^*. Received: 13 December 1999/Accepted: 4 January 2000     

Rheology of SiO2/(acrylic polymer/epoxy) suspensions. I. Linear viscoelasticity

Linear viscoelastic properties of SiO₂/(AP/EP) suspension with various SiO₂ volume fractions (ϕ) in a blend of acrylic polymer (AP) and epoxy (EP) were investigated at various temperatures (T). The AP/EP contained 70 vol.% of EP. The SiO₂ particles were treated with epoxy silane coupling agent. The effects of the SiO₂ particles are more pronounced in the terminal zone: a transition from viscoelastic liquid (ϕ ≤ 30 vol.%) to viscoelastic solid (ϕ ≥ 40 vol.%) was observed which can be interpreted as a critical gelation occurring at a critical particle content and critical gel temperature. The SiO₂/(AP/EP) systems exhibited a critical gel behavior at ϕ ≅ 35 vol.% and T ≅ 100°C characterized with a power–law relationship between the storage and loss moduli (G ^′ and G ^″) and frequency (ω); G ^′ = G ^″/tan(nπ/2) ∝ ω ⁿ . The critical gel exponent (n) was estimated to be about 0.45. The gelation occurred with increasing T.     

Miniaturized Compression Test at Very High Strain Rates by Direct Impact

A modified miniaturized version of the Direct Impact Compression Test (DICT) technique is described in this paper. The method permits determination of the rate-sensitive plastic properties of materials up to strain rate ∼10⁵ s⁻¹. Miniaturization of the experimental setup with specimen dimensions: diameter d _S = 2.0 mm and thickness l _S = 1.0 mm, Hopkinson bar diameter 5.2 mm, with application of a novel optical arrangement in measurement of specimen strain, makes possible compression tests at strain rates from ∼10³ s⁻¹ to ∼10⁵ s⁻¹. In order to estimate the rate sensitivity of a low-alloy construction steel, quasi-static, Split Hopkinson Pressure Bar (SHPB) and DICT tests have been performed at room temperature within the rate spectrum ranging from 5*10⁻⁴ s⁻¹ to 5*10⁴ s⁻¹. Adiabatic heating and friction effects are analyzed and the final true stress versus true strain curves at different strain rates are corrected to a constant temperature and zero friction. The results have been analyzed in the form of true stress versus the logarithm of strain rate and they show two regions of a constant rate sensitivity : relatively low up to the strain rate threshold ∼50 s⁻¹, and relatively high above the threshold, up to strain rate ∼4.5*10⁴ s⁻¹.     

Effect of a hydrotrope on the viscoelastic properties of polymer-like micellar solutions

Low-viscosity micellar aqueous solutions of cetyltrimethylammonium bromide (CTAB) undergo a major change in the presence of the hydrotrope, potassium 1-phenylmethylsulfate (KPhMS), producing a highly viscoelastic entanglement network of polymer-like micelles. The system studied here shows typical shear banding flow behavior, which tends to disappear with increasing the hydrotrope-to-surfactant concentration ratio (C _H / C _S). The linear rheological response was analyzed with the model of Granek–Cates, whereas the nonlinear behavior was reproduced with the Bautista–Manero–Puig (BMP) model. Both models introduce a kinetic equation to account for the breaking and reformation of the micelles, and they predict the linear and nonlinear rheological data very well. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Vortex ring generation due to the coalescence of a water drop at a free surface

 Results are presented of an experimental investigation of vortex ring formation by a fluid drop contacting a free surface with negligible velocity. The pool fluid is mixed with fluorescein dye, and a laser sheet is used to illuminate a plane of the flow. A series of representative images is recorded by a CCD camera and speculation is made regarding specific sources of vorticity flux through the free surface. Two scaling analyses previously presented by other investigators are demonstrated to be equivalent under the assumptions of this experiment, and they provide the motivation for a series of test runs in which the duration of the coalescence process, τ_*, is related to variations in drop diameter L and fluid surface tension σ. Experimental results are in agreement with the analyses, showing τ_*∼σ^-1/2 and τ_*∼L ^3/2. Received: 22 December 1995 / Accepted: 15 October 1996     

