Electrorheological determination of the Leslie viscosity coefficient (α2) of a main-chain liquid crystal polymer in a nematic solvent

Analysis of the electrorheological response of thermotropic solutions of a main-chain liquid crystal polymer (MCLCP) in a low molar mass nematic solvent is performed at a fixed shear rate as a function of the applied field strength. The Leslie viscosity coefficient α₂ can be obtained by least squares fits to an equation describing the balance between the viscous and electric torques, formulated via the two dimensional Leslie-Ericksen-Parodi theory. We find that the increment Δα₂ on dissolving the MCLCP increases linearly with molecular weight, consistent with earlier light scattering measurements of the increment in the twist viscosity, Δγ₁, and also with previous electrorheological measurements of the increment in the Miesowicz viscosity Δη_c. Received: 1 December 1998 Accepted: 28 April 1999     

Rheological behavior of dilute solutions of a side-chain liquid-crystalline polysiloxane in 4,4′-n-octylcyanobiphenyl

The electrorheological (ER) behavior and stress transient response of dilute solutions of a side-chain liquid-crystalline polysiloxane (LCP) in 4,4′-n-octylcyanobiphenyl (8CB) is studied. In the flow-tumbling regime of 8CB, i.e. from T = 34–38 °C, the stress transients of both 8CB and LCP/8CB solutions show oscillatory responses, but with shorter oscillation periodicities for the solution. In the flow-aligning regime of 8CB, i.e. at 39 and 40 °C, a transformation to flow-tumbling is observed in the stress transients of the LCP/8CB solution. In both cases, analysis of the transient responses indicates that the change in Leslie viscosity coefficients on dissolving the LCP are δα₂ < 0 and δα₃ > 0. The amplitude of the ER response, defined as the viscosity difference between the on and off states, Δη = η_on − η_off, is only weakly affected by the dissolution of LCP. These rheological results can be interpreted consistently using a modified version of a hydrodynamic theory by Brochard, provided an additional dissipation mechanism is included, which derives from the presence of an elastic torque between director rotation and LCP orientation. Received: 8 September 1999/Accepted: 13 December 1999     

Dynamic melt flow of nanocomposites based on poly-ɛ-caprolactam

 The dynamic flow behavior of polyamide-6 (PA-6) and a nanocomposite (PNC) based on it was studied. The latter resin contained 2 wt% of organoclay. The two materials were blended in proportions of 0, 25, 50, 75, and 100 wt% PNC. The dynamic shear rheological properties of well-dried specimens were measured under N₂ at T=240 °C, frequency ω=0.1–100 rad/s, and strains γ=10 and 40%. At constant T, γ, and ω the time sweeps resulted in significant increases of the shear moduli. The γ and ω scans showed a complex rheological behavior of all clay-containing specimens. At γ=10% the linear viscoelasticity was observed for all compositions only at ω>1 rad/s, while at γ=40% only for 0 and 25 wt% of PNC. However, the effect was moderate, namely decreasing G′ and G′′ (at ω=6.28 rad/s; γ=50%) by 15 and 7.5%, respectively. For compositions containing >25 wt% PNC two types of non-linearity were detected. At ω≤ω_c=1.4 ± 0.2 rad/s yield stress provided evidence of a 3-D structure. At ω > ω_c, G′ and G′′ were sensitive to shear history – the effect was reversible. From the frequency scans at ω > ω_c the zero-shear relative viscosity vs concentration plot was constructed. The initial slope gave the intrinsic viscosity from which the aspect ratio of organoclay particles, p=287 ± 9 was calculated, in agreement with the value calculated from the reduced permeability data, p=286. Received: 24 May 2001 Accepted: 27 August 2001     

Rheo-Dielectric behavior of low molecular weight liquid crystals.

Dielectric relaxation behavior was examined for 4-4′-n-pentyl-cyanobiphenyl (5CB) and 4-4′-n-heptyl-cyanobiphenyl (7CB) under flow. In quiescent states at all temperatures examined, both 5CB and 7CB exhibited dispersions in their complex dielectric constant ε*(ω) at characteristic frequencies ω _c above 10⁶ rad s^–1. This dispersion reflected orientational fluctuation of individual 5CB and 7CB molecules having large dipoles parallel to their principal axis (in the direction of C≡N bond). In the isotropic state at high temperatures, these molecules exhibited no detectable changes of ε*(ω) under flow at shear rates . In contrast, in the nematic state at lower temperatures the terminal relaxation intensity of ε*(ω) as well as the static dielectric constant ε′(0) decreased under flow at . This rheo-dielectric change was discussed in relation to the flow effects on the nematic texture (director distribution) and anisotropy in motion of individual molecules with respect to the director. Received: 14 April 1998 Accepted: 29 July 1998     

