Effects on the melt rheology of systems of Nd‐Fe‐B particles suspended in a poly(phenylene sulfide) and liquid crystalline polymer blend

The melt rheology of blends of a liquid crystalline polymer (LCP) and poly(phenylene sulfide) (PPS) and their composites with ferromagnetic Nd‐Fe‐B particles (MQP) was studied. We investigated the effects of LCP concentration, Nd‐Fe‐B particle volume fraction and size, distribution, and shear rate on the rheological properties of these composites. Enthalpy of fusion changes that were observed resulted from the addition of the LCP and Nd‐Fe‐B particles to the polymer blends/composites. The shear rate and frequency dependencies of the materials revealed a viscosity reduction at low (1–3 wt%) and moderate (10–15 wt%) LCP concentrations, and strong effects on the shear‐thinning characteristics of the melt. The suspensions of polydispersed Nd‐Fe‐B particle configurations in PPS that were of lower size ratios gave better processability, which is contradictory to previously reported behavior of suspensions containing spherical particles. Specifically, the compositions with unimodal and a bimodal distribution of Nd‐Fe‐B particles gave the lowest viscosities. The experimental data were correlated with semi‐empirical viscosity model equations of Maron‐Pierce, Krieger‐Dougherty, Eilers, and Thomas and were found to be consistent with the data. The maximum packing fraction, ϕ_m, of the MQP particles was estimated to be within the range of 0.78 ϕ ≤_m ≤ 1.0 through graphical and parametric evaluation methods.     

Physical properties of hydrogels of poly(2‐hydroxyethyl methacrylate) and copolymers with mono‐methyl itaconate synthesized by bulk and solution polymerization

The physical properties found during the swelling process of poly(2‐hydroxyethyl methacrylate) (PHEMA) and of copolymers of HEMA with mono‐n‐methyl itaconate, synthesized by solution and bulk polymerization, are reported. The swelling kinetics were followed at four different temperatures (295, 300, 305 and 310 K). Experimental data follow second‐order swelling kinetics, from where the kinetic rate constant k_∞ and the swelling capacity at equilibrium W_∞ were calculated as a function of temperature. The kinetic rate constant obeys Arrhenius behaviour. The following network parameters were determined for the hydrogels: Young's moduli E, effective crosslinking density v_e, molar mass per crosslink M_C, volume fraction ϕ₂ and polymer‐liquid interaction parameter χ. © 2000 Society of Chemical Industry     

Gas hold‐up in bubble columns: Operation with concentrated slurries versus high viscosity liquid

The hydrodynamics of bubble columns with concentrated slurries of paraffin oil (density, ρ_L = 790 kg/m³; viscosity, μ_L = 0.0029 Pa·s; surface tension, σ = 0.028 N·m¹) containing silica particles (mean particle diameter d_p = 38 μm) has been studied in columns of three different diameters, 0.1, 0.19 and 0.38 m. With increasing particle concentration, the total gas hold‐up decreases significantly. This decrease is primarily caused by the destruction of the small bubble population. The hold‐up of large bubbles is practically independent of the slurry concentration. The measured gas hold‐up with the 36% v paraffin oil slurry shows remarkable agreement with the corresponding data obtained with Tellus oil (ρ_L = 862 kg/m³; μ_L = 0.075 Pa·s; σ = 0.028 N·m^?1) as the liquid phase. Dynamic gas disengagement experiments confirm that the gas dispersion in Tellus oil also consists predominantly of large bubbles. The large bubble hold‐up is found to decrease significantly with increasing column diameter. A model is developed for estimation of the large bubble gas hold‐up by introduction of an wake‐acceleration factor into the Davies‐Taylor‐Collins relation (Collins, 1967), describing the influence of the column diameter on the rise velocity of an isolated spherical cap bubble.     