On Finite Shear

If a pair of material line elements, passing through a typical particle P in a body, subtend an angle Θ before deformation, and Θ+γ after deformation, the pair of material elements is said to be sheared by the amount γ. Here all pairs of material elements at P are considered for arbitrary deformations. Two main problems are addressed and solved. The first is the determination of all pairs of material line elements at P which are unsheared. The second is the determination of that pair of material line elements at P which suffers the maximum shear. All unsheared pairs of material elements in a given plane π(S) with normal S passing through P are considered. Provided π(S) is not a plane of central circular section of the C-ellipsoid at P (where C is the right Cauchy-Green strain tensor), it is seen that corresponding to any material element in π(S) there is, in general, one companion material element in π(S) such that the element and its companion are unsheared. There are, however, two elements in π(S) which have no companions. We call their corresponding directions \textit{limiting directions.} Equally inclined to the direction of least stretch in the plane π(S), the limiting directions play a central role. It is seen that, in a given plane π(S), the pair of material line elements which suffer the maximum shear lie along the limiting directions in π(S). If Θ _L is the acute angle subtended by the limitig directions in π(S) before deformation, then this angle is sheared into its supplement π−Θ _L so that the maximum shear γ^*;(S) is γ^*=π− 2 Θ _L . If S is given and C is known, then Θ _L may be determined immediately. Its calculation does not involve knowing the eigenvectors or eigenvalues of C. When all possible planes through P are considered, it is seen that the global maximum shear γ^* _G occurs for material elements lying along the limiting directions in the plane spanned by the eigenvectors of C corresponding to the greatest principal stretch λ₃ and the least λ₁. The limiting directions in this principal plane of C subtend the angle and . Generally the maximum shear does not occur for a pair of material elements which are originally orthogonal. For a given material element along the unit vector N, there is, in general, in each plane π(S passing through N at P, a companion vector M such that material elements along N and M are unsheared. A formula, originally due to Joly (1905), is presented for M in terms of N and S. Given an unsheared pair π(S), the limiting directions in π(S) are seen to be easily determined, either analytically or geometrically. Planar shear, the change in the angle between the normals of a pair of material planar elements at X, is also considered. The theory of planar shear runs parallel to the theory of shear of material line elements. Corresponding results are presented. Finally, another concept of shear used in the geology literature, and apparently due to Jaeger, is considered. The connection is shown between Cauchy shear, the change in the angle of a pair of material elements, and the Jaeger shear, the change in the angle between the normal N to a planar element and a material element along the normal N. Although Jaeger's shear is described in terms of one direction N, it is seen to implicitly include a second material line element orthogonal to N. Accepted: May 25, 1999     

Comparison of the vortex shedding behavior of a single plate and a plate array

This study compares the shedding behavior around and downstream of a single plate positioned in a flow field alone with the shedding behavior around and downstream of the same plate positioned in an array of identical plates. The shedding frequencies and corresponding Strouhal numbers based on chord [S _r (c)] and based on thickness [S _r (t)] are obtained using a hot-wire anemometer. In comparison with the plate positioned as a single plate, the same plate placed in a plate array shows increases in S _r (c) of up to 55.5% and produces a dominant peak in the power spectra that is wider by a factor of 3.5. In contrast to the single-plate results, which exhibit step changes in S _r (c) of about 0.6 at c/t ≈ 6, 8 and 11, the plate positioned in an array shows only one abrupt transition at c/t ≈ 4. Received: 26 January 1999/Accepted: 7 February 2000     

Viscoelastic properties of ultra-high viscosity alginates

Ultra-high viscosity alginates were extracted from the brown seaweeds Lessonia nigrescens (UHV_N, containing 61% mannuronate (M) and 2% guluronate (G)) and Lessonia trabeculata (UHV_T, 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 [(g)\dot]\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–[(g)\dot]\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.     

Shear banding during nonlinear creep with a solution of monodisperse polystyrene

Creep experiments with a solution of polystyrene (M _w = 2.6 MDa, 16 vol.%, 25 °C) in diethyl phthalate are reported for stresses between 100 and 2,500 Pa (≈ 3G _N ⁰/4). The aim was to look for a flow transition as reported for strongly entangled poly(isobutylene) solutions. The experiments with the polystyrene solution were repeated for cone angles of 2, 4, and 6° (radius 15 mm) and showed no dependence on cone angle. The Cox–Merz rule was not fulfilled for stresses beyond about 800 Pa. The tangential observation with a CCD camera showed that the edge took a concave shape because of the second normal stress difference. Beyond 1,000 Pa, the concave edge develops into a crevice, thus substantially reducing the effective cross-section. This leads to runaway in a constant torque experiment. At p ₂₁ = 800 Pa, head-on particle tracking confirms that the originally linear velocity profile takes a gooseneck shape, thus revealing shear banding. When the creep stress is stepped down to 100 Pa, this velocity profile evolves back to a linear one. The conclusion from this work is that even if nonlinear creep experiments are reproducible and a steady state is reached, this does not mean that the flow field is homogeneous. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

