Self-consistent modeling of entangled network strands and linear dangling structures in a single-strand mean-field slip-link model

Linear viscoelastic (LVE) measurements as well as non-linear elongation measurements have been performed on stoichiometrically imbalanced polymeric networks to gain insight into the structural influence on the rheological response (Jensen et al., Rheol Acta 49(1):1–13, 2010). In particular, we seek knowledge about the effect of dangling ends and soluble structures. To interpret our recent experimental results, we exploit a molecular model that can predict LVE data and non-linear stress–strain data. The slip-link model has proven to be a robust tool for both LVE and non-linear stress–strain predictions for linear chains (Khaliullin and Schieber, Phys Rev Lett 100(18):188302–188304, 2008, Macromolecules 42(19):7504–7517, 2009; Schieber, J Chem Phys 118(11):5162–5166, 2003), and it is thus used to analyze the experimental results. Initially, we consider a stoichiometrically balanced network, i.e., all strands in the ensemble are attached to the network in both ends. Next we add dangling strands to the network representing the stoichiometric imbalance, or imperfections during curing. By considering monodisperse network strands without dangling ends, we find that the relative low-frequency plateau, G₀/G_N⁰G_0/G_N^0, decreases linearly with the average number of entanglements. The decrease from G_N⁰G_N^0 to G ₀ is a result of monomer fluctuations between entanglements, which is similar to “longitudinal modes” in tube theory. It is found that the slope of G′ is dependent on the fraction of network strands and the structural distribution of the network. The power-law behavior of G ^″ is not yet captured quantitatively by the model, but our results suggest that it is a result of polydisperse dangling and soluble structures.     

The MSF model: relation of nonlinear parameters to molecular structure of long-chain branched polymer melts

The elongational viscosity data of model PS combs (Hepperle J, Einfluss der Molekularen Struktur auf Rheologische Eigenschaften von Polystyrol- und Polycarbonatschmelzen. Doctoral Thesis, University Erlangen-Nürnberg, 2003) are reconsidered by including the interchain pressure term of Marrucci and Ianniruberto [Macromolecules 37:3934–3942, 2004] in the Molecular Stress Function model [Wagner et al., J Rheol 47(3):779–793, 2003, Wagner et al., J Rheol 49:1317–1327, 2005d]. Two nonlinear model parameters are needed to describe elongational flow, β and . The parameterβ determines the slope of the elongational viscosity after the inception of strain hardening. It is directly related to the molecular structure of the polymer and represents the ratio of the molar mass of the (branched) polymer to the molar mass of the backbone alone. β follows from the hypothesis of Wagner et al. [J Rheol 47(3):779–793, 2003] that side chains are compressed onto the backbone. We consider also the case that side chains are oriented by deformation, but not stretched, and found little difference in the model predictions. The parameter represents the maximum strain energy stored in the polymeric system and determines the steady-state value of the viscosity in extensional flows. The relation of this energy parameter to the molecular structure is discussed. Good correlations between the energy parameter and different coil contraction ratios, as determined either experimentally or calculated theoretically by considering the topology of the macromolecule, are found. The smaller the relative size of the polymer coil, the larger is the energy parameter and the more strain energy can be stored in the polymeric system. Presented at the 3rd Annual European Rheology Conference, AERC2006, Crete, Greece.     

Characterizing developing adverse pressure gradient flows subject to surface roughness

An experimental study was conducted to examine the effects of surface roughness and adverse pressure gradient (APG) on the development of a turbulent boundary layer. Hot-wire anemometry measurements were carried out using single and X-wire probes in all regions of a developing APG flow in an open return wind tunnel test section. The same experimental conditions (i.e., T _∞, U _ref, and C _p) were maintained for smooth, k ⁺ = 0, and rough, k ⁺ = 41–60, surfaces with Reynolds number based on momentum thickness, 3,000 < Re _θ < 40,000. The experiment was carefully designed such that the x-dependence in the flow field was known. Despite this fact, only a very small region of the boundary layer showed a balance of the various terms in the integrated boundary layer equation. The skin friction computed from this technique showed up to a 58% increase due to the surface roughness. Various equilibrium parameters were studied and the effect of roughness was investigated. The generated flow was not in equilibrium according to the Clauser (J Aero Sci 21:91–108, 1954) definition due to its developing nature. After a development region, the flow reached the equilibrium condition as defined by Castillo and George (2001), where Λ = const, is the pressure gradient parameter. Moreover, it was found that this equilibrium condition can be used to classify developing APG flows. Furthermore, the Zagarola and Smits (J Fluid Mech 373:33–79, 1998a) scaling of the mean velocity deficit, U _∞δ*/δ, can also be used as a criteria to classify developing APG flows which supports the equilibrium condition of Castillo and George (2001). With this information a ‘full APG region’ was defined.     

