Viscosity behavior and surface and interfacial activities of hydrophobically modified water‐soluble acrylamide/N‐phenyl acrylamide block copolymers

In this study, the viscosity behavior and surface and interfacial activities of associative water‐soluble polymers, which were prepared by an aqueous micellar copolymerization technique from acrylamide and small amounts of N‐phenyl acrylamide (1.5 and 5 mol %), were investigated under various conditions, including the polymer concentration, shear rate, temperature, and salinity. The copolymer solutions exhibited increased viscosity due to intermolecular hydrophobic associations, as the solution viscosity of the copolymers increased sharply with increasing polymer concentration, especially above a critical overlap concentration. An almost shear‐rate‐independent viscosity (Newtonian plateau) was also displayed at high shear rates, and typical non‐Newtonian shear‐thinning behavior was exhibited at low shear rates and high temperatures. Furthermore, the copolymers exhibited high air–water and oil–water interfacial activities, as the surface and interfacial tensions decreased with increasing polymer concentration and salinity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2290–2300, 2003     

Wetting kinetics of polymer solutions and force‐based contact angles

The effect of the shear thinning behavior and elasticity of polymer solutions on the dynamic contact angles are investigated. Under dynamic conditions, the contact angle of a liquid on a solid surface changes significantly with the substrate velocity from its equilibrium value. The dynamic contact angles for polyethylene oxide (PEO) solutions of two molecular weights 3 × 10⁵ and 4 × 10⁶ have been measured using a polyethylene terephthalate (PET) plate. The three‐parameter Ellis model to fit the rheological data to obtain shear thinning power n, characteristic shear stress, and the zero‐shear viscosity is used. The theory indicates that dynamic contact angles follow power law in this instance instead of showing Newtonian behavior with zero‐shear viscosity when the shear thinning effects are considered. The elastic effect becomes important at larger polymer concentrations that reduces the dependence on capillary number, that is, reduces n keeping with the experiments. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2533–2541, 2016     

Experimental investigations of non‐Newtonian/Newtonian liquid‐liquid flows in microchannels

The plug flow of a non‐Newtonian and a Newtonian liquid was experimentally investigated in a quartz microchannel (200‐µm internal diameter). Two aqueous glycerol solutions containing xanthan gum at 1000 and 2000 ppm were the non‐Newtonian fluids and 0.0046 Pa s silicone oil was the Newtonian phase forming the dispersed plugs. Two‐color particle image velocimetry was used to obtain the hydrodynamic characteristics and the velocity profiles in both phases under different fluid flow rates. The experimental results revealed that the increase in xanthan gum concentration produced longer, bullet‐shaped plugs, and increased the thickness of the film surrounding them. From the shear rate and viscosity profiles, it was found that the polymer solution was in the shear‐thinning region while the viscosity was higher in the middle of the channel compared to the region close to the wall. Circulation times in the aqueous phase increased with the concentration of xanthan gum. © 2017 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 63: 3599–3609, 2017     

Nonlinear rheological behavior of a novel oil displacing agent

In this work, the shear and elongational rheologies have been investigated for a newly developed oil displacing agent, polymeric surfactant‐PSf. It was found that the PSf solutions exhibited Newtonian, shear‐thinning, and shear‐thickening behavior, respectively, depending on the polymer concentration and shear rate, and Cox–Merz rule was not applicable to these systems. The first normal stress difference (N₁) versus shear rate plots for PSf were complicated, which varied with the composition of the solutions. The uniaxial elongation in capillary breakup experimental results indicated that Exponential model could be used to fit the experimental data of the PSf solutions at lower polymer concentrations. In addition, it was found that PSf was more effective in improving shear viscosity than partially hydrolyzed polyacrylamide, but not in the case of elongational viscosity. The experimental results indicated that the microstructural mechanisms are responsible for the rheological behavior of the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40813.     

