Effect of entrance geometry on the capillary flow of cellulose acetate–acetone solution

Capillary flow data were obtained for a 27.5% solution of cellulose acetate in acetone. The solution temperature was 50°C, and the range of apparent shear rates investigated was 1.7 × 10⁵ to 1.7 × 10⁶ sec^?1. Capillaries having tapered entrance angles of 37.88° to 120.63° were used. A power-law model was adequate to describe the shear stress at the wall (τ_w) and the corrected shear rate \documentclass{article}\pagestyle{empty}\begin{document}$(\dot \gamma )$\end{document} relationship. Entrance angle affected the entrance pressure drop corrected for kinetic energy, (ΔP_0,c); ΔP_0,c increased as the angle widened. Treating the entrance flow as an elongational flow situation facilitated superposition of the Delta;P_0,c data on a single curve. Estimated elongational viscosities decreased with increasing applied stress.     

Effect of flow field heterogeneity in coagulators on aggregate size and structure

Aggregate size and structure were investigated under turbulent conditions in stirred tank (ST) and Taylor–Couette‐type (TC‐type) devices. Root‐mean‐square radius of gyration, 〈Rg〉, and zero‐angle intensity of scattered light, I(0), were acquired as a function of stirring intensity, characterized by an experimentally obtained average hydrodynamic stress, 〈τ〉exp, determined by torque measurements. Evaluating aggregate images revealed that aggregate structure and shape are independent of the device type. However, in TC‐type devices, the aggregates grow to three to four times larger sizes than inside ST, although the same 〈τ〉exp was used in both coagulators. As confirmed by computational fluid dynamics, this can be attributed to the differences in the maximum hydrodynamic stress in ST compared with those in TC‐type devices. In contrast, the power‐law scaling of 〈Rg〉 and I(0) with 〈τ〉exp is preserved for all investigated devices, with an exponent approximately equal to ?0.5 and ?0.7, respectively. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

The Influence of Macroscopic Elongational Flow on Dispersion Processes in Agitated Tanks

The influence of elongational and shear gradients in the macroscopic flow field in agitated tanks on dispersion processes is investigated. Measurements of droplet size distribution for a liquid‐liquid dispersion process using phase‐Doppler anemometry (PDA) reveal that axial‐flow impellers, such as the 24°‐pitched‐blade turbine and propeller, produce smaller droplets than the Rushton turbine at the same average specific power and energy input. These results stand in contradiction to the usual assumption that only the maximum turbulent shear stress determines the breakup process and the Rushton turbine is well known to produce higher turbulent shear stresses. Particle image velocimetry (PIV) measurements of the macroscopic flow field indicate that the 24°‐pitched‐blade turbine and propeller produce larger areas with higher elongational gradients. Therefore, the proposed consideration of particle breakup due to macroscopic elongational flow in addition to turbulent stresses improves the understanding of dispersion processes in agitated tanks.     

Investigation of Absorption and Scattering Properties of Soot Aggregates of Different Fractal Dimension at 532 nm Using RDG and GMM

Radiative properties of numerically generated fractal soot aggregates of different fractal dimensions were studied using the numerically accurate generalized Mie-solution method (GMM) and the Rayleigh-Debye-Gans (RDG) approximate theory. Fractal aggregates of identical prefactor but different fractal dimensions, namely, 1.4, 1.78, and 2.1, were generated numerically using a tunable algorithm of cluster–cluster aggregation for aggregates containing up to 800 primary particles. Radiative properties of these aggregates were calculated at a wavelength of 532 nm assuming a soot refractive index of 1.6 + 0.6i. Four commonly used structure factors in the RDG approximation were used to investigate the effect of structure factor on the differential and total scattering cross-sections and the asymmetry factor. The differential and total scattering properties calculated using the RDG approximation become increasingly sensitive to the structure factor with increasing the fractal dimension. Primary particle interactions are the fundamental mechanism for the aggregate absorption enhancement for small aggregates and the shielding effect for larger aggregates. The extent of these two competing factors is dependent on the fractal dimension and aggregate size. RDG reasonably predicts the effect of fractal dimension on the scattering properties, but fails to account for the effect of aggregation or fractal morphology on the absorption property of fractal soot aggregates, though the error is in general less than 15%.

