Rheology of SiO 2 /(acrylic polymer/epoxy) suspensions. III. Uniaxial elongational viscosity

Uniaxial elongational viscosity of SiO₂/(acrylic polymer/epoxy (AP/EP)) suspensions with various SiO₂ volume fractions (?) in a blend of acrylic polymer and epoxy was investigated at various temperatures (T). The matrix polymer ((AP/EP) blend) contained 70?vol.% of EP. At ?????35?vol.% at T????80°C, where the suspensions were in sol state, strain-hardening behavior was observed. This strain hardening of the suspensions is attributable to the elongational flow properties of (AP/EP) medium. At critical gel state (??=?35?vol.% and T?=?100°C) and in gel state (?????40?vol.%), the elongational viscosity exhibited the strain-softening behavior. These results strongly suggest that the strain softening results from the strain-induced disruption of the network structure of the SiO₂ particles therein.     

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.     

Rheology of suspensions of spherical particles in a newtonian and a non-newtonian fluid

Properties of suspensions of spherical glass beads (25–38 μm dia.) in a Newtonian fluid and a non-Newtonian (NBS Fluid 40) fluid were measured at volume fractions, φ, of 0%, 10%, 20% and 30%. Measurements were made using a modified and computerized Weissenberg Rheogoniometer. Properties measured included steady shear viscosity, η($\text{γ}\text{.}$), first normal stress difference, N₁($\text{γ}\text{.}$), linear viscoelastic properties, η′(ω) and G′(ω), shear stress relaxation, σ^? ($\text{γ}\text{.}$, t), and growth, σ⁺($\text{γ}\text{.}$, t) and normal stress relaxation, N₁^?($\text{γ}\text{.}$, t).For a the Newtonian fluid, increasing φ causes both η and η′ to increase, with η′ showing a slight frequency dependence. Both N₁ and G′ are zero and stress relaxation and growth occur essentially instantaneously. For the NBS fluid, both η and η′ increse with φ at all $\text{γ}\text{.}$ and ω, respectively, the increase being greater as $\text{γ}\text{.}$ and ω approach zero. N₁ and G′ are less affected by the presence of the particles than η and η′ with the effect on G′ being more pronounced than on N₁. For fixed $\text{γ}\text{.}$, stress relaxation and growth exhibit greater non-linear effects as φ is increased. A model for predicting a priori the linear viscoelastic properties for suspensions was found to yeild reasonable estimates up to φ = 20%.     

On the use of stretched-exponential functions for both linear viscoelastic creep and stress relaxation

The use of the stretched-exponential function to represent both the relaxation function g(t)=(G(t)-G _∞)/(G ₀-G _∞) and the retardation function r(t) = (J _∞+t/η-J(t))/(J _∞-J ₀) of linear viscoelasticity for a given material is investigated. That is, if g(t) is given by exp (?(t/τ)^β), can r(t) be represented as exp (?(t/λ)^µ) for a linear viscoelastic fluid or solid? Here J(t) is the creep compliance, G(t) is the shear modulus, η is the viscosity (η^?1 is finite for a fluid and zero for a solid), G _∞ is the equilibrium modulus G _e for a solid or zero for a fluid, J _∞ is 1/G _e for a solid or the steady-state recoverable compliance for a fluid, G ₀= 1/J ₀ is the instantaneous modulus, and t is the time. It is concluded that g(t) and r(t) cannot both exactly by stretched-exponential functions for a given material. Nevertheless, it is found that both g(t) and r(t) can be approximately represented by stretched-exponential functions for the special case of a fluid with exponents β=µ in the range 0.5 to 0.6, with the correspondence being very close with β=µ=0.5 and λ=2τ. Otherwise, the functions g(t) and r(t) differ, with the deviation being marked for solids. The possible application of a stretched-exponential to represent r(t) for a critical gel is discussed.     