Viscosity Behaviour of Dilute and Moderately Concentrated Solutions. 1. Poly(vinylpyrrolidone) in 2-propanol

Abstract

The zero-shear viscosity of dilute to moderately concentrated poly(vinylpyrrolidone) solutions in 2-propanol were measured at different temperatures in the newtonian flow range. The viscosity data were analyzed in terms of Martin's and Fedor's equations. The viscosity-concentration data were generalized in terms of reduced variables. The relation between the K_M parameter for the rheological interaction and some characteristics of polymer solutions such as the flexibility of the PVP chain is discussed. The temperature dependence of viscosities was expressed by the Arrhenius-Frenkel-Eyring equation and the activation energy of viscous flow of polymer solutions (ΔGv) was calculated. It was shown that ΔGv increases with concentration and it is independent of the temperature.     

Spontaneous imbibition of liquid in glass fiber wicks,Part II: Validation of a diffuse‐front model

In Part I (Zarandi MAF, Pillai KM. Spontaneous Imbibition of Liquids in Glass‐Fiber Wicks. Part I: Usefulness of a Sharp‐Front Approach. AIChE J, 64: 294–305, 2018), a model based on sharp liquid‐front was proposed where a good match with the experimental data was achieved. However, the model failed to account for partial saturations in the wicks. Here, Richard's equation to predict liquid saturation is tried where the equation is solved numerically in 3D using COMSOL and analytically in 1D using Mathematica for glass‐fiber wicks after treating them as transversely‐isotropic porous media. As a novel contribution, relative permeability and capillary pressure are determined directly from pore‐scale simulations in wick microstructure using the state‐of‐the‐art software GeoDict. The saturation along the wick length is determined experimentally through a new liquid‐N₂ based freezing technique. After including the gravity effect, good agreements between the numerical/analytical predictions and experimental results are achieved in saturation distributions. We also validated the Richard's equation based model while predicting absorbed liquid‐mass into the wick as function of time. © 2017 American Institute of Chemical Engineers AIChE J, 63: 306–315, 2018     

Effect of filler content and surface treatment on the tensile properties of glass‐bead‐filled polypropylene composites

The tensile properties of polypropylene (PP) filled with two A‐glass beads with the same size, PP/3000 (glass bead surface pretreated with a silane coupling agent) and PP/3000U (no surface pretreatment), have been measured by using an Instron materials testing machine at room temperature, to identify the effects of the filler surface pretreatment and its content on the tensile properties of these composites. The results show that the Young's modulus E_c of the composites increases non‐linearly with increasing volume fraction of glass beads ϕ_f, while the tensile yield strength σ_yc and tensile stress at break σ_bc of the composites decrease with an increase of ϕ_f, in the ϕ_f range 0–30%. Furthermore, the values of E_c and σ_bc of the PP/3000 system are somewhat higher than those of the PP/3000U system under the same test conditions, but this is in contrast to the tensile strain at break ε_bc and tensile fracture energy E_bc, especially at higher ϕ_f values. Good agreement is shown between the measured tensile strength and the predicted value by using an equation proposed in previous work. In addition, ε_bc and E_bc reach maximum values at ϕ_f = 25% for both systems. This indicates that there is a brittle–ductile transition for the composites in tension. © 2000 Society of Chemical Industry     

Effects of glass bead content and surface treatment on viscoelasticity of filled polypropylene/elastomer hybrid composites

The dynamic mechanical properties of A‐glass bead filled polypropylene (PP)/ethylene–propylene–diene monomers polymer (EPDM) ternary composites have been measured over a temperature range from −80 °C to 100 °C and at a fixed frequency of 1 Hz, using a dynamic mechanical analyser (DMA), to identify the effects of the filler content and its surface treatment with a silane coupling agent on the dynamic viscoelastic behaviour. The results show that the storage modulus (E′_c) and loss modulus (E ″_c) of these composites with 10% volume fraction of EPDM at 25 °C increase non‐linearly with increasing volume fraction of glass beads (ϕ_g). At the same test conditions, the E′_c value of the PP/EPDM filled with pretreated glass beads is higher than that of the uncoated glass bead filled PP/EPDM system, especially at higher ϕ_g, while the difference in E ″_c between both systems is very small. The mechanical damping for the former decreases with increasing ϕ_g, but the opposite is true for the latter. The glass transition temperature of these composites varies irregularly with ϕ_g. The dynamic complex viscosity increases nonlinearly with an increase of ϕ_g. In addition, the interfacial structure between the matrix and inclusions has been observed by means of a scanning electron microscope. © 1999 Society of Chemical Industry     

