Rheological behavior of poly(methyl methacrylate)/polystyrene (PMMA/PS) blends with the addition of PMMA-<Emphasis Type="BoldItalic">ran</Emphasis>-PS

In this work, the dynamic behavior of poly(methyl methacrylate)/polystyrene blend to which P(S_0.5-ran-MMA_0.5) was added was studied. Several blend (ranging from 5 to 20 wt% of dispersed phase) and copolymer (up to 20 wt% with respect to dispersed phase) concentrations were studied. The rheological behavior of the blends was compared to Bousmina’s (Rheol Acta 38:73–83, 1999) and Palierne’s (Rheol Acta 29:204–214, 1990) generalized models. The relaxation spectra of the blends were also inferred, and the results were analyzed in light of the analysis of Jacobs et al. [J Rheol 43:1495–1509, 1999]. The relaxation spectra of the blends with smaller dispersed phase (below 10 wt%) and larger copolymer concentrations (above 0.4 wt%) showed the presence of four relaxation times, two corresponding to the blend phases, τ _F , corresponding to the relaxation of the shape of the dispersed phase of the blend and that can be attributed to the relaxation of Marangoni stresses tangential to the interface between the dispersed phase and matrix. The experimental values of and were used to infer the interfacial tension (Γ) and the interfacial complex shear modulus (β) for the different blends, Γ decreased with increasing copolymer concentration. β decreased with increasing blend dispersed phase concentration and decreasing copolymer concentration. The predictions of Palierne’s generalized model were found to corroborate the experimental data once the values of Γ and β, found analyzing the relaxation spectra, were used in the calculations. Bousmina’s model was found to corroborate the data only for larger dispersed phase concentration. Paper was presented at the 3rd Annual Rheology Conference, AERC 2006, April 27–29, 2006, Crete, Greece.     

The interchain pressure effect in shear rheology

Recently, the tube diameter relaxation time in the evolution equation of the molecular stress function (MSF) model (Wagner et al., J Rheol 49: 1317–1327, 2005) with the interchain pressure effect (Marrucci and Ianniruberto, Macromolecules 37:3934–3942, 2004) included was shown to be equal to three times the Rouse time in the limit of small chain stretch. From this result, an advanced version of the MSF model was proposed, allowing modeling of the transient and steady-state elongational viscosity data of monodisperse polystyrene melts without using any nonlinear parameter, i.e., solely based on the linear viscoelastic characterization of the melts (Wagner and Rolón-Garrido 2009a, b). In this work, the same approach is extended to model experimental data in shear flow. The shear viscosity of two polybutadiene solutions (Ravindranath and Wang, J Rheol 52(3):681–695, 2008), of four styrene-butadiene random copolymer melts (Boukany et al., J Rheol 53(3):617–629, 2009), and of four polyisoprene melts (Auhl et al., J Rheol 52(3):801–835, 2008) as well as the shear viscosity and the first and second normal stress differences of a polystyrene melt (Schweizer et al., J Rheol 48(6):1345–1363, 2004), are analyzed. The capability of the MSF model with the interchain pressure effect included in the evolution equation of the chain stretch to model shear rheology on the basis of linear viscoelastic data alone is confirmed.     

Elongational viscosity of LDPE with various structures: employing a new evolution equation in MSF theory

Molecular stress function theory with new strain energy function is used to analyze transient extensional viscosity data of seven low-density polyethylene (LDPE) melts with various molecular structures as published by Stadler et al. (Rheol Acta 48:479–490, 2009) Pivokonsky et al. (J Non Newton Fluid Mech 135:58–67, 2006) and Wagner et al. (J Rheol 47(3):779–793, 2003). The new strain energy function has three nonlinear viscoelastic material parameters and assumes that the total stored energy of a branched molecule is given by different backbone and side chains stretching. The model parameters have been fitted for each LDPE in order to correlate with the supposed macromolecular structure expected from the type of synthesis. Most probable molecular structures for these LDPEs are comb and Cayley tree structures for respectively low- and high-molecular weight parts.     