The effect of surfactants on deformation of falling non‐Newtonian drops in a Newtonian liquid

Deformation of settling non‐Newtonian ellipsoidal drops in a Newtonian liquid was experimentally observed. Corn oil was used as the Newtonian phase and solutions of polyacrylamide in aqueous glycerine as the non‐Newtonian phase. The shear‐thinning behaviour of the drops fluid was controlled by the amount of polymer dissolved, while the effect of interfacial tension was examined using different concentrations of sodium dodecyl sulphate (SDS). In the range of 1 < E < 2.9, 0.2 < Eo, < 23, and 0 < Ma < 17.2, drop eccentricity increased linearly with a modified Eötvös number taking into account the effect of surfactants. For the range of experimental conditions tested, drop deformation was mainly controlled by viscous and interfacial tension forces, while shear‐thinning and inertia effects were negligible.     

Altering the viscosity of cationically modified cellulose polymers by the addition of salt

The concentration dependence of viscosity is examined for four cationically modified cellulose polymers (UCARE? JR400, UCARE? JR30M, UCARE? LR400, and UCARE? LR30M) in both salt‐free and 50 mM NaCl solution. Similarities in the four polymer systems include: Newtonian viscosity in the dilute regime, shear thinning at higher concentrations, four concentration regimes in salt‐free solution, and three concentration regimes in salt solution. The zero shear rate viscosity and the degree of shear thinning increase with increasing polymer concentration in both salt and salt‐free solutions. While the addition of salt to the lower molecular weight polymers JR400 and LR400 resulted in small changes in viscosity across all concentrations, JR30M and LR30M exhibited significant decreases (up to 81%) and increases (up to 57%) in viscosity upon the addition of salt in the semidilute and entangled regimes, respectively. This viscosity increase in the entangled regime (when comparing salt‐free and 50 mM NaCl solutions) is reported for the first time in cationically modified cellulose polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41616.     

Experimental and Numerical Analysis of the Viscous Fingering Instability of Shear‐Thinning Fluids

Miscible flow displacements in a rectilinear Hele‐Shaw cell of Newtonian as well as rheologically well‐characterized shear‐thinning fluids are examined through experimental measurements and numerical modelling. Water is used as a displacing fluid while the displaced fluid consists of either a reference Newtonian glycerol solution or shear‐thinning solutions of Alcoflood? polymers of different molecular weights. The experimental measurements revealed that the shear‐thinning behaviour of the non‐Newtonian solutions resulted in more complex instability patterns and new finger structures not previously observed in the case of Newtonian displacements are identified and characterized. An analysis of the effects of the rheological behaviour of the shear‐thinning fluids on instability characteristics such as the finger width and finger tip velocity is presented. Numerical simulations using a pseudo‐spectral method are conducted and allowed to compare the predictions of the mathematical model based on an effective Darcy's law with the experimental measurements.     

Pressure drop in a split‐and‐recombine caterpillar micromixer in case of newtonian and non‐newtonian fluids

Microreactors are very promising tools for the design of future chemical processes. For example, emulsions of very narrow size distribution are obtained at much lower energy consumption than the one spent with usual processes. Micromixers play thereby an eminent role. The goal of this study is to better understand the hydrodynamic properties of a split‐and‐recombine Caterpillar micromixer (CPMM) specially with regard to handling viscoelastic fluids, a topic hardly addressed so far in the context of micromixers in general, although industrial fluids like detergent, cosmetic, or food emulsions are non‐Newtonian. Friction factor was measured in a CPMM for both Newtonian and non‐Newtonian fluids. For Newtonian fluids, the friction factor in the laminar regime is f/2 = 24/Re. The laminar regime exists up to Reynolds numbers of 15. For shear‐thinning fluids like Carbopol 940 or viscoelastic fluids like Poly Acryl Amide (PAAm) aqueous solutions, the friction factor scales identically within statistical errors up to a generalized Reynolds number of 10 and 0.01, respectively. Above that limit, there is an excess pressure drop for the viscoelastic PAAm solution. This excess pressure drop multiplies the friction factor by more than a decade over a decade of Reynolds numbers. The origin of this excess pressure drop is the high elongational flow present in the Caterpillar static mixer applied to a highly viscoelastic fluid. This result can be extended to almost all static mixers, because their flows are generally highly elongational. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2679–2685, 2013     

Inkjet printing of polyvinyl alcohol multilayers for additive manufacturing applications