Experimental study of the rheological properties of butadiene-styrene gum elastomers and compounds

The linear viscoelastic properties of a polybutadiene and three butadiene-styrene copolymers were determined using stress relaxation measurements. The Tobolsky-Murakami Procedure X was applied to the data to characterize a discrete relaxation spectrum. The nonlinear behavior was studied using transient shear stress buildup experiments. A single integral nonlinear constitutive equation was able to represent both the linear and nonlinear data if a Bogue-type relaxation time was used which involves a time-averaged second invariant of the rate of deformation matrix. The linear viscoelastic behavior is in essence represented by a single function G(t) (or the parameters G_m, τ_m, G_m?1, τ_m?1, G_m?2, τ_m?2, ?). Similar studies were carried out on a butadiene-styrene copolymer based tread and sidewall compounds but the shear stress transient data were incompatible with the stress relaxation results. The reasons for this are discussed.     

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     

Rheology of carbon black suspensions. II. Well dispersed system

Linear viscoelastic properties were investigated for the suspensions of carbon black (CB) particles having covalently-fused aggregate structures of an average diameter a=120 nm. The suspending medium, an alkyd resin (AR), had a high affinity toward the CB particles, and the aggregates of these particles were well dispersed to form no higher-order agglomerates. Consequently, the suspensions obeyed the time-temperature superposition and their Arrhenius-type activation energy was identical to that of the medium. From comparison of the zero shear viscosity η₀ for the CB suspensions and hard-sphere silica suspensions, an effective volume fraction φ_eff of the CB particles was found to be 2.7 times larger than the bare volume fraction of the particles. The CB particles exhibited a slow relaxation process, and the terminal relaxation time of this process was close to the Peclet time (Brownian diffusion time) evaluated from the aggregate size a and a high frequency viscosity. Furthermore, the terminal relaxation mode distribution of the CB suspensions was well scaled with an intensity factor H_t that was evaluated from the φ_eff in a way utilized for the hard-sphere silica suspensions. These results demonstrated that the slow relaxation in the CB suspensions was dominated by the Brownian diffusion of the CB aggregates, as similar to the situation for the silica suspensions.     

Suspensions of titania nanoparticle networks in nematic liquid crystals: rheology and microstructure

We study the influence of confinement on the rheology and structure of nematic liquid crystals (NLCs). NLCs get confined in networks of titania (TiO₂, primary particle size = 21 nm) nanoparticles in suspensions of TiO₂ and NLC, N-(4-methoxybenzylidene)-4-butylaniline (MBBA). Suspensions with TiO₂ nanoparticle volume fraction (?) of 0.006–0.017, form viscoelastic solids with low elastic modulus (G′) of 10¹ Pa–10² Pa and short relaxation times. Increase in TiO₂ nanoparticle ? leads to a rise in G′ with TiO₂ nanoparticles forming a percolating network at a critical volume fraction (? _c) = 0.023, and G′ of ~10³ Pa. TiO₂/MBBA NLC suspensions at and above ? _c = 0.023 show G′ ~ ω ^x?1 scaling, where ω is the angular frequency and the minimum in loss modulus (G′′) with ω. The effective noise temperature, x decreases and approaches 1 with the increase in the TiO₂ nanoparticle ? from 0.023–0.035, is indicative of an increase in the glassy dynamics. Through the polarized light microscopy and differential scanning calorimetry experiments, we propose that the progressive addition of TiO₂ nanoparticles introduces a quenched random disorder (QRD) in the NLC medium which disturbs the nematic order. This results in metastable TiO₂/MBBA NLC suspensions in which NLC domains get confined in the network of flocs of TiO₂ nanoparticles. We also show that the salient rheological signatures of soft glassy rheology develop only in the presence of NLC MBBA and are absent in the isotropic phase of MBBA.     

Linearized Stability for Semiflows Generated by a Class of Neutral Equations,with Applications to State-Dependent Delays

We prove a principle of linearized stability for semiflows generated by neutral functional differential equations of the form x′(t) = g(? x _t , x _t ). The state space is a closed subset in a manifold of C ²-functions. Applications include equations with state-dependent delay, as for example x′(t) = a x′(t + d(x(t))) + f (x(t + r(x(t)))) with \({a\in\mathbb{R}, d:\mathbb{R}\to(-h,0), f:\mathbb{R}\to\mathbb{R}, r:\mathbb{R}\to[-h,0]}\).     