Rheo-dielectric behavior of low molecular weight liquid crystal 2. Behavior of 8CB in nematic and smectic states

Rheo-dielectric behavior was examined for 4−4^′−n-octyl-cyanobiphenyl (8CB) having large dipoles parallel to its principal axis (in the direction of the C≡N bond). In the quiescent state at all temperatures (T) examined, orientational fluctuation of the 8CB molecules was observed as dielectric dispersions at characteristic frequencies ω_c>10⁶ s⁻¹. In the isotropic state at high T, no detectable changes of the complex dielectric constant ɛ^*(ω) were found under slow flow at shear rates ˙γ≫ω_c. In the nematic state at intermediate T, the terminal relaxation intensity of ɛ^*(ω) was decreased under such slow flow. In the smectic state at lower T, the flow effect became much less significant. These results were related to the flow-induced changes of the liquid crystalline textures in the nematic and smectic states, and the differences of the rheo-dielectric behavior in these states are discussed in relation to a difference of the symmetry of molecular arrangements in the nematic and smectic textures. Received: 1 October 1998 Accepted: 13 January 1999     

Nonlinear rheology for threadlike micelles of tetraethylammonium perfluorooctyl sulfonate

Nonlinear rheological features were investigated for an aqueous solution of tetraethylammonium perfluorooctyl sulfonate (C₈F₁₇SO₃ ^–N⁺(C₂H₅)₄; abbreviated as FOSTEA). In the solution (c=0.045 mol/l; 28.3 g/l), spherical micelles of FOSTEA were connected with each other to form threads of pearl-necklace shape. These threads were further organized into a transient network to exhibit linear relaxation characteristic of living polymers, single-mode terminal relaxation widely separated from faster relaxation processes. Nonlinear relaxation experiments against large step-strains γ(≤8) revealed that the terminal relaxation mode had a γ-insensitive relaxation time but its relaxation intensity exhibited significant damping (much stronger than that for entangled polymers). In contrast, the relaxation time and intensity for the fast relaxation modes first increased and then decreased with increasing γ. Under shear flow, the FOSTEA threads exhibited strong thinning of the viscosity. These nonlinear features of the FOSTEA threads were compared with those of other threadlike micelles, analyzed on the basis of an empirically introduced constitutive equation, and discussed in relation to strain/low-induced scission of the living threads. Received: 20 February 1998 Accepted: 30 July 1998     

Anti-electroviscous effect of near-surface 5CB liquid crystal and its boundary lubrication property

The rheological properties of the near-surface 5CB (4-pentyl-4′-cyanobiphenyl) liquid crystal (LC) under an external electric field (EEF) are investigated using a dynamic quartz crystal microbalance (QCM). The real-time film-forming process and shearing response of the EEF-induced absorbed LC liquid are studied. The results indicate that the EEF-induced adsorbed LC is composed of a bulk liquid layer and a near-surface boundary layer. Within the boundary layer, the nematic 5CB LC presents an anti-electroviscous effect which may be due to the EEF-induced ordered structure. According to the estimation from QCM measurements, this near-surface layer is about 100 nm thick under certain electric strength and is irreversible even after the EEF is removed. Based on a QCM model, the near-surface LC layer presents a decreased and irreversible viscosity as the EEF voltage increases against the reversible electro-viscous effect of the bulk 5CB liquid crystal measured by rheometer and Raman spectrum measurements. The anti-electroviscous effect of the near-surface 5CB layer is also proved by an improved boundary lubrication property tested on a tribometer. The coefficient of friction of 5CB LC after a preliminary induction of EEF is the lowest one compared to those without EEF and during the application of EEF. The unique anti-electroviscous property of near-surface 5CB LC revealed in this article suggests a potential method to actively reduce shear resistance in boundary lubrication and in microfluidics.     