Copyright 2013 American Association for Aerosol Research     

Influence of melt deformation history on orientation in vitrified polymers

An experimental study of the development of orientation in polystyrene melts during flow and its retention in vitrified parts is described. It is shown on the basis of elongational and shear flow experiments that orientation in vitrified polystyrenes may be predicted from a knowledge of the stress field at the time of vitrification and application of stress-optical laws. More generally a relationship between birefringence and principal stress difference is found which correlates (1) on-line isothermal shear flow, (2) on-line non-isothermal elongational flow (melt spinning), and (3) vitrified samples formed in both shear and elongational flow. It is further proposed that orientation in polymer chains in deforming melts is uniquely dependent on stress—specifically, that the ratio of the stress-optical constant C to the intrinsic birefringence Δ° is approximately a constant.     

Wet dispersion mechanism of fine aggregates in multiphase flow with solid beads under simple shear

Clarifying the disintegration mechanism of aggregates in multiphase fluid flow coupled with beads and particulates is important for the optimum design of a wet dispersion process using a stirred media mill. Thus, we develop a numerical method for simulating multiphase flow with beads and particulates using a discrete element method and computational fluid dynamics, and we use the four‐way coupling simulation to study the fluid‐bead‐particulate‐coupled phenomenon that occurs in a simple shear box. The results show that the dominant force causing aggregate disintegration is the fluid force, rather than the bead contact force, because aggregates rarely collide with beads, contact force of which is too small to disintegrate aggregates. Furthermore, aggregates with strong aggregation force are effectively disintegrated by the fluid flow with a dominant high pure‐shear rate induced near the bead surfaces by the expansive force, rather than the compressive force. © 2014 American Institute of Chemical Engineers AIChE J 60: 4076–4085, 2014     

Rheological behavior of polypropylene/layered silicate nanocomposites prepared by melt compounding in shear and elongational flows

Melt rheology and processability of exfoliated polypropylene (PP)/layered silicate nanocomposites were investigated. The nanocomposites were prepared by melt compounding process in the presence or absence of a PP‐based maleic anhydride compatibilizer. PP/layered silicate nanocomposites showed typical rheological properties of exfoliated nanocomposites such as nonterminal solid‐like plateau behavior at low frequency region in oscillatory shear flow, higher steady shear viscosity at low shear rate region, and outstanding strain hardening behavior in uniaxial elongational flow. The melt processability of exfoliated PP/layered silicate nanocomposites was significantly improved due to good dispersion of layered silicates and increased molecular interaction between the PP matrix and the layered silicate organoclay. Small‐angle X‐ray scattering and transmission electron microscopy results revealed that the layered silicate organoclay was exfoliated and good interaction between PP matrix and organoclay was achieved by using the PP‐g‐MAH compatibilizer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3506–3515, 2007     

Molecular orientation in injection molding

A semiquantitative model is proposed to explain the complex molecular orientation distribution, observed in injection moldings of amorphous polymers. The model incorporates flow and heat transfer mechanisms coupled with molecular theories. The orientation in the surface skin is related to steady elongational flow in the advancing front, whereas the orientation in the core is related to the shear flow, behind the front, between two solidyfying layers. Coupled with the elongational and shear-induced orientations, a molecular relaxation process takes place which is determined by the rate of heat transfer. The bead-and-spring macromolecular theory was used to calculate root mean end-to-end distances of macromolecules in the various flow fields, as well as the relaxation process.     

Structure and properties of ultrahigh molecular weight polyethylene processed under a consecutive elongational flow

Herein, a novel eccentric rotor extruder (ERE) capable of generating a continuous elongational flow was used to process ultrahigh molecular weight polyethylene (UHMWPE) without any processing aids and then compare with a conventional rotational batch mixer based on a shear flow. The morphological and rheological characterization verify that the technique based on the elongational flow could effectively reduce melting defects and yield more homogeneous morphology within the extruding samples relative to the conventional bath mixing based on a shear flow. The extrusion processing under an elongational flow can largely maintain the viscosity average molecular weight (M_η) of the UHMWPE nascent powder with only a 5.0% decrease at 200 °C, implying considerably low thermal oxidative degradation in sharp contrast to the conventional processing with significantly reduced M_η by 40.3%. Furthermore, the crystallinity for the sample prepared under an elongational flow is lower than that processed under a shear flow. These differences lies in the higher normal stress, rapider heat transfer and shorter duration generated by the ERE.     

