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

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.     

Radial filtration during constant-force squeeze flow of soft solids

Various soft solid suspensions were squeezed at constant force between polished and roughened circular glass plates and the time-dependence of the interplate separation was measured. The filterability of suspensions was quantified by their desorptivity S obtained from measurements of capillary suction time. The squeeze flow (SF) of suspensions for which S < 2 μm s^−1/2 was largely consistent with rheological theory, which neglected radial filtration: the relative motion between the liquid and solid phases of the suspension in the radial pressure gradient. Suspensions having S > 2 μm s^−1/2 showed SF behavior that was consistent with the presence of radial filtration.     

Flow-induced crystallization of high-density polyethylene: the effects of shear and uniaxial extension

The effects of shear, uniaxial extension and temperature on the flow-induced crystallization of two different types of high-density polyethylene (a metallocene and a ZN-HDPE) are examined using rheometry. Shear and uniaxial extension experiments were performed at temperatures below and well above the peak melting point of the polyethylenes in order to characterize their flow-induced crystallization behavior at rates relevant to processing (elongational rates up to 30 s^− 1 and shear rates 1 to 1,000 s^− 1 depending on the application). Generally, strain and strain rate found to enhance crystallization in both shear and elongation. In particular, extensional flow was found to be a much stronger stimulus for polymer crystallization compared to shear. At temperatures well above the melting peak point (up to 25°C), polymer crystallized under elongational flow, while there was no sign of crystallization under simple shear. A modified Kolmogorov crystallization model (Kolmogorov, Bull Akad Sci USSR, Class Sci, Math Nat 1:355–359, 1937) proposed by Tanner and Qi (Chem Eng Sci 64:4576–4579, 2009) was used to describe the crystallization kinetics under both shear and elongational flow at different temperatures.     

Experimental investigation on turbulence modification in a horizontal channel flow at relatively low mass loading

Particle-laden flows in a horizontal channel were investigated by means of a two-phase particle image velocimetry (PIV) technique. Experiments were performed at a Reynolds number of 6 826 and the flow is seeded with polythene beads of two sizes, 60 μm and 110 μm. One was slightly smaller than and the other was larger than the Kolmogorov length scale. The particle loadings were relatively low, with mass loading ratio ranging from 5×10⁻⁴ to 4×10⁻² and volume fractions from 6×10⁻⁷ to 4.8×10⁻⁵, respectively. The results show that the presence of particles can dramatically modify the turbulence even under the lowest mass loading ratio of 5×10⁻⁴. The mean flow is attenuated and decreased with increasing particle size and mass loading. The turbulence intensities are enhanced in all the cases concerned. With the increase of the mass loading, the intensities vary in a complicated manner in the case of small particles, indicating complicated particle-turbulence interactions; whereas they increase monotonously in the case of large particles. The particle velocities and concentrations are also given. The particles lag behind the fluid in the center region but lead in the wall region, and this trend is more prominent for the large particles. The streamwise particle fluctuations are larger than the gas fluctuations for both sizes of particles, however their varying trend with the mass loadings is not so clear. The wall-normal fluctuations increase with increasing mass loadings. They are smaller in the 60 μm particle case but larger in the 110 μm particle case than those of the gas phase. It seems that the small particles follow the fluid motion to certain extent while the larger particles are more likely dominated by their own inertia. Finally, remarkable non-uniform distributions of particle concentration are observed, especially for the large particles. The inertia of particles is proved to be very important for the turbulence modification and particles behaviors and thus should be considered in horizontal channels. The project supported by the National Natural Science Foundation of China (50276021), and Program for New Century Excellent Talents in University, Ministry of Education (NCET-04-0708) The English text was polished by Yunming Chen.     

Rheostructural studies of a discotic mesophase pitch at processing flow conditions

The flow-induced microstructure of a mesophase pitch was studied within custom-made dies for changing wall shear rates from 20 to 1,100 s^− 1, a flow scenario that is typically encountered during fiber spinning. The apparent viscosity values, measured at the nominal wall shear rates ranging from 500 to 2,500 s^− 1 using these dies, remain fairly constant. The microstructure was studied in two orthogonal sections: r–θ (cross section) and r–z (longitudinal mid plane). In these dies, the size of the microstructure gradually decreases toward the wall (to as low as a few micrometers), where shear rate is highest. Furthermore, as observed in the r–θ plane of the capillary, for a significant fraction of the cross section, discotic mesophase has a radial orientation. Thus, the directors of disc-like molecules were aligned in the vorticity (θ) direction. As confirmed from the microstructure in the r–z plane, most of the discotic molecules remain nominally in the flow plane. Orientation of the pitch molecules in the shear flow conditions is consistent with that observed in controlled low-shear rheometric experiments reported earlier. Microstructral investigation suggests that the radial orientation of carbon fibers obtained from a mesophase pitch originates during flow of pitch through the die.     