Quantitative rheological evaluation of phase inversion in two-phase polymer blends with cocontinuous morphology

 The present work is focused on the rheological properties of two-phase polymer blends in the phase inversion region. A large number of PS/PMMA- and PSAN/PMMA-blends has been investigated in order to establish a rheological criterion which allows the quantitative determination of the phase inversion concentration φ_PI by rheological means. Three rheological criteria based on the viscous and elastic blend properties such as maximum of dynamic viscosity η′, slope of G′, and maximum of G′ at a constant evaluation frequency have been tested. By correlating the rheological results to data from quantitative morphological analysis we could prove that the chosen rheological criteria are differently suitable for the determination of φ_PI. It has turned out that the G′ criterion is the most robust and most suitable one yielding an excellent correlation with morphological data. Based on these findings we propose a new simple equation for the prediction of φ_PI-values. Received: 14 March 2001 Accepted: 15 May 2001     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> phases on the enhancement of thermal conductivity and viscosity of nanofluids in engine oil

Thermal conductivity of α-Al₂O₃ was measured using hot wire method. α-Al₂O₃ (20 nm in size) was synthesized by microwave method for which, the results were compared with commercially available γ-Al₂O₃. Thermal conductivity of nanofluids was investigated considering, it is dependency on Al₂O₃ phase. It was observed that by adding 3 wt% of nano γ-Al₂O₃ and α-Al₂O₃ to the engine oil, thermal conductivity increases by 37 and 31%, respectively. The corresponding viscosity increase for the same amount of nano γ-Al₂O₃ and α-Al₂O₃ were 36 and 38%, respectively. It was concluded that the differences in thermal conductivity originate from higher specific surface area of γ-Al₂O₃ compared to the α-Al₂O₃ which is the result of porosity difference, obtained during the synthesis process.     

Conoscopic observations of shear-induced rotations in nematic liquid crystals

Orientational changes in monodomains of flow-aligning liquid crystals, 4-n-pentyl-4′-cyanobiphenyl and N-(4-methoxybenzylidene)-4-butylaniline, were studied during shear and recovery in a linear shearing device fitted to an optical microscope. Planar alignment (director in the shear plane) allows the study of twist effects and was generated by strong planar anchoring at the walls with orientations in a range of 0–90° with the shear direction. While being held back by the anchoring walls, shear caused the bulk director to rotate towards a steady-state alignment angle in the shear direction (Leslie angle θ_L). The transient director rotation was observed with conoscopy. It was found that increasing the initial alignment towards the vorticity direction increased the measured θ_L. Upon stopping the flow, the bulk director returned to its initial state. With initial alignment orientation changing from parallel to perpendicular to the flow direction, the rate of the twist-driven recovery process increases. This rate increase is not seen in the splay-driven recovery which is constant and consistently faster than twist-driven recovery at all orientations studied. Received: 10 December 1998/Accepted: 7 June 1999     

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.     

Positive Solutions of Boundary Value Problems for Second-Order Singular Nonlinear Differential Equations

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｔｈｉｓｐａｐｅｒ,ｗｅｓｈａｌｌｃｏｎｓｉｄｅｒｔｈｅｆｏｌｌｏｗｉｎｇｓｉｎｇｕｌａｒｂｏｕｎｄａｒｙｖａｌｕｅｐｒｏｂｌｅｍｓ (ＢＶＰ)ｕ″ ｇ(ｔ)ｆ(ｕ) =0 ,　　 0 <ｔ<1 ,αｕ(0 ) -βｕ′(0 ) =0 ,　　γｕ(1 ) δｕ′(1 ) =0 ,(1 )ｗｈｅｒｅα ,β,γ ,δ≥ 0 ,ρ:=βγ αγ αδ>0 ,ｆ∈Ｃ([0 ,∞ ) ,[0 ,∞ ) ) ,ｇｍａｙｂｅｓｉｎｇｕｌａｒａｔｔ=0ａｎｄ/ｏｒｔ=1 .Ｔｈｉｓｐｒｏｂｌｅｍａｒｉｓｅｓｎａｔｕｒａｌｌｙｉｎｔｈｅｓｔｕｄｙｏｆｒａｄｉａｌｌｙｓｙｍｍｅｔ…     

Transport properties in mixtures involving carbon dioxide at low and moderate density: test of several intermolecular potential energies and comparison with experiment

It is the purpose of this paper to extract unlike intermolecular potential energies of five carbon dioxide-based binary gas mixtures including CO₂–He, CO₂–Ne, CO₂–Ar, CO₂–Kr, and CO₂–Xe from viscosity data and compare the calculated potentials with other models potential energy reported in literature. Then, dilute transport properties consisting of viscosity, diffusion coefficient, thermal diffusion factor, and thermal conductivity of aforementioned mixtures are calculated from the calculated potential energies and compared with literature data. Rather accurate correlations for the viscosity coefficient of afore-cited mixtures embracing the temperature range 200 K < T < 3273.15 K is reproduced from the present unlike intermolecular potentials energy. Our estimated accuracies for the viscosity are to within ±2%. In addition, the calculated potential energies are used to present smooth correlations for other transport properties. The accuracies of the binary diffusion coefficients are of the order of ±3%. Finally, the unlike interaction energy and the calculated low density viscosity have been employed to calculate high density viscosities using Vesovic–Wakeham method.     