Bubble shape,gas flow and gas–liquid mass transfer in pulp fibre suspensions

Gas–liquid mass transfer in pulp fibre suspensions in a batch‐operated bubble column is explained by observations of bubble size and shape made in a 2D column. Two pulp fibre suspensions (hardwood and softwood kraft) were studied over a range of suspension mass concentrations and gas flow rates. For a given gas flow rate, bubble size was found to increase as suspension concentration increased, moving from smaller spherical/elliptical bubbles to larger spherical‐capped/dimpled‐elliptical bubbles. At relatively low mass concentrations (C_m = 2–3% for the softwood and C_m ? 7% for the hardwood pulp) distinct bubbles were no longer observed in the suspension. Instead, a network of channels formed through which gas flowed. In the bubble column, the volumetric gas–liquid mass transfer rate, k_La, decreased with increasing suspension concentration. From the 2D studies, this occurred as bubble size and rise velocity increased, which would decrease overall bubble surface area and gas holdup in the column. A minimum in k_La occurred between C_m = 2% and 4% which depended on pulp type and was reached near the mass concentration where the flow channels first formed.     

Enhanced thermal conductivity of semi‐aliphatic liquid crystalline polybenzoxazoles using magnetic orientation

Polybenzoxazole (PBO) model compounds consisting of benzoxazole mesogenic units linked with long alkyl chains via ether or ester groups were prepared from flexible dicarboxylic acids with two kinds of bis(o‐aminophenol)s, i.e. 4,4′‐diamino‐3,3′‐dihydroxybiphenyl (p‐HAB) and 3,3′‐diamino‐4,4′‐dihydroxybiphenyl (m‐HAB). The results revealed that the use of p‐HAB completely erased the thermotropic liquid crystallinity and that the m‐HAB‐based ether‐linked model compound was much more advantageous for the formation of a stable liquid crystal phase than the corresponding ester‐linked one. However, the relevant high‐molecular‐weight PBOs showed quite opposite results. Only the m‐HAB‐based ester‐linked C₁₀ PBO system showed a liquid crystal‐like texture among various semi‐aliphatic PBO systems examined. A very high thermal conductivity of 1.79 W m^?1 K^?1 along the thickness direction for the m‐HAB‐based ester‐linked C₁₀ PBO film was achieved by heat treatment in the liquid crystalline state under a strong magnetic field of 10 T. Copyright © 2011 Society of Chemical Industry     

Gas hold-up and oxygen transfer in three-phase external-loop airlift bioreactors: Non-Newtonian fermentation broths

The effects of solids loading on gas hold-up and oxygen transfer in external-loop airlift bioreactors with non-Newtonian fermentation media are discussed. Experiments were performed in two model external-loop airlift bioreactors with aqueous solutions of carboxymethyl cellulose (CMC) and xanthan gum representing non-Newtonian flows. Low-density plastic particles of 1030 and 1300 kg m⁻³ were used and the solids loading was varied in the range 0–20% (v/v). For the inelastic non-Newtonian CMC aqueous solutions, the presence of low-density solid particles slightly increased the riser gas hold-up, ϕ_gr, but decreased the volumetric mass transfer coefficient, k_La. On the other hand, ϕ_gr decreased but k_La increased with solids loading in the viscoelastic non-Newtonian xanthan gum aqueous solution. The extent of these effects depended on non-Newtonian flow behavior. Theoretical models of riser gas hold-up and volumetric mass transfer coefficient have been developed. The capability of the proposed models was examined using the present experimental data obtained in the model external-loop airlift bioreactors and the available data in the literature. The data were successfully correlated by the proposed correlations except the results for k_La coefficient in the xanthan gum solution.     