Pressure probe with five embedded flush-mounted sensors: unsteady pressure and velocity measurements in hydraulic turbine model

Picosecond Unstable-resonator Spatially Enhanced Detection Coherent Anti-Stokes Raman Scattering (USED-CARS) is used for the measurement of nitrogen Q-branch (ΔJ = 0) spectra in the subsonic plenum and supersonic flow of a highly nonequilibrium Mach 5 wind tunnel. Spectra are processed to infer rotational/translational (T _rot) and first-level vibrational (T _vib) temperatures in the 200–370 torr plenum simultaneously. Operation of the nominally high reduced electric field (E/n _peak ~ 500 Td), nsec pulsed discharge alone results in fairly significant vibrational loading, T _vib ~ 720 K/T _rot ~ 380 K; addition of an orthogonal low E/n (~10 Td) DC sustainer discharge produces substantial vibrational loading, T _vib ~ 2,000 K/T _rot ~ 450 K. Effects of injection of CO₂, NO, and H₂ downstream of the pulser–sustainer discharge are examined, which result in vibrational relaxation accompanied by simultaneous gas heating, T _vib ~ 800–1,000 K/T _rot ~ 600 K. CARSk measurements within very low-density flows in the Mach 5 expansion nozzle are also performed, with T _vib measured in both the supersonic free-stream and downstream of a bow shock created by a 5-mm-diameter cylindrical test object in the Mach 5 flow. Measurements within 300 μm of the cylinder leading edge show that for pure N₂, or N₂ with 0.25 torr CO₂ injection, no vibrational relaxation is observed behind the bow shock.     

Nonlinear rheological behavior of a concentrated spherical silica suspension

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 (0.2) while the nonlinear relaxation modulus G(t, ) characterizing strong stress damping behavior was obtained for large (>0.2). G(t, ) obeyed the time-strain separability at long time scales, and the damping function h() (–G(t, )/G(t)) was determined. Steady flow measurements revealed shear-thinning of the steady state viscosity () for small shear rates (< ^–1; = linear viscoelastic relaxation time) and shear-thickening for larger (>^–1). Corresponding changes were observed also for the viscosity growth and decay functions on start up and cessation of flow, + (t, ) and _– (t, ). In the shear-thinning regime, the and dependence of ₊(t,) and _–(t,) as well as the dependence of () were well described by a BKZ-type constitutive equation using the G(t) and h() 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.Dedicated to the memory of Prof. Dale S. Parson     

Viscoelastic behavior of PMMA/grafted PBA nanoparticle systems in the molten state

The viscoelastic properties of poly(methyl methacrylate) (PMMA)/grafted poly(butyl acrylate) (PBA) nanoparticle systems were investigated. The rubber particles consist of PBA core (60 nm in diameter) and grafted PMMA shell. The grafting degree, defined as the weight ratio of grafted PMMA to PBA particles, ranges from 0.8 to 1.5. Two series of samples, A series with 7.5 wt.% of PBA content and B series with 12 wt.% of PBA content, were used. The systems exhibited fast and slow relaxation process, the former reflecting the relaxation of the matrix PMMA chains and the latter being attributed to grafted PBA particles. For A series samples, time-temperature superposition (TTS) was held well over the frequency (ω) and temperature (T) ranges measured. However, for B series samples, TTS was not satisfied at low ω due to the particle-particle interaction of grafted PBA particles, although the samples obeyed TTS at high ω associated with the relaxation with entanglement of matrix PMMA. At high T and low ω region, the B series samples showed a sol-gel transition at elevating T and the critical gel behavior characterized with a power-law relationship, G′ = G″/tan(nπ/2) ∝ ωⁿ, was observed. This behavior suggested formation of a self-similar, fractal structure of grafted PBA particles. The critical gel temperature (T _gel) and the critical exponent (n) were determined for the B series samples. TEM observations revealed that as-prepared A and B samples had well-dispersed particles but the B samples after viscoelastic measurements had fragmented networks of the PBA particles, confirming that the sol-gel transition occurred for the PMMA/grafted PBA systems at elevating T.     