Using oscillatory squeezing flow to measure the viscoelastic properties of dental composite resin cements during curing

We have investigated the rheological changes in two particulate-filled dental composite resin cements during the curing process using a Micro-Fourier Rheometer (MFR). In the MFR, the sample was sandwiched between two parallel plates, and pseudorandom small amplitude squeezing was applied by oscillating the upper plate over a range of frequencies. Fourier transforms of the displacement signal and the resulting time dependent force signal enabled the rapid determination of the dynamic properties G′ and G′′ over the frequency range 2π–200π rad/s . This technique permitted us to follow changes in the rheological properties of the resin cements through the setting period. A typical result was that G′ increased from 2×10³ Pa to 2×10⁵ Pa after about 120 s, and that G′′ changed from 4×10³ Pa to 4×10⁴ Pa over the same period at frequency 40π rad/s. We also found that the dental composite resin cements show linear viscoelastic behaviour over a range of strain amplitudes before curing, but the response becomes distinctly non-linear at the later stages of curing for strain amplitudes γ>0.067%.     

The role of the mathematical mean value theorem (MVT) in rheometry: an easy way to convert apparent flow curves into correct ones

The mean value theorem of integral calculus guarantees that the apparent viscosity η _a can easily be converted into the correct viscosity η. For ordinary liquids there is a direct identity between η _a and η but the apparent shear rate (or apparent shear stress) has to be shifted to the representative shear rate γ˙^ (or representative shear stress τ^). A model free approximation scheme is introduced which implies a constant shift factor. The corresponding approximation for η is acceptable for liquids most commonly encountered. For plastic fluids the relation between η and η _a is more complex since it involves a function depending upon α; the yield stress relative to the maximum stress within the viscometer. Using the same approximation scheme as before the shift factor will involve α as well. The corresponding approximation of η is shown to be acceptable for the whole range of α. Received: 7 February 2000/Accepted: 15 February 2000     

Experimental studies on drag reduction and rheology of mixed cationic surfactants with different alkyl chain lengths

Experimental studies of the effects of mixtures of cationic surfactants on their drag reduction and rheological behaviors are reported. Cationic alkyl trimethyl quaternary ammonium surfactants with alkyl chain lengths of C₁₂ and C₂₂ were mixed at different molar ratios (total surfactant concentrations were kept at 5 mM with 12.5 mM sodium salicylate (NaSal) as counterion). Drag reduction tests showed that by adding 10% (mol) of C₁₂, the effective drag reduction range expanded to 4–120 °C, compared with 80–130 °C with only the C₂₂ surfactant. Thus mixing cationic surfactants with different alkyl chain lengths is an effective way of tuning the drag reduction temperature range. Cryo-TEM micrographs revealed thread-like micellar networks for surfactant solutions in the drag reducing temperature range, while vesicles were the dominant microstructures at non-drag reducing temperatures. High extensional viscosity was the main rheological feature for all solutions except 50% C₁₂ (mol) solution, which also does not show strong viscoelasticity. It is not clear why this low extensional viscosity solution with relatively weak viscoelasticity is a good drag reducer. Received: 3 November 1999/Accepted: 5 January 2000     

Nonlinear rheology of concentrated spherical silica suspensions: 3. Concentration dependence

Nonlinear rheology was examined for concentrated suspensions of spherical silica particles (with radius of 40 nm) in viscous media, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture and pure ethylene glycol. The particles were randomly and isotropically dispersed in the media in the quiescent state, and their effective volume fraction φ_eff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σ_B due to their diffusion. For large step strains γ, the nonlinear relaxation modulus G(t,γ) exhibited strong damping and obeyed the time-strain separability. This damping was related to γ-insensitivity of strain-induced anisotropy in the particle distribution that resulted in decreases of σ_B/γ. The damping became stronger for larger φ_eff. This φ_eff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φ_eff. Under steady/transient shear flow, the particles exhibited thinning and thickening at low and high γ˙, respectively. The thinning behavior was well described by a BKZ constitutive equation using the G(t,γ) data and attributable to decreases of a Brownian contribution, σ_B/γ˙. The thickening behavior, not described by this equation, was related to dynamic clustering of the particles and corresponding enhancement of the hydrodynamic stress at high γ˙. In this thickening regime, the viscosity growth η₊ after start-up of flow was scaled with a strain γ˙t. Specifically, critical strains γ_d and γ_s for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φ_eff. This φ_eff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φ_eff. Received: 26 June 1998 Accepted: 9 December 1998     