The rheological characterisation of bread dough using capillary rheometry

An Australian hard wheat flour–water dough has been characterised using parallel plate and capillary rheometers over an extensive range of apparent shear rates (10^− 3–10³ s^− 1) relevant to process conditions. Torsional measurements showed that the shear viscosity of the dough increased with strain to a maximum value and then decreased, suggesting a breakdown of the dough structure. Both torsional and capillary experiments revealed the shear-thinning behaviour of the dough. The wall slip phenomenon in capillary rheometry was investigated and found to be diameter dependent and occurred at a critical shear stress of approximately 5–10 kPa. A two-regime power law behaviour was observed, with the power law index approximately 0.3 in the low shear rate range increasing to 0.67 in the high shear rate range. Pressure fluctuation was observed in the capillary data and increased with shear rate, in particular, at shear rates approaching 10⁴ s^− 1. The results demonstrate that capillary rheometry is a viable means of rheologically testing dough at high shear rates provided pressure fluctuation is carefully monitored and capillary rheometry corrections, including wall slip, are accounted for.     

Irradiation-Induced Solute Clustering in a Low Nickel FeMnNi Ferritic Alloy

Understanding the radiation embrittlement of reactor pressure vessel (RPV) steels is required to be able to operate safely a nuclear power plant or to extend its lifetime. The mechanical properties degradation is partly due to the clustering of solute under irradiation. To gain knowledge about the clustering process, a Fe−1.1 Mn−0.7 Ni (at.%) alloy was irradiated in a test reactor at two fluxes of 0.15 and 9 ×10¹⁷ n _E > 1MeV .m^− 2.s^− 1 and at increasing doses from 0.18 to 1.3 ×10²⁴ n _E > 1MeV .m^− 2 at 300°C. Atom probe tomography (APT) experiments revealed that the irradiation promotes the formation in the α iron matrix of Mn/Mn and/or Ni/Ni pair correlations at low dose and Mn–Ni enriched clusters at high dose. These clusters dissolve partially after a thermal treatment at 400°C. Based on a comparison with thermodynamic calculations, we show that the solute clustering under irradiation can just result from an induced mechanism.     

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.     

Shear Failure of Inconel 718 under Dynamic Loads

Kinetics of deformation and fracture of nickel–iron alloy Inconel 718 under dynamic shear loading was measured using a split torsional Hopkinson bar facility and high-speed photography. Tubular specimens with a reduced gage length and a starter notch were sheared at strain rates up to 6 × 10³ s⁻¹. High-speed photographs of fiducial lines scribed on the specimen surface showed the development of local strains and cracking. This paper describes the experimental and analytical procedures, illustrates average and local plastic strain evolution, and presents shear crack initiation times and propagation speeds.     

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     

Effects of deformed volume, volume fraction and particle size on the deformation behaviour of W/Cu composites

Tungsten/copper (W/Cu) particle reinforced composites were used to investigate the scaling effects on the deformation and fracture behaviour. The effects of the volume fraction and the particle size of the reinforcement (tungsten particles) were studied. W/Cu-80/20, 70/30 and 60/40 wt.% each with tungsten particle size of 10 μm and 30 μm were tested under compression and shear loading. Cylindrical compression specimens with different volumes (D_S = H) were investigated with strain rates between 0.001 s⁻¹ and about 5750 s⁻¹ at temperatures from 20 °C to 800 °C. Axis-symmetric hat-shaped shear specimens with different shear zone widths were examined at different strain rates as well. A clear dependence of the flow stress on the deformed volume and the particle size was found under compression and shear loading. Metallographic investigation was carried out to show a relation between the deformation of the tungsten particles and the global deformation of the specimens. The size of the deformed zone under either compression or shear loading has shown a clear size effect on the fracture of the hat-shaped specimens.The quasi-static flow curves were described with the material law from Swift. The parameters of the material law were presented as a function of the temperature and the specimen size. The mechanical behaviour of the composite materials were numerically computed for an idealized axis-symmetric hat-shaped specimen to verify the determined material law.     