Modelling elongational and shear rheology of two LDPE melts

Experimental data of two low-density polyethylene (LDPE) melts at 200°C for both shear flow (transient and steady shear viscosity as well as transient and steady first normal stress coefficient) and elongational flow (transient and steady-state elongational viscosity) as published by Pivokonsky et al. (J Non-Newtonian Fluid Mech 135:58–67, 2006) were analysed using the molecular stress function model for broadly distributed, randomly branched molecular structures. For quantitative modelling of melt rheology in both types of flow and in a very wide range of deformation rates, only three nonlinear viscoelastic material parameters are needed: Whilst the rotational parameter, a ₂, and the structural parameter, β, are found to be equal for the two melts considered, the melts differ in the parameter describing maximum stretch of the polymer chains.     

Modeling elongational viscosity of blends of linear and long-chain branched polypropylenes

To enhance the melt strength of a conventional linear polypropylene (L-PP), blends with a long-chain branched polypropylene (LCB-PP) were produced by adding 2, 5, 10, 25, 50, and 75 wt% of LCB-PP to L-PP and mixing in a twin screw extruder. It was found that, already, an addition of 10% or less of LCB-PP to L-PP leads to significant strain hardening. Elongational viscosity data of L-PP and LCB-PP and those of their blends were analyzed by the use of the molecular stress function (MSF) theory. While L-PP is characterized by the MSF parameter, β=1 (typical for linear melts), and shows very little chain stretch (), melt elongational behavior of LCB-PP is characterized by the MSF parameters, β=2 (typical of LCB melts), and (which corresponds to a maximum stretch of molecular chains by a factor of 15). By extruding LCB-PP, a refining effect is observed similar to the refining effects seen in low density polyethylene (LDPE), which reduces the steady-state elongational viscosity and reduces to 121. A second-order mixing rule for the fractional relaxation moduli, g _i , was found to show good agreement with the linear-viscoelastic data of the blends. To simulate the elongational viscosities of the L-PP/LCB-PP blends, a similar second-order mixing rule was used for the MSF parameter, β, while a first-order mixing rule was found to be appropriate for . This allows for a quantitative prediction of the time-dependent elongational viscosities of all L-PP/LCB-PP blends on the basis of the linear and nonlinear parameters of the mixing components L-PP and LCB-PP only. Comparison between the steady-state elongational viscosities as obtained from creep experiments shows good agreement with predictions.     

The Semigeostrophic Equations Discretized in Reference and Dual Variables

We study the evolution of a system of n particles in . That system is a conservative system with a Hamiltonian of the form , where W ₂ is the Wasserstein distance and μ is a discrete measure concentrated on the set . Typically, μ(0) is a discrete measure approximating an initial L ^∞ density and can be chosen randomly. When d  =  1, our results prove convergence of the discrete system to a variant of the semigeostrophic equations. We obtain that the limiting densities are absolutely continuous with respect to the Lebesgue measure. When converges to a measure concentrated on a special d–dimensional set, we obtain the Vlasov–Monge–Ampère (VMA) system. When, d = 1 the VMA system coincides with the standard Vlasov–Poisson system.     

Solutions of the Dirac–Fock Equations and the Energy of the Electron-Positron Field

We consider atoms with closed shells, i.e. the electron number N is 2, 8, 10,..., and weak electron-electron interaction. Then there exists a unique solution γ of the Dirac–Fock equations with the additional property that γ is the orthogonal projector onto the first N positive eigenvalues of the Dirac–Fock operator . Moreover, γ minimizes the energy of the relativistic electron-positron field in Hartree–Fock approximation, if the splitting of into electron and positron subspace is chosen self-consistently, i.e. the projection onto the electron-subspace is given by the positive spectral projection of. For fixed electron-nucleus coupling constant g:=α Z we give quantitative estimates on the maximal value of the fine structure constant α for which the existence can be guaranteed.     