Darcy's law for two‐dimensional flows: Singularities at corners and a new class of models

As is known, Darcy's model for fluid flows in isotropic homogeneous porous media gives rise to singularities in the velocity field for essentially two‐dimensional flow configuration, like flows over corners. Considering this problem from the modeling viewpoint, this study aims at removing this singularity, which cannot be regularized via conventional generalizations of the Darcy model, like Brinkman's equation, without sacrificing Darcy's law itself for unidirectional flows where its validity is well established experimentally. The key idea is that as confirmed by a simple analogy, the permeability of a porous matrix with respect to flow is not a constant independent of the flow but a function of the flow field (its scalar invariants), decreasing as the curvature of the streamlines increases. This introduces a completely new class of models where the flow field and the permeability field are linked and, in particular problems, have to be found simultaneously. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Novel method for determination of gas solubilities in low vapor pressure liquids

A modified version of a standard device for measuring gas adsorption and desorption isotherms and surface area of adsorbents and catalysts (ASAP (Accelerated Surface Area and Porosimetry System) 2020, Micromeritics USA) is used for the first time to measure gas solubilities (i.e., CO₂) in low vapor pressure liquids (i.e., the IUPAC standard ionic liquid 1‐hexyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₆mim][Tf₂N])) in the Henry's law region. The solubility data are in very good agreement with the reported data in literature. Furthermore, the Henry's law constants are calculated from the solubility data and compared to the experimental data found in literature. The results from this study demonstrate that Micromeritics ASAP 2020 is a suitable apparatus for gas absorption by solvents with reduced vapor pressures. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2981–2986, 2017     

Computational modelling of industrial pulp stock chests

Agitated pulp stock chests are the most widely used mixers in pulp and paper manufacture. Stock chests are used for a number of purposes, including attenuation of high‐frequency disturbances in pulp properties (such as mixture composition, fibre mass concentration, and suspension freeness) and are designed using semi‐empirical rules based largely on previous experience. Tests made on both laboratory and industrial‐scale pulp chests indicate that they are subject to non‐ideal flows, including channelling and creation of dead zones. In the present work, a commercial computational fluid dynamic (CFD) software (Fluent) is used to model two industrial pulp stock chests. The first chest is rectangular, agitated using a single side‐entering impeller, and feeds a mixture of chemical pulps at 3.5% mass concentration (C_m) to a papermachine. The second chest has rectangular geometry, with a mid‐feather wall used to direct suspension flow through a U‐shaped trajectory past four side‐entering impellers. This chest is used to remove latency from a C_m = 3.5% thermomechanical pulp suspension ahead of stock screening. For CFD computations, pulp rheology was described using a modified Hershel–Buckley model. Steady‐state simulations were made corresponding to process conditions during mill tests. The calculated steady‐state flows were then used to determine the dynamic response of the virtual chests and then compared with experimental measurements and found to agree reasonably well. The computed flow fields provided insight into mixing processes occurring within the chests, showing cavern formation around the impellers (which reduced the agitated volume available for mixing). Mass‐less particle tracking, using the steady‐state flow field, gave insight into the stagnant regions and bypassing zones created in the vessels. This paper discusses difficulties encountered in characterising the mixing (both experimentally and computationally) and the limitations of the industrial data.     