Measurements and model predictions of transient elongational rheology of polymeric nanocomposites

Transient elongational rheology of two commercial-grade polypropylene (PP) and the organoclay thermoplastic nanocomposites is investigated. A specifically designed fixture consisting of two drums (SER Universal Testing Platform) mounted on a TA Instruments ARES rotational rheometer was used to measure the transient uniaxial extensional viscosity of both polypropylene and nanoclay/PP melts. The Hencky strain rate was varied from 0.001 to 2 s^− 1, and the temperature was fixed at 180°C. The measurements show that the steady-state elongational viscosity was reached at the measured Hencky strains for the polymer and for the nanocomposites. The addition of nanoclay particles to the polymer melt was found to increase the elongation viscosity principally at low strain rates. For example, at a deformation rate of 0.3 s^− 1, the steady-state elongation viscosity for polypropylene was 1.4 × 10⁴ Pa s which was raised to 2.8 × 10⁴ and 4.5 × 10⁴ Pa s after addition of 0.5 and 1.5 vol.% nanoclay, respectively. A mesoscopic rheological model originally developed to predict the motion of ellipsoid particles in viscoelastic media was modified based on the recent developments by Eslami and Grmela (Rheol Acta 47:399–415, 2008) to take into account the polymer chain reptation. We show that the orientation states of the particles and the rheological behavior of the layered particles/thermoplastic hybrids can be quantitatively explained by the proposed model.     

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

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

Transfer model and kinetic characteristics of $${\rm NH}_{4}^{+}$$ –K+ ion exchange on K-zeolite

Based on the mass transfer theory, a new mass transfer model of ion-exchange process on zeolite under liquid film diffusion control is established, and the kinetic curves and the mass transfer coefficients of –K⁺ ion-exchange under different conditions were systemically determined using the shallow-bed experimental method. The results showed that the –K⁺ ion-exchange rates and transfer coefficients are directly proportional to solution flow rate and temperature, and inversely proportional to solution viscosity and the size of zeolite granules. It also showed that the transfer coefficient is not influenced by the ion concentrations. For a large ranges of operational conditions including temperatures (10 − 75°C), flow rates (0.031 m s⁻¹ −0.26 m s⁻¹), liquid viscosities (1.002 × 10⁻³ N s m⁻² − 4.44 × 10⁻³ N s m⁻²), and zeolite granular sizes (0.2 − 1.45 mm), the average mass transfer coefficients calculated by the model agree with the experimental results very well.     

Three views of viscoelasticity for Cox–Merz materials

A slight rearrangement of the classical Cox and Merz rule suggests that the shear stress value of steady shear flow, , and complex modulus value of small amplitude oscillatory shear, G^∗(ω) = (G^′2 + G^″2)^1/2, are equivalent in many respects. Small changes of material structure, which express themselves most sensitively in the steady shear stress, τ, show equally pronounced in linear viscoelastic data when plotting these with G^∗ as one of the variables. An example is given to demonstrate this phenomenon: viscosity data that cover about three decades in frequency get stretched out over about nine decades in G^∗ while maintaining steep gradients in a transition region. This suggests a more effective way of exploiting the Cox–Merz rule when it is valid and exploring reasons for lack of validity when it is not. The τ −G^∗ equivalence could also further the understanding of the steady shear normal stress function as proposed by Laun.     

Simultaneous determination of shear and extensional viscosities and wall slip by on-line rheometry with parameter fitting: an application to EPDM rubber

Shear and extensional viscosities and wall slip are determined simultaneously under extrusion processing conditions using an on-line rheometer. Because it is not possible to independently control flow rate and temperature, classical methods for interpretation of capillary data cannot be used with on-line rheometry. This limitation is overcome using computational optimization to fit parameters in a flow model. This consists of three parts, representing shear viscosity, extensional viscosity, and wall slip. Three-parameter, power law forms, based on local instantaneous deformation rates and including temperature dependence, are used for each, and analytic solutions applied for entry flow and flow in the capillary. For entry flow, the Cogswell–Binding approach is used, and for developed flow in the capillary a solution incorporating wall slip is derived. The rheometer, with interchangeable capillaries, is mounted in place of the die on a rubber profile extrusion line. Pressure drops and temperatures for extrusion of an EPDM rubber through 2 mm diameter capillaries of length 0, 2, 3, 4, and 5 mm are logged and flow rates determined for a range of extruder speeds (5 to 20 rpm). Pressures ranged from 60 to 75 bar and temperatures from 86 to 116 °C. Mean flow velocity in the capillaries was between 5 × 10⁻³ and 5 × 10⁻¹ m s⁻¹. The nine material parameters are optimized for best fit of the analytic pressure drops to experimental data, using about 100 data points, with the Levenberg–Marquardt method. It is concluded that flow is dominated by extension and wall slip. Shear flow appears to play little part. The slip model indicates that slip velocity increases much more rapidly than the wall shear stress (in the range 0.5–1 MPa) and decreases with temperature for a given stress level. Results for the (uniaxial) extensional viscosity represent an engineering approximation to this complex phenomenon at the high strains (approximately 200) and high extension rates (up to 800 s⁻¹) applying in the extrusion. Results indicate a slight extension hardening and a decrease with temperature. Results are put into the context of the available studies in the literature, which, particularly with regard to wall-slip and extensional flow, consider conditions far removed from those applying in industrial extrusion. The present methods provide a powerful means for flow characterization under processing conditions, providing data suitable for use in computer simulations of extrusion and optimization of die design.     