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.     

A mesoscopic tube model of polymer/layered silicate nanocomposites

Rheology of isothermal suspensions of completely exfoliated silicate lamellae in polymer melts is investigated. In order to express more faithfully the physics involved in low shear rates and low frequencies, we model the polymer molecules composing the melt as chains whose motion is confined to a tube formed by surrounding chains and lamellae. In the absence of lamellae, the model reduces to the mesoscopic model of reptating chains developed in Eslami and Grmela (Rheol Acta, 2008). If the chains are seen only as FENE-P dumbbells, the model reduces to the model developed in Eslami et al. (J Rheol 51:1189–1222, 2007). Responses to oscillatory, transient, and steady shear flows are calculated and compared with available experimental data. Particular attention is payed to the region of low shear rate and low frequency.     

Prediction of multiple overshoots in shear stress during fast flows of bidisperse polymer melts

We present a differential constitutive model of stress relaxation in polydisperse linear polymer melts and solutions that contains contributions from reptation, contour-length fluctuations, and chain stretching. The predictions of the model during fast start-up and steady shear flows of polymer melts are in accord with experimental observations. Moreover, in accordance with reported experimental literature (Osaki et al. in J Polym Sci B Polym Phys 38:2043–2050, 2000), the model predicts, for a range of shear rates, two overshoots in shear stress during start-up of steady shear flows of bidisperse polymer melts having components with widely separated molar masses. Two overshoots result only when the stretch or Rouse relaxation time of the higher molar mass component is longer than the terminal relaxation time of the lower molar mass component. The “first overshoot” is the first to appear with increasing shear rate and occurs as a result of the stretching of longer chains. Transient stretching of the short chains is responsible for the early time second overshoot. The model predictions in steady and transitional extensional flows are also remarkable for both monodisperse and bidisperse polymer solutions. The computationally efficient differential model can be used to predict rheology of commercial polydisperse polymer melts and solutions.     

A new ALS model for dilute polymer solutions in flows with strong shear components

Ghosh et al. (J Rheol 46:1057–1089, 2002) developed a new model for dilute polymer solutions in flows with strong extensional components. The model based on introducing an adaptive length scale (ALS) as an internal variable was developed to reproduce the fine-scale physics of the Kramers chain. The ALS model describes the polymer molecule as a set of identical segments in which each segment represents a fragment of the polymer that is short enough so that it can sample its entire configuration space on the time scale of an imposed deformation and therefore stretch reversibly. As the molecule unravels, the number of the segments decreases, but the maximum length of each segment increases, so that the constant maximum contour length of the molecule is preserved. Though the single-segment-based ALS model accounts for the orientability of the polymer molecules, it cannot describe the internal motions of the molecules due to the lack of internal nodes. Hence, in this work we consider the more realistic chain (multi-segments) model composed of N _seg springs connected linearly. The model presented in this work is an extension of the ALS model developed by Ghosh et al. (J Rheol 46:1057–1089, 2002). We demonstrate that the ALS varies with the flow strength. Specifically, it is found that as the flow strength increases, the ALS decreases. This implies that as the flow strength increases, the polymer molecule is required to divide into finer and finer segments such that each segment can locally equilibrate with the imposed flow. However, there is a critical number of such subdivisions beyond which further subdivision of the polymer molecule is not required to capture the polymer dynamics for a given flow strength. Both shear viscosity and first normal stress coefficient predictions from ALS model show shear thinning behavior with Weissenberg number. In weak flows, the ALS model and the finitely extensible non-linear elastic model exhibit the same behavior.     

Degradation of homogeneous polymer solutions in high shear turbulent pipe flow

This study quantifies degradation of polyethylene oxide (PEO) and polyacrylamide (PAM) polymer solutions in large diameter (2.72 cm) turbulent pipe flow at Reynolds numbers to 3 × 10⁵ and shear rates greater than 10⁵ 1/s. The present results support a universal scaling law for polymer chain scission reported by Vanapalli et al. (2006) that predicts the maximum chain drag force to be proportional to Re ^3/2, validating this scaling law at higher Reynolds numbers than prior studies. Use of this scaling gives estimated backbone bond strengths from PEO and PAM of 3.2 and 3.8 nN, respectively. Additionally, with the use of synthetic seawater as a solvent the onset of drag reduction occurred at higher shear rates relative to the pure water solvent solutions, but had little influence on the extent of degradation at higher shear rates. These results are significant for large diameter pipe flow applications that use polymers to reduce drag.     