Hydrodynamic behavior of an internally circulating fluidized bed with tubular gas distributors

To better understand the hydrodynamic behavior of an internally circulating fluidized bed, solids holdup in the down-comer （Eso）, solids circulation rate （Gs） and gas bypassing fraction （from down-comer to riser y~R, and from riser to down-comer yRD） were experimentally studied. The effects of gas velocities in the riser and in the down-comer （UR and UD）, orifice diameter in the draft tube （dor）, and draft tube height （HR） were investigated. Experimental results showed that increase of gas velocities led to increase in Gs and yDR, and slight decrease in yeD. Larger orifice diameter on the draft tube led to higher 8sD, Gs and yDR, but had insignificant influence on YRD. with increasing draft tube height, both Gs and YDR first increased and then decreased, while yRD first decreased and then increased. Proposed correlations for predicting the hydrodynamic parameters agreed reasonably well with experimental values.     

On the sensitivity of interconversion between relaxation and creep

The interconversion equation of linear viscoelasticity defines implicitly the interrelations between the relaxation and creep functions G(t) and J(t). It is widely utilised in rheology to estimate J(t) from measurements of G(t) and conversely. Because different molecular details can be recovered from G(t) and J(t), it is necessary to work with both. This leads naturally to the need to identify whether it is better to first measure G(t) and then determine J(t) or conversely. This requires an understanding of the stability (sensitivity) of the recovery of J(t) from G(t) compared with that of G(t) from J(t). Although algorithms are available that work adequately in both directions, numerical experimentation strongly suggests that the recovery of J(t) from G(t) measurements is the more stable. An elementary theoretical rationale has been given recently by Anderssen et al. (ANZIAM J 48:C346–C363, 2007) for single exponential models of G(t) and J(t). It explicitly exploits the simple algebra of such functions. In this paper, corresponding bounds are derived that hold for arbitrary sums of exponentials. The paper concludes with a discussion, from a practical rheological perspective, about the implications and implementations of the results.     

Determination of source parameter in parabolic equations

The authors consider the problem of finding u=u(x, t) and p=p(t) which satisfy u = Lu + p(t) + F(x, t, u, _x, p(t)) in Q _T=Ω×(0, T], u(x, 0)=ø(x), x∈Ω, u(x, t)=g(x, t) on ?Ω×(0, T] and either ∫_G(t) Φ(x,t)u(x,t)dx = E(t), 0 ? t ? T or u(x₀, t)=E(t), 0≤t≤T, where Ω?R ⁿ is a bounded domain with smooth boundary ?Ω, x ₀∈Ω, L is a linear elliptic operator, G(t)?Ω, and F, ø, g, and E are known functions. For each of the two problems stated above, we demonstrate the existence, unicity and continuous dependence upon the data. Some considerations on the numerical solution for these two inverse problems are presented with examples.     

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

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

An analysis of the fracture initiation of falling type impact test for toughened rigid plastics

A quasi-static linear viscoelastic model for the dart impact type test on toughened rigid plastics is proposed and analysed. Based on the modified Maxwell element model of viscoelastic behavior of material with relaxation modulus E(t) = E_f + (E_o ? E_f)e${}^{\mathrm{<mtext>?t</mtext><mtext>t</mtext><mtext>R</mtext>}}$, some approximate computations are performed to assess the relative importance of various parameters such as the impact velocity, fracture initiation.energy and critical stress.     

Forced Convection Heat Transfer from a Heated Cylinder in an Axial Background Flow in a Porous Medium: Three Exactly Solvable Cases

Assuming a background flow of velocity U = U(x) in the axial direction x of a circular cylinder with surface temperature distribution T _w = T _w (x) in a saturated porous medium, for the temperature boundary layer occurring on the cylinder three exactly solvable cases are identified. The functions {U(x), T _w (x)} associated with these cases are given explicitly, and the corresponding exact solutions are expressed in terms of the modified Bessel function K ₀ (z), the incomplete Gamma function Γ (a, z) and the confluent hypergeometric function U(a, b, z), respectively. The correlation between the Nusselt number and the Péclet number as well as the curvature effects on the heat transfer are discussed in all these cases in detail. Some “universal” features of the exponential surface temperature distribution are also pointed out.