Investigation of liquid crystalline and photocrosslinkable poly[4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamate]s

Three series of liquid‐crystalline‐cum‐photocrosslinkable polymers were synthesized from 4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamates (x = ? H, ? OCH₃ and ? CN; m = 6, 8 and 10) by free radical solution polymerization using azobisisobutyronitrile as an initiator in tetrahydrofuran at 60 °C. All the monomers and polymers were characterized using intrinsic viscosity, and FTIR, ¹H NMR and ¹³C NMR spectroscopy. The liquid crystalline behavior of these polymers was examined using a hot stage optical polarizing microscope. All the polymers exhibited liquid crystalline behavior. The hexamethylene spacer‐containing polymers exhibited grainy textures; in contrast, the octamethylene and decamethylene spacer‐containing polymers showed nematic textures. Differential scanning calorimetry data confirmed the liquid crystalline property of the polymers. Thermogravimetric analysis revealed that all the polymers were stable between 236 and 344 °C in nitrogen atmosphere and underwent degradation thereafter. As the methylene chain length increases in the polymer side‐chain, the thermal stability and char yield of the polymers decrease. The photocrosslinking property of the polymers was investigated using the technique of exposing the polymer solution to UV light and using UV spectroscopy. The crosslinking reaction proceeds via 2π–2π cycloaddition reactions of the ? CH?CH? of the pendant cinnamate ester. The polymers containing electron‐releasing substituents (? OCH₃) showed faster crosslinking than the unsubstituted polymers and those containing electron‐withdrawing substituents (? CN). Copyright © 2007 Society of Chemical Industry     

Gas‐Liquid Mass Transfer in Pulp Retention Towers

The volumetric gas‐liquid mass transfer rate, k_La, was measured under batch conditions in a 0.28 m diameter laboratory‐scale retention column. Tests on water, and on unbleached kraft (UBK) pulp suspensions (mass fractions, C_m from 0.013 to 0.09) were made with air or nitrogen sparged through the column at superficial gas velocities between 0.0015 to 0.05 m/s. k_La varied with suspension mass concentration and superficial gas velocity, initially decreasing with increasing mass concentration, reaching a minimum between C_m = 0.03 and 0.06, and then increasing. The minimum in k_La coincided with a change in hydrodynamics within the column, from bubble column behaviour below C_m = 0.03 to porous solid behaviour above C_m = 0.06.     

Synthesis and liquid‐crystal‐aligning properties of novel aromatic poly(amide imide)s bearing n‐alkyloxy side chains

Novel aromatic poly(amide imide)s (m‐PAIs, m = 8, 12, 16) containing preformed isophthalamide unit and pendent n‐alkyloxy (‐O‐n‐C_mH_2m+1, m = 8, 12, 16) side chains were prepared in thin films by polymerization of pyromellitic dianhydride (PMDA) with N,N′‐bis(4‐aminophenyl)‐5‐(n‐alkyloxy)isophthalamides (m‐DAs) obtained from N,N′‐bis(4‐nitrophenyl)‐5‐(n‐alkyloxy)isophthalamides (m‐DNs). The m‐PAI films were tough, flexible and transparent with inherent viscosities in the 1.25–1.67 dL/g range in DMAc and soluble in DMAc and NMP on heating. In TGA m‐PAIs began to degrade around 440°C and in DSC no phase transitions were detected. In X‐ray diffractometry the m‐PAIs appeared amorphous with loosely developed layered crystalline structure. In liquid crystal (LC)‐aligning performance measured using 4‐n‐pentyl‐4′‐cyanobiphenyl (5CB) on thin film surfaces rubbed with standard velvet fibers, the m‐PAIs showed homogeneous LC alignment parallel to the rubbing direction with 2.5–17.5° pretilt angles, depending on the rubbing density and n‐alkyloxy side chain length. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystallization behavior of glass bead‐filled low‐density polyethylene composites

The effects of the filler content and the filler size on the crystallization and melting behavior of glass bead‐filled low‐density polyethylene (LDPE) composites have been studied by means of a differential scanning calorimeter (DSC). It is found that the values of melting enthalpy (ΔH_c) and degree of crystallinity (x_c) of the composites increase nonlinearly with increasing the volume fraction of glass beads, ϕ_f, when ϕ_f is greater than 5%; the crystallization temperatures (T_c) and the melting temperatures (T_m) of the composites are slightly higher than those of the pure LDPE; the effects of glass bead size on x_c, T_c, and T_m are insignificant at lower filler content; but the x_c for the LDPE filled with smaller glass beads is obviously greater than that of the filled system with bigger ones at higher ϕ_f. It suggests that small particles are more beneficial to increase in crystallinity of the composites than big ones, especially at higher filler content. In addition, the influence of the filler surface pretreated with a silane coupling agent on the crystallization behavior are not too outstanding at lower inclusion concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 687–692, 1999     