Testing of Model Equations for the Mean Dissipation using Kolmogorov Flows

Direct Numerical Simulations (DNS) of Kolmogorov flows are performed at three different Reynolds numbers Re _λ between 110 and 190 by imposing a mean velocity profile in y-direction of the form U(y) = F sin(y) in a periodic box of volume (2π)³. After a few integral times the turbulent flow turns out to be statistically steady. Profiles of mean quantities are then obtained by averaging over planes at constant y. Based on these profiles two different model equations for the mean dissipation ε in the context of two-equation RANS (Reynolds Averaged Navier–Stokes) modelling of turbulence are compared to each other. The high Reynolds number version of the k-ε-model (Jones and Launder, Int J Heat Mass Transfer 15:301–314, 1972), to be called the standard model and a new model by Menter et al. (2006), to be called the Menter–Egorov model, are tested against the DNS results. Both models are solved numerically and it is found that the standard model does not provide a steady solution for the present case, while the Menter–Egorov model does. In addition a fairly good quantitative agreement of the model solution and the DNS data is found for the averaged profiles of the kinetic energy k and the dissipation ε. Furthermore, an analysis based on flow-inherent geometries, called dissipation elements (Wang and Peters, J Fluid Mech 608:113–138, 2008), is used to examine the Menter–Egorov ε model equation. An expression for the evolution of ε is derived by taking appropriate moments of the equation for the evolution of the probability density function (pdf) of the length of dissipation elements. A term-by-term comparison with the model equation allows a prediction of the constants, which with increasing Reynolds number approach the empirical values.     

Simplified model for mass diffusivity estimation based on dynamic pendant drop volume analysis

We present a simplified correlation for calculating the dissolved gas moles in a pendant drop during the diffusion time, for several drop shapes. After this correlation is determined, the Yang and Gu (Ind Eng Chem Res 44:4474–4483, 2005) dynamic pendant drop volume analysis (DPDVA) method for calculation of mass diffusivity from the pendant drop volume variation against time can be used. We solved the differential equation in cylindrical coordinates for the mass transfer model of the gas diffusion into the liquid inside the pendant drop, using a different characteristic length (L_C), instead of the outer radius of the syringe needle (r_n) used in Yang and Gu (Ind Eng Chem Res 44:4474–4483, 2005) for defining the dimensionless variables. L_C is the relationship between the pendant drop volume and its mass transfer surface area at the initial conditions. The generalized correlation saves time, simplifies the method application and the deviations in the diffusion coefficient calculation respect to the complete Yang and Gu model are below 6%.     

Elasticity and dynamics of particle gels in non-Newtonian melts

We investigate the relation between the structure and the viscoelastic behavior of a model polymer nanocomposite system based on a mixture of titanium dioxide (TiO₂) nanoparticles and polypropylene. Above a critical volume fraction, Φ _c, the elasticity of the hybrids dramatically increases, and the frequency dependence of the elastic and viscous moduli reflects the superposition of the independent responses of the suspending polymer melt and of an elastic particle network. In addition, the elasticity of the hybrids shows critical behavior around Φ _c. We interpret these observations by hypothesizing the formation of a transient network, which forms due to crowding of particle clusters. Consistent with this interpretation, we find a long-time, Φ-dependent, structural relaxation, which emphasizes the transient character of the structure formed by the particle clusters. For times below this characteristic relaxation time, the elasticity of the network is Φ-independent and reminiscent of glassy behavior, with the elastic modulus, G^′, scaling with frequency, ω, as G^′∼ω ^0.3. We expect that our analysis will be useful for understanding the behavior of other complex fluids where the elasticity of the components could be superimposed.     

Modeling of Rocks and Cement Alteration due to CO<Subscript>2</Subscript> Injection in an Exploited Gas Reservoir