Aggregate structures formed via a bridging flocculation mechanism

A high molecular weight cationic polyelectrolyte has been used to flocculate a colloidal dispersion of anionic polystyrene latex particles. The polymer used had a high charge density and the flocculation occurred at a solution pH where both the polymer and the particles were fully charged. Under these conditions, flocculation is expected to occur through a bridging flocculation mechanism. Low angle laser light scattering has been used to follow the flocculation process as a function of time; parameters of interest were the aggregate sizes, size distributions, and aggregate mass fractal dimensions. The light scattering measurements showed that the flocs formed had a mass fractal character. All the systems examined here were overdosed with respect to the optimum flocculation concentration of polymer. Under these conditions, decreasing the polymer concentration was seen to result in an increased flocculation efficiency. A secondary growth process was also observed whereby initially formed fractal aggregates can subsequently aggregate again. These larger aggregates are also expected to be mass fractals although this cannot be determined from the light scattering measurements due to the superposition of Fraunhofer diffraction effects. This type of fractal-in-fractal character is unusual.     

Measurement of the equibiaxial elongational viscosity of polystyrene using lubricated squeezing

The equibiaxial elongational viscosity of polystyrene was determined using a lubricated squeezing technique. Constant strain rates up to Hencky strains of 4.5 could be maintained by a newly constructed instrument. Test results from controlled stress and controlled strain rate measurement were consistent and yielded well-defined steady-state viscosities. Measurements appeared to be unaffected by sample geometry, although proper lubrication is important in achieving steady state. The measured biaxial viscosity appeared to be strain rate thinning above a biaxial strain rate of ≈ 0.01 s⁻¹ at 160°C. As anticipated in the Newtonian region, biaxial elongational viscosity was approximately six times the shear viscosity. Thinning indices of both shear and biaxial elongational viscosities were 0.75. Data obtained at various temperatures were shifted following the timetemperature superposition principle. The resulting master curve could be fitted by a Carreau model with n ≈ 0.3 and a time constant of 110 s.     

Simulation of Aggregate Deformation and Breakup in Simple Shear Flows Using a Combined Continuum and Discrete Model

The evolution of aggregates suspended in liquid and subjected to simple (elongational) shear flows is reported under different shear rates and for varying strengths of interparticle interactions. This is carried out using simulations via the combined continuum and discrete model, offering a combined approach of distinct element method and computational fluid dynamics. In such a model, the motion of individual particles is obtained by solving Newton's second law of motion and flow of continuum fluid by the locally-averaged Navier–Stokes equations. The results demonstrate the dependence of both the dominating aggregate breakup mechanism and final aggregate morphology on shear rates and strength of interparticle interactions.     

Modeling of nonlinear extensional and shear rheology of low-viscosity polymer melts

The hierarchical multi-mode molecular stress function (HMMSF) model developed by Narimissa and Wagner [Rheol. Acta 54, 779–791 (2015), and J. Rheol. 60, 625–636 (2016)] for linear and long-chain branched (LCB) polymer melts were used to analyze the set of transient elongational and shear viscosity data of two LCB low-density polyethylenes (1840H and 2426 k), and a linear poly-(ethylene-co-α-butene), PEB A-780090 as reported by [Li et al. J. Rheol. 64, 177 (2020)], who had developed a new horizontal extensional rheometer to extend the lower limits of elongational viscosity measurements of polymer melts. Comparison between model predictions and elongational stress growth data reveals excellent agreement within the experimental window, and good consistency with shear stress growth data, based exclusively on the linear-viscoelastic relaxation spectrum and only two nonlinear model parameters, the dilution modulus G_D for extensional flows, and in addition a constraint release parameter for shear flow.     

Urea/NaOH aqueous solution as new solvent of aeromonas gum

Aeromonas (A) gum, an acidic heteropolysaccharide, formed aggregates easily in NaCl aqueous solution. A novel solvent of the A gum, which can prevent aggregation, was found to be 0.20M urea/0.25M NaOH aqueous solution. The weight‐average molecular weight (M_w), radius of gyration (〈s²〉^1/2), and intrinsic viscosity ([η]) of the samples were determined in 0.20M urea/0.25M NaOH aqueous solution at 25°C by light scattering (M_w, 〈s²〉^1/2) and viscometry ([η]). The values of M_w, 〈s²〉^1/2, and [η] were close to those in 0.20M lithium chloride/dimethylsulfoxide, in which the A gum exists as a semiflexible single chain, implying the same conformation for the A gum in 0.20M urea/0.25M NaOH aqueous solution. The results revealed that 0.20M urea/0.25M NaOH aqueous solution is a good solvent, which effectively avoids the aggregates of the A gum in aqueous solution. Moreover, it can be used to investigate the solution properties and chain conformation of water‐insoluble polysaccharides or the polysaccharides that are easily aggregated in aqueous systems. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1710–1713, 2005     