The motion of long bubbles through viscoelastic fluids in capillary tubes

The penetration of long gas bubble through a viscoelastic fluid in a capillary tube has been studied in order to investigate the influence of viscoelastic material properties on the hydrodynamic coating thickness and local flow kinematics. Experiments are conducted for three tailored ideal elastic (Boger) fluids, designed to exhibit similar steady shear properties but substantially different elastic material functions. This allows for the isolation of elastic and extensional material effects on the bubble penetration process. The shear and extensional rheology of the fluid is characterized using rotational and filament stretching rheometers (FSR). The fluids are designed such that the steady-state extensional viscosity measured by the FSR at a Deborah number (De) greater than 1 differs over three orders of magnitude (Trouton ratio = 10³–10⁶). The experiment set up to measure the hydrodynamic coating thickness is designed to provide accurate data over a wide range of capillary numbers (0.01 < Ca < 100). The results indicate that the coating thickness in this process increases with an increase in the extensionally thickening nature of the fluid. Experiments are also conducted using several different capillary tube diameters (0.1 < D < 1 cm), in order to compare responses at similar Ca but different flow De. Suitable scaling methods and nonlinear viscoelastic constitutive equations are explored to characterize the displacement process for polymeric fluids. Bubble tip shapes at different De are recorded using a CCD camera, and measured using an edge detection algorithm. The influence of the mixed flow field on the bubble tip shape is examined. Particle tracking velocimetry experiments are conducted to compare the influence of viscoelastic properties on the velocity field in the vicinity of the bubble tip. Local shear and extension rates are calculated in the vicinity of the bubble tip from the velocity data. The results provide quantitative information on the influence of elastic and extensional properties on the bubble penetration process in gas-assisted injection molding. The bubble shape and velocity field information provides a basis for evaluating the performance of constitutive equations in mixed flow. Received: 19 January 1999 Accepted: 30 June 1999     

Non-linear dynamics of semi-dilute polydisperse polymer solutions in microfluidics: effects of flow geometry

The non-linear dynamics of a semi-dilute (c/c* = 15) polydisperse polyethylene oxide (PEO) solution in microfluidics are studied experimentally using benchmark contraction–expansion flow geometries with three contraction–expansion ratios (4:1:4, 8:1:8 and 16:1:16) and two narrow channel lengths (L _c/D _h = 53 and 5.3, where L _c is the length of the narrow channel and D _h is its hydraulic diameter). Complex flows over a range of elasticity numbers (El), Weissenberg numbers (Wi) and Reynolds numbers (Re) are characterized using micro-particle image velocimetry ( \upmu\upmu-PIV) and pressure drop measurements. The evolution of vortex formation and dynamics has been visualized through a step-flow-rate experiment. Various flow dynamics regimes have been quantified and are presented in a Wi–Re diagram. The experimental results reveal that the contraction ratio can result in qualitatively different vortex dynamics of semi-dilute polymer solutions in microfluidics, whereas the length of the narrow channel merely affects the dynamics at a quantitative level. A single elasticity number, if defined by the size of the narrow channel, is not sufficient to account for the effects of contraction ratio on the non-linear vortex dynamics.     

Three-dimensional viscoelastic simulation of coextrusion process: comparison with experimental data