The injection of CO₂ in exploited natural gas reservoirs as a means to reduce greenhouse gas (GHG) emissions is highly attractive as it takes place in well-known geological structures of proven integrity with respect to gas leakage. The injection of a reactive gas such as CO₂ puts emphasis on the possible alteration of reservoir and caprock formations and especially of the wells’ cement sheaths induced by the modification of chemical equilibria. Such studies are important for injectivity assurance, wellbore integrity, and risk assessment required for CO₂ sequestration site qualification. Within a R&D project funded by Eni, we set up a numerical model to investigate the rock–cement alterations driven by the injection of CO₂ into a depleted sweet natural gas pool. The simulations are performed with the TOUGHREACT simulator (Xu et al. in Comput Geosci 32:145–165, 2006) coupled to the TMGAS EOS module (Battistelli and Marcolini in Int J Greenh Gas Control 3:481–493, 2009) developed for the TOUGH2 family of reservoir simulators (Pruess et al. in TOUGH2 User’s Guide, Version 2.0, 1999). On the basis of field data, the system is considered in isothermal (50°C) and isobaric (128.5 bar) conditions. The effects of the evolving reservoir gas composition are taken into account before, during, and after CO₂ injection. Fully water-saturated conditions were assumed for the cement sheath and caprock domains. The gas phase does not flow by advection from the reservoir into the interacting domains so that molecular diffusion in the aqueous phase is the most important process controlling the mass transport occurring in the system under study.     

Group classification of one-dimensional nonisentropic equations of fluids with internal inertia

A systematic application of the group analysis method for modeling fluids with internal inertia is presented. The equations studied include models such as the nonlinear one-velocity model of a bubbly fluid (with incompressible liquid phase) at small volume concentration of gas bubbles (Iordanski Zhurnal Prikladnoj Mekhaniki i Tekhnitheskoj Fiziki 3, 102–111, 1960; Kogarko Dokl. AS USSR 137, 1331–1333, 1961; Wijngaarden J. Fluid Mech. 33, 465–474, 1968), and the dispersive shallow water model (Green and Naghdi J. Fluid Mech. 78, 237–246, 1976; Salmon 1988). These models are obtained for special types of the potential function W(r,[(r)\dot],S){W(\rho,\dot \rho,S)} (Gavrilyuk and Teshukov Continuum Mech. Thermodyn. 13, 365–382, 2001). The main feature of the present paper is the study of the potential functions with W _S  ≠ 0. The group classification separates these models into 73 different classes.     

Statistically Steady Incompressible DNS to Validate a New Correlation for Turbulent Burning Velocity in Turbulent Premixed Combustion

Incompressible 3-D DNS is performed in non-decaying turbulence with single step chemistry to validate a new analytical expression for turbulent burning velocity. The proposed expression is given as a sum of laminar and turbulent contributions, the latter of which is given as a product of turbulent diffusivity in unburned gas and inverse scale of wrinkling at the leading edge. The bending behavior of U _T at higher u′ was successfully reproduced by the proposed expression. It is due to decrease in the inverse scale of wrinkling at the leading edge, which is related with an asymmetric profile of FSD with increasing u′. Good agreement is achieved between the analytical expression and the turbulent burning velocities from DNS throughout the wrinkled, corrugated and thin reaction zone regimes. Results show consistent behavior with most experimental correlations in literature including those by Bradley et al. (Philos Trans R Soc Lond A 338:359–387, 1992), Peters (J Fluid Mech 384:107–132, 1999) and Lipatnikov et al. (Progr Energ Combust Sci 28:1–74, 2002).     

Self-assembled nanoribbons and nanotubes in water: energetic vs entropic networks

We present a comparative investigation of two opposite classes of self-assembled fibrillar networks. Ribbons and tubes having cross-sectional dimensions in the nanoscale can be formed in aqueous solutions of steroids derived, respectively, from deoxycholic (DC) and lithocholic (LC) acids. Rheological features distinguish energetic networks of DC ribbons rigidly fixed in cylindrical bundles and entropic transient networks of LC tubes weakly interacting in shear-sensitive suspensions. The two classes are characterized by their frequency sweep profiles, viscoelastic linear domains, scaling laws of the elastic shear modulus vs concentration, kinetics of formation of the networks, and their optical birefringence aspects. A theoretical context for networks of rigid fibers is used to account for the scaling exponents α in the G’ (and σ*) ∝C ^α laws (α=2.0 and 1.0, respectively, for DC and LC). The evolution observed in DC gels from ribbons to cylindrical fibers with monodisperse sections made up with four ribbons is an indication of an equilibrated balance between face-to-face attractions and untwisting elastic processes of the constitutive ribbons.Paper presented at the Annual Meeting of the European Society of Rheology, Grenoble, April 2005     

Validity of the bead-spring model for describing the linear viscoelastic properties of single-strand DNA under strongly denaturing conditions