Scherk-Type Capillary Graphs

This paper concerns the regularity of a capillary graph (the meniscus profile of liquid in a cylindrical tube) over a corner domain of angle α. By giving an explicit construction of minimal surface solutions previously shown to exist (Indiana Univ. Math. J. 50 (2001), no. 1, 411–441) we clarify two outstanding questions. Solutions are constructed in the case α = π/2 for contact angle data (γ₁, γ₂) = (γ, π − γ) with 0 < γ < π. The solutions given with |γ − π/2| < π/4 are the first known solutions that are not C² up to the corner. This shows that the best known regularity (C^{1, ∈}) is the best possible in some cases. Specific dependence of the H?lder exponent on the contact angle for our examples is given. Solutions with γ = π/4 have continuous, but horizontal, normal vector at the corners in accordance with results of Tam (Pacific J. Math. 124 (1986), 469–482). It is shown that our examples are C^{0, β} up to and including the corner for any β < 1. Solutions with |γ − π/2| > π/4 have a jump discontinuity at the corner. This kind of behavior was suggested by numerical work of Concus and Finn (Microgravity sci. technol. VII/2 (1994), 152–155) and Mittelmann and Zhu (Microgravity sci. technol. IX/1 (1996), 22–27). Our explicit construction, however, allows us to investigate the solutions quantitatively. For example, the trace of these solutions, excluding the jump discontinuity, is C^2/3.     

Stability of Degenerate Stationary Waves for Viscous Gases

This paper is concerned with the asymptotic stability of degenerate stationary waves for viscous gases in the half space. We discuss the following two cases: (1) viscous conservation laws and (2) damped wave equations with nonlinear convection. In each case, we prove that the solution converges to the corresponding degenerate stationary wave at the rate t ^−α/4 as t → ∞, provided that the initial perturbation is in the weighted space L²_a=L²(\mathbb R₊; (1+x)^a dx){L^2_\alpha=L^2({\mathbb R}_+;\,(1+x)^\alpha dx)} . This convergence rate t ^−α/4 is weaker than the one for the non-degenerate case and requires the restriction α < α_*(q), where α_*(q) is the critical value depending only on the degeneracy exponent q. Such a restriction is reasonable because the corresponding linearized operator for viscous conservation laws cannot be dissipative in L²_a{L^2_\alpha} for α > α^*(q) with another critical value α^*(q). Our stability analysis is based on the space–time weighted energy method in which the spatial weight is chosen as a function of the degenerate stationary wave.     

Non-linear rheology and flow-induced transition of a lamellar-to-vesicle phase in ternary systems of alkyldimethyl oxide/alcohol/water

 The time-dependent transformation of an ionically charged lamellar phase (L _α-phase) into a vesicle phase under the influence of shear is investigated using rheological and conductivity measurements. The L _α-phase consists of the zwitterionic surfactant tetradecyldimethylaminoxide (C₁₄DMAO), hexanol, oxalic acid and water. The experiments were carried out on the L _α-phase in a well defined state. It was prepared by a special route from the neighbouring L ₃-phase that consists of 100 mM C₁₄DMAO, 250 mM hexanol and 5 mM oxalicdiethylester (OEE). The OEE hydrolyses in the L ₃ -phase to oxalic acid and ethanol. The result is a virgin L _α-phase which consists of stacked bilayers and which has not been exposed to shear. When this low-viscous phase is subjected to shear it is transformed into a highly viscous vesicle phase. The transformation of the L _α-phase into vesicles under constant shear was monitored by recording the viscosity and conductivity with time. It is observed that at least three different time constants can be distinguished in the transformation process. The conductivity passes through a minimum (τ₁) in the direction of shear. The viscosity first passes through a minimum (τ₂) and then over a maximum (τ₃). It is concluded that τ₁ belongs to the complete alignment of the bilayer parallel to the wall, τ₂ to the beginning of the break-up of the bilayers to the vesicles and τ₃ to the complete transformation of the L _α- to the vesicle phase. When the shear rate was varied, it was noted that the product of the time constants and shear is constant. Received: 30 June 1999/Accepted: 30 August 1999