 Three-dimensional numerical simulation of viscoelastic coextrusion process has been performed and numerical results were compared with the experimental data of Karagiannis et al. (1990). By varying the magnitude of the second normal stress difference and its ratio of Fluid I and Fluid II, we were able to control the interface profile and the degree of encapsulation along the downstream direction. By increasing the parameter α (α_Fluid I=α_Fluid II) from 0.1 to 0.4 in the Giesekus model and increasing the α ratio (α_Fluid Iα_Fluid II) between Fluid I and Fluid II from 2.0 to 4.0 in the permissible range of realistic polymeric systems, the interface profile and the degree of encapsulation along the downstream direction were fitted with the experimental results. There was little difference between the numerical results and the experimental data in the interface profile and the degree of encapsulation along the downstream direction when the α ratio was set to 3.0 (0.3:0.1). Fluid I with larger magnitude of the second normal stress difference protrudes into Fluid II with smaller magnitude of the second normal stress difference around the symmetric plane, while Fluid II wraps around Fluid I near the side walls. As the ξ ₁ ratio (ξ _{1 ,Fluid I}ξ _{1 ,Fluid II}) increases from 1.0 to 3.0 for the two-mode Phan-Thien and Tanner model, it was found that the curvature of the interface profile increased, and the difference between the numerical results and the experimental data in the interface profile and the degree of encapsulation along the downstream direction was almost negligible when the ξ ₁ ratio was set to 3.0 (0.54:0.18). Although the parameters of viscoelastic models were fitted by using the shear viscosity data only, quantitative agreements between the numerical results and the experimental coextrusion data were quite satisfactory. Received: 24 April 2001 Accepted: 5 June 2001     

Precursor vacuum-ultraviolet radiation ahead of strong shock waves in a shock tube

The profile and excitation mechanism of vacuum-ultraviolet radiation emitted from shock wave is investigated in a shock tube. For shock wave in argon, the rdiation is due to resonant transition excited by argon-argon collision in the shock front with excitation cross section coefficientS ^*=1.0×10⁻¹⁷ cm²·ev⁻¹ and activation energyE ^*=11.4 ev. For shock wave in air the radition is emitted from a very thin shock layer in which the mechanism ofX ¹∑→b ¹∑ of N₂ is excited with excitation cross sectionQ=2×10⁻¹⁶cm² and activation energyE ^*=12.1 ev. Institute of Mechanics, Academia Sinica     

Planar elongation of soft polymeric networks

A new test fixture for the filament stretch rheometer (FSR) has been developed to measure planar elongation of soft polymeric networks with application towards pressure-sensitive adhesives (PSAs). The concept of this new geometry is to elongate a tube-like sample by keeping the perimeter constant. To validate this new technique, soft polymeric networks of poly(propylene oxide) (PPO) were investigated during deformation. Particle tracking and video recording were used to detect to what extent the imposed strain rate and the sample perimeter remained constant. It was observed that, by using an appropriate choice of initial sample height, perimeter, and thickness, the planar stretch ratio will follow l(t) = h(t)/h₀ = exp([(e)\dot] t)\lambda(t) = h(t)/h_0= \exp({\dot{\varepsilon}} t), with h(t) being the height at time t and [(e)\dot]{\dot{\varepsilon}} the imposed constant strain rate. The perimeter would decrease by a few percent only, which is found to be negligible. The ideal planar extension in this new fixture was confirmed by finite element simulations. Analysis of the stress difference, σ _zz  − σ _xx , showed a network response similar to that of the classical neo-Hookean model. As the Deborah number was increased, the stress difference deviated more from the classical prediction due to the dynamic structures in the material. A modified Lodge model using characteristic parameters from linear viscoelastic measurements gave very good stress predictions at all Deborah numbers used in the quasi-linear regime.     

Rheological and mechanical properties of silica colloids: from Newtonian liquid to brittle behaviour

Rheological and mechanical properties of aqueous mono-disperse silica suspensions (Ludox? HS40) are investigated as a function of particle volume fraction (ϕ _p ranging from 0.22 to 0.51) and water content, using shear rate tests, oscillatory methods, indentation and an ultrasonic technique. As the samples are progressively dried, four regimes are identified; they are related to the increasing particle content and the existence and behaviour of the electrical double layer (EDL) around each particle. For 0.22 ≤ ϕ _p ≤ 0.30), the suspensions are stable due to the strong electrostatic repulsion between particles and show Newtonian behaviour (I). As water is removed, the solution pH decreases and the ionic strength increases. The EDL thickness therefore slowly decreases, and screening of the electrostatic repulsion increases. For 0.31 ≤ ϕ _p ≤ 0.35, the suspensions become turbid and exhibit viscoelastic (VE) shear thinning behaviour (II), as they progressively flocculate. For 0.35 ≤ ϕ _p ≤ 0.47, the suspensions turn transparent again and paste-like, with VE shear thinning behaviour and high elastic modulus (III). At higher particle concentration, the suspensions undergo a glass transition and behave as an elastic brittle solid (IV, ϕ _p = 0.51).