Non-autonomous 2D Navier–Stokes System with Singularly Oscillating External Force and its Global Attractor

We study the global attractor of the non-autonomous 2D Navier–Stokes (N.–S.) system with singularly oscillating external force of the form . If the functions g ₀(x, t) and g ₁ (z, t) are translation bounded in the corresponding spaces, then it is known that the global attractor is bounded in the space H, however, its norm may be unbounded as since the magnitude of the external force is growing. Assuming that the function g ₁ (z, t) has a divergence representation of the form where the functions (see Section 3), we prove that the global attractors of the N.–S. equations are uniformly bounded with respect to for all . We also consider the “limiting” 2D N.–S. system with external force g ₀(x, t). We have found an estimate for the deviation of a solution of the original N.–S. system from a solution u ⁰(x, t) of the “limiting” N.–S. system with the same initial data. If the function g ₁ (z, t) admits the divergence representation, the functions g ₀(x, t) and g ₁ (z, t) are translation compact in the corresponding spaces, and , then we prove that the global attractors converges to the global attractor of the “limiting” system as in the norm of H. In the last section, we present an estimate for the Hausdorff deviation of from of the form: in the case, when the global attractor is exponential (the Grashof number of the “limiting” 2D N.–S. system is small).      

On the Rank 1 Convexity of Stored Energy Functions of Physically Linear Stress-Strain Relations

The rank 1 convexity of stored energy functions corresponding to isotropic and physically linear elastic constitutive relations formulated in terms of generalized stress and strain measures [Hill, R.: J. Mech. Phys. Solids 16, 229–242 (1968)] is analyzed. This class of elastic materials contains as special cases the stress-strain relationships based on Seth strain measures [Seth, B.: Generalized strain measure with application to physical problems. In: Reiner, M., Abir, D. (eds.) Second-order Effects in Elasticity, Plasticity, and Fluid Dynamics, pp. 162–172. Pergamon, Oxford, New York (1964)] such as the St.Venant–Kirchhoff law or the Hencky law. The stored energy function of such materials has the form

Random Kick-Forced 3D Navier–Stokes Equations in a Thin Domain

We consider the Navier–Stokes equations in the thin 3D domain , where is a two-dimensional torus. The equation is perturbed by a non-degenerate random kick force. We establish that, firstly, when ε ≪ 1, the equation has a unique stationary measure and, secondly, after averaging in the thin direction this measure converges (as ε → 0) to a unique stationary measure for the Navier–Stokes equation on . Thus, the 2D Navier–Stokes equations on surfaces describe asymptotic in time, and limiting in ε, statistical properties of 3D solutions in thin 3D domains.     

Vortices for a Rotating Toroidal Bose–Einstein Condensate

We construct local minimizers of the Gross–Pitaevskii energy, introduced to model Bose–Einstein condensates (BEC) in the Thomas–Fermi regime which are subject to a uniform rotation. Our sample domain is taken to be a solid torus of revolution in with starshaped cross-section. We show that for angular speeds ω_ε = O(|ln ε|) there exist local minimizers of the energy which exhibit vortices, for small enough values of the parameter ε. These vortices concentrate at one or several planar arcs (represented by integer multiplicity rectifiable currents) which minimize a line energy, obtained as a Γ-limit of the Gross–Pitaevskii functional. The location of these limiting vortex lines can be described under certain geometrical hypotheses on the cross-sections of the torus.     

Relaxation time spectrum molecular weight distribution relationships

Single exponential decay relationships, which define the molecular weight distribution (MWD) of a polymer as a function of the polymer’s relaxation time spectrum (RTS), have been derived by Wu (Polym Eng Sci 28:538–543, 1988) and Thimm et al. (J Rheol 43:1663–1672, 1999). Experimental validation studies with monodisperse polymers, with quite precisely known MWDs, have been used to test their reliability. It has been established that neither formula is always able to accurately recover the MWDs of monodisperse polymers from their experimentally determined RTS. In this paper, different and more general relationships, based on theoretical results of Anderssen and Loy (Bull Aust Math Soc 65:449–460, 2002a) for decays of the form , where the derivative of θ(t) is a completely monotone function, are derived, analyzed, and applied. It is shown how to transform these general relationships to equivalent single exponential decay relationships for which Laplace transform solutions are derived. In order to illustrate the interrelationship between an RTS and its corresponding MWD, an explicit analytic solution is given. The paper concludes with a discussion of the rheological implications for the BSW model.     