Rheology and birefringence of Fomblin YR at very high shear rates

The rheological and structural properties of perfluoropolyether (PFPE) lubricant films including viscosity, shear stress, and birefringence were measured at relatively low to extremely high shear rates using a rotational optical rheometer. The viscosity of various films with different thicknesses exhibit Newtonian behavior up to a shear rate 1 × 10⁴ s⁻¹, with a transition to shear-thinning behavior obvious at higher shear rates. Birefringence of these films was also measured for the first time, and these results indicate chain alignment with shear in the shear-thinning regime. The shear rate at which alignment occurs is similar to that of the onset of shear thinning. This correlation between chain alignment and shear thinning provides direct evidence that the ability of PFPEs to lubricate hard drives at high shear rates is a direct consequence of the ability of the applied shear field to align the molecules on a molecular level.     

Experimental Investigation of Strain Rate Dependence of Nanocrystalline Pt Films

A new microscale uniaxial tension experimental method was developed to investigate the strain rate dependent mechanical behavior of freestanding metallic thin films for MEMS. The method allows for highly repeatable mechanical testing of thin films for over eight orders of magnitude of strain rate. Its repeatability stems from the direct and full-field displacement measurements obtained from optical images with at least 25 nm displacement resolution. The method is demonstrated with micron-scale, 400-nm thick, freestanding nanocrystalline Pt specimens, with 25 nm grain size. The experiments were conducted in situ under an optical microscope, equipped with a digital high-speed camera, in the nominal strain rate range 10⁻⁶–10¹ s⁻¹. Full field displacements were computed by digital image correlation using a random speckle pattern generated onto the freestanding specimens. The elastic modulus of Pt, E = 182 ± 8 GPa, derived from uniaxial stress vs. strain curves, was independent of strain rate, while its Poisson’s ratio was v = 0.41 ± 0.01. Although the nanocrystalline Pt films had the elastic properties of bulk Pt, their inelastic property values were much higher than bulk and were rate-sensitive over the range of loading rates. For example, the elastic limit increased by more than 110% with increasing strain rate, and was 2–5 times higher than bulk Pt reaching 1.37 GPa at 10¹ s⁻¹.     

Drag reduction change of polyethyleneoxide solutions in pipe flow

Change of drag reduction (DR) along a tube (D=2 mm, L=4 m) was experimentally investigated. To attain turbulent flow with Re=8 × 10⁴, a tank operated under high pressure up to 16 MPa. Solutions of different brands of polyethyleneoxide (PEO) with concentrations from 1 ppm to 100 ppm were tested. The results indicate that DR is not a constant value but depends on the time and intensity of interaction between the polymer and the turbulent flow. There are three regions with different behaviors of DR: growth, maximum, and slope down. Maximum DR coincides with the Virk ultimate DR and can be described by the suggested simple formula . A decrease in the DR maximum has not been found even for high shear stresses τ _p < 800 Pa. DR dynamics for four brands of PEO with different molecular weight was studied. Direct experimentally determined DR may be greater than the Virk ultimate value if the change in velocity profile is not taken into account. The corrected DR never exceeds the ultimate DR. Received: 10 April 2000/Accepted: 24 May 2001     

Characterization of the flow properties of sodium carboxymethylcellulose via mechanical and optical techniques

Sodium carboxymethylcellulose (NaCMC) in solution represents a complex rheological system, since it forms aggregates and associations and hence higher-level structures and, depending on the synthesis, is only found in a molecularly dispersed form in exceptional cases. Rheo-mechanical investigations of the viscoelasticity showed that the Cox-Merz rule is not fulfilled. The aim was therefore to examine whether rheo-optics could be employed to provide more detailed conclusions about the parameters that influence the flow behavior of NaCMC than has hitherto been available with mechanical methods. The flow birefringence, Δn ^′, rises as the degree of polymerization increases, and exhibits the same dependence on molar mass as does the viscosity: Δn ^′∝M _w ^3.4. As the degree of polymerization increases while the shear rate remains constant, the polymer segments become more distinctly aligned in the direction of shear. Hence increasing the degree of polymerization also affects the solution structure, i.e. the interaction of the molecules with one another. The stress-optical rule only applies to a limited extent for this system. The stress-optical coefficient, C, is almost independent of the shear rate, but is strongly influenced by the concentration and attains a limiting value of 3 × 10⁻⁸ Pa⁻¹. C was determined for a polymer in dilute solution and the curve obtained also enabled transitions in the solution structure to be recognized. Received: 1 May 1998 Accepted: 5 October 1998