Modelling of the Nonlinear Behavior of Compatibilized Polyethylene/Polyamide Blends in Shear and Extensional Flows

We have studied the effect of the amount Φ_c of a reactive compatibilizer on the rheological properties of a polyethylene/polyamide blend, under steady shear and transient extensional flows. Here, we propose to describe the viscosity η(γ) and the first normal stress coefficient γ₁(γ) using a Carreau‐type power‐law model, which is a three‐parameter model. A single model is sufficient to express the behavior of γ₁(γ) On the other hand, the complete η(γ) curve is described by the superposition of two Carreau models, in relation to the presence of two relaxation mechanisms. Moreover, the extentional viscosity η_E(?), estimated using the end pressure drop observed in capillary flow experiments, is expressed by a two‐parameter power‐law model.     

Gas‐liquid mass transfer in low‐ and medium‐consistency pulp suspensions

The volumetric gas—liquid mass transfer coefficient (k_La) was measured for low‐ and medium‐consistency pulp suspensions using the cobalt‐catalyzed sulfite oxidation technique. Mass transfer rates were measured in a high‐shear mixer for a range of operating parameters, including the rotor speed (N = 10 to 50 rev/s), gas void fraction (X_g = 0.10 to 0.40) and fibre mass concentration (C_m = 0.0 to 0.10). k_La measurements were compared with the macroscale flow regime in the vessel (characterized using photographic techniques) and correlated with energy dissipation, gas void fraction and suspension mass concentration in the mixer. We found that gas‐liquid mass transfer was significantly reduced in pulp suspensions, even for low suspension concentrations. Part of this reduction was associated with dissolved components leached from the fibres into the liquid phase. This could account for reductions in k_La of up to 30% when compared with distilled water. The fibres further reduced k_La, with the magnitude of the decrease depending on the fibre mass concentration. Correlations were developed for k_La and compared with results available in the literature.     

Measurement and prediction of LDPE/CO2 solution viscosity

When CO₂ is dissolved into a polymer, the viscosity of the polymer is drastically reduced. In this paper, the melt viscosities of low‐density polyethylene (LDPE)/supercritical CO₂ solutions were measured with a capillary rheometer equipped at a foaming extruder, where CO₂ was injected into a middle of its barrel and dissolved into the molten LDPE. The viscosity measurements were performed by varying the content of CO₂ in the range of 0 to 5.0 wt% and temperature in the range of 150°C to 175°C, while monitoring the dissolved CO₂ concentration on‐line by Near Infrared spectroscopy. Pressures in the capillary tube were maintained higher than an equilibrium saturation pressure so as to prevent foaming in the tube and to realize single‐phase polymer/CO₂ solutions. By measuring the pressure drop and flow rate of polymer running through the tube, the melt viscosities were calculated. The experimental results indicated that the viscosity of LDPE/CO₂ solution was reduced to 30% of the neat polymer by dissolving CO₂ up to 5.0 wt% at temperature 150°C. A mathematical model was proposed to predict viscosity reduction owing to CO₂ dissolution. The model was developed by combining the Cross‐Carreau model with Doolittle's equation in terms of the free volume concept. With the Sanchez‐Lacombe equation of state and the solubility data measured by a magnetic suspension balance, the free volume fractions of LDPE/CO₂ solutions were calculated to accommodate the effects of temperature, pressure and CO₂ content. The developed model can successfully predict the viscosity of LDPE/CO₂ solutions from PVT data of the neat polymer and CO₂ solubility data.