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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 24 (1991), S. 2955-2962 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 25 (1992), S. 1699-1704 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 24 (1991), S. 6175-6181 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1435-1528
    Keywords: Suspension ; Brownian motion ; hydrodynamic interaction ; stress relaxation ; damping function ; shear-thinning ; shear-thickening ; BKZ constitutive equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Linear and nonlinear viscoelastic properties were examined for a 50 wt% suspension of spherical silica particles (with radius of 40 nm) in a viscous medium, 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The effective volume fraction of the particles evaluated from zero-shear viscosities of the suspension and medium was 0.53. At a quiescent state the particles had a liquid-like, isotropic spatial distribution in the medium. Dynamic moduli G* obtained for small oscillatory strain (in the linear viscoelastic regime) exhibited a relaxation process that reflected the equilibrium Brownian motion of those particles. In the stress relaxation experiments, the linear relaxation modulus G(t) was obtained for small step strain γ(≤0.2) while the nonlinear relaxation modulus G(t, γ) characterizing strong stress damping behavior was obtained for large γ(〉0.2). G(t, γ) obeyed the time-strain separability at long time scales, and the damping function h(γ) (−G(t, γ)/G(t)) was determined. Steady flow measurements revealed shear-thinning of the steady state viscosity η(γ) for small shear rates γ(〈 τ −1; τ = linear viscoelastic relaxation time) and shear-thickening for larger γ (〉τ−1). Corresponding changes were observed also for the viscosity growth and decay functions on start up and cessation of flow, η + (t, γ) and η− (t, γ). In the shear-thinning regime, the γ and τ dependence of η+(t,γ) and η−(t,γ) as well as the γ dependence of η(γ) were well described by a BKZ-type constitutive equation using the G(t) and h(γ) data. On the other hand, this equation completely failed in describing the behavior in the shear-thickening regime. These applicabilities of the BKZ equation were utilized to discuss the shearthinning and shear-thickening mechanisms in relation to shear effects on the structure (spatial distribution) and motion of the suspended particles.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1435-1528
    Keywords: Suspension ; Brownian motion ; hydrodynamic interaction ; shear-thinning ; shear thickening ; dynamic clustering ; BKZ constitutive equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Time-dependent nonlinear flow behavior was investigated for a model hard-sphere suspension, a 50 wt% suspension of spherical silica particles (radius = 40 nm; effective volume fraction = 0.53) in a 2.27/1 (wt/wt) ethylene glycol/glycerol mixture. The suspension had two stress components, the Brownian stress σ B and the hydrodynamic stress σ H After start-up of flow at various shear rates $$\dot \gamma $$ , the viscosity growth function η+ (t, $$\dot \gamma $$ ) was measured with time t until it reached the steady state. The viscosity decay function η− (t, $$\dot \gamma $$ ) was measured after cessation of flow from the steady as well as transient states. At low $$\dot \gamma $$ where the steady state viscosity η ( $$\dot \gamma $$ ) exhibited the shear-thinning, the η− (t, $$\dot \gamma $$ ) and η+ (t, $$\dot \gamma $$ ) data were quantitatively described with a BKZ constitutive equation utilizing data for nonlinear relaxation moduli G (t, γ). This result enabled us to attribute the thinning behavior to the decrease of the Brownian contribution η B = σ B / $$\dot \gamma $$ (considered in the BKZ equation through damping of G (t, γ)). On the other hand, at high $$\dot \gamma $$ where η ( $$\dot \gamma $$ ) exhibited the thickening, the BKZ prediction largely deviated from the η+ (t, $$\dot \gamma $$ ) and η+ (t, $$\dot \gamma $$ ) data, the latter obtained after cessation of steady flow. This result suggested that the thickening was due to an enhancement of the hydrodynamic contribution η H = σ H / $$\dot \gamma $$ (not considered in the BKZ equation). However, when the flow was stopped at the transient state and only a small strain (〈0.2) was applied, η H was hardly enhanced and the η− (t, $$\dot \gamma $$ ) data agreed with the BKZ prediction. Correspondingly, the onset of thickening of η+ (t, $$\dot \gamma $$ ) was characterized with a $$\dot \gamma $$ -insensitive strain (≌ 0.2). On the basis of these results, the enhancement of η H (thickening mechanism) was related to dynamic clustering of the particles that took place only when the strain applied through the fast flow was larger than a characteristic strain necessary for close approach/collision of the particles.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 1435-1528
    Keywords: Key words Suspension ; Brownian motion ; hydrodynamic interaction ; shear-thinning ; shear thickening ; dynamic clustering ; BKZ ; constitutive equation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract Time-dependent nonlinear flow behavior was investigated for a model hard-sphere suspension, a 50wt% suspension of spherical silica particles (radius=40nm; effective volume fraction=0.53) in a 2.27/1(wt/wt) ethylene glycol/glycerol mixture. The suspension had two stress components, the Brownian stress σ B and the hydrodynamic stress σ H . After start-up of flow at various shear rates , the viscosity growth function was measured with time t until it reached the steady state. The viscosity decay function was measured after cessation of flow from the steady as well as transient states. At low ˙γ where the steady state viscosity ) exhibited the shear-thinning, the and data were quantitatively described with a BKZ constitutive equation utilizing data for nonlinear relaxation moduli . This result enabled us to attribute the thinning behavior to the decrease of the Brownian contribution (considered in the BKZ equation through damping of ). On the other hand, at high ˙γ where exhibited the thickening, the BKZ prediction largely deviated from the and data, the latter obtained after cessation of steady flow. This result suggested that the thickening was due to an enhancement of the hydrodynamic contribution (not considered in the BKZ equation). However, when the flow was stopped at the transient state and only a small strain (〈〉;0.2) was applied, was hardly enhanced and the data agreed with the BKZ prediction. Correspondingly, the onset of thickening of was characterized with a ˙γ-insensitive strain (≅0.2). On the basis of these results, the enhancement of (thickening mechanism) was related to dynamic clustering of the particles that took place only when the strain applied through the fast flow was larger than a characteristic strain necessary for close approach/collision of the particles.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1435-1528
    Keywords: Key words Suspension ; small angle neutron ; scattering ; shear-thinning ; shear-thickening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1435-1528
    Keywords: Key words Hard sphere suspension ; Brownian motion ; Nonlinear damping ; Shear-thinning ; Shear-thickening ; Hard-core volume
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract 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 φeff ranged from 0.36 to 0.59. For small strains, the particles exhibited linear relaxation of the Brownian stress σB 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 σB/γ. The damping became stronger for larger φeff. This φeff dependence was related to a hard-core volume effect, i.e., strain-induced collision of the particles that is enhanced for larger φeff. 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, σB/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 γd and γs for the onset of thickening and achievement of the steadily thickened state were independent of γ˙ but decreased with increasing φeff. This φeff dependence was again related to the hard-core volume effect, flow-induced collision of the particles enhanced for larger φeff.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1435-1528
    Keywords: Key words Rheo-dielectric behavior ; 8CB ; Nematic phase ; Smectic phase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract 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 ωc〉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≫ωc. 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.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1435-1528
    Keywords: Key words ; Living threadlike micelles ; strain/flow-induced scission ; nonlinear damping ; shear thinning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract 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.
    Type of Medium: Electronic Resource
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