The Asymptotic Finite-dimensional Character of a Spectrally-hyperviscous Model of 3D Turbulent Flow

We obtain attractor and inertial-manifold results for a class of 3D turbulent flow models on a periodic spatial domain in which hyperviscous terms are added spectrally to the standard incompressible Navier–Stokes equations (NSE). Let P _m be the projection onto the first m eigenspaces of A =−Δ, let μ and α be positive constants with α ≥3/2, and let Q _m =I − P _m , then we add to the NSE operators μ A _φ in a general family such that A _φ≥Q _m A ^α in the sense of quadratic forms. The models are motivated by characteristics of spectral eddy-viscosity (SEV) and spectral vanishing viscosity (SVV) models. A distinguished class of our models adds extra hyperviscosity terms only to high wavenumbers past a cutoff λ _m0 where m ₀ ≤ m, so that for large enough m ₀ the inertial-range wavenumbers see only standard NSE viscosity. We first obtain estimates on the Hausdorff and fractal dimensions of the attractor (respectively and ). For a constant K _α on the order of unity we show if μ ≥ ν that and if μ ≤ ν that where ν is the standard viscosity coefficient, l ₀ = λ₁^−1/2 represents characteristic macroscopic length, and is the Kolmogorov length scale, i.e. where is Kolmogorov’s mean rate of dissipation of energy in turbulent flow. All bracketed constants and K _α are dimensionless and scale-invariant. The estimate grows in m due to the term λ _m /λ₁ but at a rate lower than m ^3/5, and the estimate grows in μ as the relative size of ν to μ. The exponent on is significantly less than the Landau–Lifschitz predicted value of 3. If we impose the condition , the estimates become for μ ≥ ν and for μ ≤ ν. This result holds independently of α, with K _α and c _α independent of m. In an SVV example μ ≥ ν, and for μ ≤ ν aspects of SEV theory and observation suggest setting for 1/c within α orders of magnitude of unity, giving the estimate where c _α is within an order of magnitude of unity. These choices give straight-up or nearly straight-up agreement with the Landau–Lifschitz predictions for the number of degrees of freedom in 3D turbulent flow with m so large that (e.g. in the distinguished-class case for m ₀ large enough) we would expect our solutions to be very good if not virtually indistinguishable approximants to standard NSE solutions. We would expect lower choices of λ _m (e.g. with a > 1) to still give good NSE approximation with lower powers on l ₀/l _ε, showing the potential of the model to reduce the number of degrees of freedom needed in practical simulations. For the choice , motivated by the Chapman–Enskog expansion in the case m = 0, the condition becomes , giving agreement with Landau–Lifschitz for smaller values of λ _m then as above but still large enough to suggest good NSE approximation. Our final results establish the existence of a inertial manifold for reasonably wide classes of the above models using the Foias/Sell/Temam theory. The first of these results obtains such an of dimension N > m for the general class of operators A _φ if α > 5/2. The special class of A _φ such that P _m A _φ = 0 and Q _m A _φ ≥ Q _m A ^α has a unique spectral-gap property which we can use whenever α ≥ 3/2 to show that we have an inertial manifold of dimension m if m is large enough. As a corollary, for most of the cases of the operators A _φ in the distinguished-class case that we expect will be typically used in practice we also obtain an , now of dimension m ₀ for m ₀ large enough, though under conditions requiring generally larger m ₀ than the m in the special class. In both cases, for large enough m (respectively m ₀), we have an inertial manifold for a system in which the inertial range essentially behaves according to standard NSE physics, and in particular trajectories on are controlled by essentially NSE dynamics.      

The Semiclassical Regime for Ablation Front Models

In this paper, we study two problems appearing in two-dimensional fluid mechanics in a constant gravity field . These two problems—the Rayleigh convection problem and the ablation front problem—generalize the Rayleigh–Taylor model in compressible flows. The analysis of their stability relies on semiclassical techniques for the linearized system around a reference solution. We consider normal modes which are approximate solutions corresponding to large wave numbers associated with , and we discuss the existence or the non-existence of such normal modes. The results depend on the value of the dimensionless growth rate Γ compared with two relevant mathematical parameters, namely σ _p (p standing for the model) and some effective semiclassical parameter h.     