Light Scattering by Fractal Aggregates: A Review

This paper presents a review of scattering and absorption of light by fractal aggregates. The aggregates are typically diffusion limited cluster aggregates (DLCA) with fractal dimensions of D     

Effect of Volume Fraction on Transient Structural Behavior of Aerosol Particles Using Off-Lattice Kinetic Monte Carlo Simulation

Fractal-like aggregates exhibit interesting properties that determine their physicochemical advantages, and thus, the control and prediction of aggregation is critical for many applications. An off-lattice kinetic Monte Carlo (KMC) simulation was performed to investigate the aggregate evolution from primary particles to three-dimensional fractal aggregates, at three different volume fractions. We have found that at low volume fraction, aggregation kinetics is slow, and aggregate morphology is widely open and stringy, with fractal dimension of (D_f) 1.8, in which the system is constantly preserved in the dilute regime. In denser volume fractions, however, the aggregation kinetics appears to be accelerated and aggregate morphology is more compact and less stringy due to the transition from dilute to dense regimes. Moreover, the volume fractions determine what kind of coagulation mechanism may occur to produce aggregates with different morphologies. At low volume fraction, coagulation is predominated by coagulation between aggregates in which the maximum probability of interpenetration event is only 18%. This suggests that aggregates at low volume fraction can maintain their self-similarity behavior. While at high volume fraction, coagulation is predominated by two subsequent coagulation mechanisms, namely, primary particle–aggregate and aggregate–aggregate interaction. The probability of interpenetration event increases up to 40%. In addition, the interpenetration process as well as the primary particle–aggregate coagulation, particularly in the dense regime, could produce superaggregates with a hybrid structure with a high fractal dimension at large size scales and a low fractal dimension at small scales. A detail mechanism for the formation of superaggregates was discussed.

Copyright © 2015 American Association for Aerosol Research     

Molecular weight and chain conformation of amylopectin from rice starch

By using laser light scattering (LS) and size exclusion chromatography combined LS, we have investigated the molecular weight and chain conformation of amylopectin from rice of India (II‐b), japonica (IJ‐b), and glutinous (IG‐b) in dimethyl sulfoxide (DMSO) solution. The weight‐average molecular weight (M_w) and radius of gyration (〈S²〉^½) of amylopectin were determined to be 4.06 × 10⁷ and 128.5 nm for India rice, 7.41 × 10⁷ and 169.6 nm for japonica rice, 2.72 × 10⁸ and 252.3 nm for glutinous rice, respectively. The 〈S²〉^½ values were much lower than that of normal polymers, indicating a small molecular volume of amylopectin, as a result of highly branched structure. Ignoring the difference of degree of branching, approximated dependences of 〈S²〉^½ and intrinsic viscosity ([η]) on M_w for amylopectin in DMSO at 25°C were estimated to be 〈S²〉^½ = 0.30M_w^0.35 (nm) and [η] = 0.331M_w^0.41 (mL g^?1) in the M_w range studied. Moreover, from the 〈S²〉^½ values of numberless fractions obtained from many experimental points in the SEC chromatogram detected with LS, the dependence of 〈S²〉^½ on M_w for the II‐b sample was estimated also to be 〈S²〉^½ = 0.34 M_w^0.347, coinciding with the above results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Experimental investigation of the influence of molecular weight distribution on the rheological properties of polypropylene melts

An experimental study of steady shear and elongational flow Theological properties of a series of polypropylene melts of varying molecular weight and distribution is reported. Broadening the molecular weight distribution increases the non-Newtonian character of the shear viscosity function and increases the principal normal stress differences at fixed shear stress. The behavior is compared to earlier rheological property-molecular weight studies. Correlations are developed for these properties in terms of molecular structure. Elongational flow studies indicate that for commercial and broader molecular weight distribution samples, ready failure by neck development occurs and the elongational viscosity appears to decrease with increasing elongation rate. For narrower molecular weight distribution samples, the elongational viscosity is an increasing function of elongation rate, The implication of these experimental results to viscoelastic fluid constitutive equations and polymer melt processing is developed.