Using a normal mode analysis, we predict the infinite dilution linear viscoelastic properties of single-strand (ss) DNA molecules and compare the results to the linear viscoelastic data of Shusterman et al. (Phys Rev Let 92(4):048303, 2004) obtained by monitoring the diffusion of a fluorescently labeled terminus of the molecule. To compute the overall best global fit, we constrain the hydrodynamic interaction parameter, h*, equilibrium root mean square spring extension, b, and the number of Kuhn steps per spring, N _K,S, to be equal for the strands compared. The fits using the bead-spring model for all but 23,100 base ss-DNA strands match the experimental data at long times with significant deviations at intermediate and short times. However, parameters fitted separately to all individual strand lengths predict results well. The best fits to data for 2,400 and 6,700 base pairs yield N _K,S ∼12 and h* = 0.12. These values are similar to those found for conventional polymers such as polystyrene which have been successfully modeled with N _K,S ∼7 and h* = 0.15, indicating ss-DNA and polystyrene exhibit analogous hydrodynamic behavior.     

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.     

Use of particle image velocimetry to study heterogeneous drag reduction

Large polymer filaments can form when drag reducing polymers are injected through wall slots. The presence of these structures enhances the performance of the drag reducing function by mechanisms which are not understood. This paper shows how particle image velocimetry (PIV) techniques can be used to study changes in the configuration of the injected polymer and in the structure of the velocity field with increasing drag reduction. The filaments are found to behave as solid bodies which break up in high shear regions close to a boundary. The breakup process provides an explanation of why the filaments are not observed close to a wall and offers the possibility of providing a heterogeneous distribution of small aggregates of polymers which could be more effective than uniformly distributed molecules as suggested by Hoyer and Gyr (J Non-Newton Fluid Mech 65:221–240, 1996; J Fluids Eng 120:818–823, 1998), Dunlop and Cox (Phys Fluids 20:203–213, 1977) and Vlachogiannis et al. (Phys Fluid 15:3786–3794, 2004). PIV measurements show dramatic qualitative changes in the velocity patterns at maximum drag reduction.     

Thermorheological properties near the glass transition of oligomeric poly(methyl methacrylate) blended with acrylic polyhedral oligomeric silsesquioxane nanocages

Two distinct oligomeric species of similar mass and chemical functionality (M _w≈2,000 g/mol), one a linear methyl methacrylate oligomer (radius of gyration R _g≈1.1 nm) and the other a hybrid organic–inorganic polyhedral silsesquioxane nanocage (methacryl-POSS, r≈1.0 nm), were subjected to thermal and rheological tests to compare the behaviors of these geometrically dissimilar molecules over the entire composition range. The glass transition temperatures of the blends varied monotonically between the glass transition temperatures of the pure oligomer (T _g=−47.3°C) and the pure POSS (T _g=−61.0°C). Blends containing high POSS contents (with volume fraction φ _POSS≥0.90) exhibited enhanced enthalpy relaxation in differential scanning calorimetry (DSC) measurements, and the degree of enthalpy relaxation was used to calculate the kinetic fragility indices m of the oligomeric MMA (m=59) and the POSS (m=74). The temperature dependences of the viscosities were fitted by the free-volume based Williams–Landel–Ferry (WLF) and Vogel–Fulcher–Tammann (VFT) framework and a dynamic scaling relation. The calculated values of the fragility from the WLF–VFT fits were similar for the POSS (m=82) and for the oligomer (m=76), and the dynamic scaling exponent was similar for the oligomeric MMA and the POSS. Within the range of known fragilities for glass-forming liquids, the temperature dependence of the viscosity was found to be similarly fragile for the two species. The difference in shape of the nanocages and oligomer chains is unimportant in controlling the glass-forming properties of the blends at low volume fractions (φ _POSS<0.20). However, at higher volume fractions, adjacent POSS cages begin to crowd each other, leading to an increase in the fractional free volume at the glass transition temperature and the observed enhanced enthalpy relaxation in DSC.     

Experimental evidence of diffusion-induced bias in near-wall velocimetry using quantum dot measurements

Near-surface velocity measurements are carried out with quantum dot (QD) nanoparticles using evanescent wave illumination. Relying on the small size of QDs, their correspondingly small hydrodynamic radius and high Brownian diffusion coefficient, we consider the situation where the tracer diffusion length over the inter-frame time Δt is large compared to the size of the interrogation region next to the wall. While keeping all other experimental parameters fixed, we systematically increase Δt by as much as a factor of 25, resulting in an increase of the QD diffusion length by a factor of 5. Data indicate a significant overestimation of the “apparent” mean velocity measured experimentally. These results provide a direct confirmation of the phenomenon of diffusion-induced bias described by the simulations of Sadr et al. (2007).