The Steady Motion of a Navier–Stokes Liquid Around a Rigid Body

Let be a body moving by prescribed rigid motion in a Navier–Stokes liquid that fills the whole space and is subject to given boundary conditions and body force. Under the assumptions that, with respect to a frame , attached to , these data are time independent, and that their magnitude is not “too large”, we show the existence of one and only one corresponding steady motion of , with respect to , such that the velocity field, at the generic point x in space, decays like |x|⁻¹. These solutions are “physically reasonable” in the sense of FINN [10]. In particular, they are unique and satisfy the energy equation. Among other things, this result is relevant in engineering applications involving orientation of particles in viscous liquid [14].     

The Toda System and Clustering Interfaces in the Allen–Cahn equation

We consider the Allen–Cahn equation in a bounded, smooth domain Ω in , under zero Neumann boundary conditions, where is a small parameter. Let Γ₀ be a segment contained in Ω, connecting orthogonally the boundary. Under certain nondegeneracy and nonminimality assumptions for Γ₀, satisfied for instance by the short axis in an ellipse, we construct, for any given N ≥ 1, a solution exhibiting N transition layers whose mutual distances are and which collapse onto Γ₀ as . Asymptotic location of these interfaces is governed by a Toda-type system and yields in the limit broken lines with an angle at a common height and at main order cutting orthogonally the boundary.     

Refined Jacobian Estimates and Gross–Pitaevsky Vortex Dynamics

We study the dynamics of vortices in solutions of the Gross–Pitaevsky equation in a bounded, simply connected domain with natural boundary conditions on ∂Ω. Previous rigorous results have shown that for sequences of solutions with suitable well-prepared initial data, one can determine limiting vortex trajectories, and moreover that these trajectories satisfy the classical ODE for point vortices in an ideal incompressible fluid. We prove that the same motion law holds for a small, but fixed , and we give estimates of the rate of convergence and the time interval for which the result remains valid. The refined Jacobian estimates mentioned in the title relate the Jacobian J(u) of an arbitrary function to its Ginzburg–Landau energy. In the analysis of the Gross–Pitaevsky equation, they allow us to use the Jacobian to locate vortices with great precision, and they also provide a sort of dynamic stability of the set of multi-vortex configurations.     

A classical problem revisited: rheology of nematic polymer monodomains in small amplitude oscillatory shear

We revisit the classical problem of the viscoelastic response of nematic (liquid crystal) polymers to small amplitude oscillatory shear. A multiple time scale perturbation analysis is applied to the Doi–Hess mesoscopic orientation tensor model to describe key features observed of longtime experiments, both physical (Moldenaers and Mewis, J Rheol, 30:567–584, 1986; Larson and Mead, J Rheol, 33:1251–1281, 1989b) and numerical (herein). First, there is a very slow time scale drift in the envelope of oscillations of the major director; we characterize the mean director angle and the envelope of oscillation. Second, there are bistable asymptotic orientational states, distinguished in that they are precisely the zero-stress orientational distributions noted in Larson and Mead (J Rheol, 33:185–206, 1989a). Third, the drift dynamics and asymptotic mean director angle are determined by the initial orientation of the director, not by material properties; we characterize the domain of attraction of each bistable state. Finally, the director drift leads to a predicted longtime decrease in the storage and loss moduli, consistent with experimental observations.

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Transient elongational viscosities of aqueous polyacrylamide solutions measured with an optical rheometer

An anionic polyacrylamide solution was characterized in elongational flow by combining laser-Doppler velocimetry to determine the strain rate in the flow direction and the two-color flow-induced birefringence method to measure the first normal stress difference along the axial centerline of a hyperbolic die. The elongational rate was constant along the axial centerline of the planar hyperbolic die as long as vortices at the die entrance did not occur. The transient elongational viscosity μ ⁺ was determined as a function of the elongational rate. The parameters varied are the Hencky strain rate and the polymer concentration. μ ⁺ showed a pronounced increase over the linear viscoelastic behavior above critical Hencky strains of 1.2 to 1.5; that is, a significant strain hardening could be observed for polyacrylamide solutions. This strain hardening is stronger the higher the elongational rate. A slight enhancement of strain hardening was found by increasing the concentration from 0.5 to 1 g/l. The stress optical coefficient was determined as 1.8 × 10⁻⁷ Pa⁻¹ (0.5 g/l) and 1.2 × 10⁻⁷ Pa⁻¹ (1 g/l).