Here we demonstrate that inkjet printing technology is capable of producing polyvinyl alcohol (PVOH) multilayer structures. PVOH water‐based inks were formulated with the addition of additives such as humectant and pigments. The intrinsic properties of the inks, such as surface tension, rheological behavior, pH, wetting, and time stability were investigated. The ink's surface tension was in the range 30–40 mN/m. All formulated inks displayed a pseudoplastic (non‐Newtonian shear thinning and thixotropic) behavior at low‐shear rates and a Newtonian behavior at high‐shear rates; were neutral solutions (pH7) and demonstrated a good time stability. A proprietary 3D inkjet printing system was utilized to print polymer multilayer structures. The morphology, surface profile, and the thickness uniformity of inkjet printed multilayers were evaluated by optical microscopy and FT‐IR microscopy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43572.     

A theory of roll coating of viscous and viscoelastic fluids

A theory for roll coating of a fluid onto a moving sheet is developed utilizing the usual “lubrication approximations.” The effects of fluid and operating parameters on coating thickness and pressure distribution are determined for a Newtonian fluid, and for a purely viscous non-Newtonian fluid obeying the Power Law. The results for these cases are obtained analytically, and are rather straightforward. A viscoelastic fluid is considered, of a type which shows typical non-Newtonian shear behavior observed in polymer melts and solutions and which also exhibits normal stress behavior. Analytical solutions are not possible, but a perturbation method, using a viscoelastic perturbation parameter related to a Deborah number, yields an approximate solution. Only terms to first order in the perturbation parameter are given. Subject to that degree of approximation, the following conclusions are drawn:

• 1 Non-Newtonian shear behavior reduces the pressure distribution, and increases the coating thickness.
• 1 Elasticity of the type usually observed in polymer solutions makes only a minor contribution to the roll-separating (load-carrying) force. The contribution is positive, but smaller than the corresponding negative contribution due to the non-Newtonian shear effects.
• 1 An increase in load-carrying capacity would require a different viscoelastic fluid than the type considered here—one that is essentially Newtonian in shear but, independently, capable of developing significant normal stresses.

     

Shear Thinning Behavior of Calcium Silicate‐Based Mold Fluxes at 1623 K

There have been consistent efforts on understanding rheological behavior of molten mold flux, used in continuous casting of steels. It is prevalent view that molten mold flux shows non‐Newtonian behavior, meaning that the viscosity varies with shear rate history. Hence, the present study attempts to evaluate shear thinning, which is one of the characteristic non‐Newtonian behaviors, by measuring its viscosity with a rotating type viscometer at 1623 K. Furthermore, Raman spectroscopy analysis is used to appreciate the structure of molten mold flux and shear thinning. Mold fluxes tested reveal definite shear thinning characteristic of decreasing viscosity with increasing shear rate. The degree of shear thinning has been well quantified by Oswald‐De Waele power law model. Lastly, the degree of polymerization, obtained from Raman spectroscopic data has proportional relationship with degree of shear thinning in the range of 1–5 s^?1 shear rate. Also, it has a downward parabolic relationship with degree of shear thinning at entire shear rate ranges up to 100 s^?1. This study also verifies possibility to use shear thinning behavior on actual continuous casting process.     

Non‐newtonian rheological behavior of semi‐dilute ultra‐high molecular weight polyethylene solution in gel‐spinning process. 1: Concentration effect on the fundamental rheological properties

The rheological properties of a semi‐dilute ultra‐high molecular weight polyethylene (UHMw‐PE)/paraffin wax solution were investigated by mainly focusing on the influence of its concentration on the shear flow viscosity. It was found that the UHMw‐PE solution exhibits a shear‐thinning behavior at a very wide shear rate range from 10^?4 to higher than 10³ sec^?1. Furthermore, this typical non‐Newtonian behavior was more obvious with a concentration increase. From the concentration dependence of the zero‐shear creep compliance or other rheological factor, it was found that the extremely large M_e value of the system gives rise to various kinds of non‐Newtonian behaviors, especially those highly elastic in nature. Finally, the origin of the abnormal stress fluctuation during the steady shear measurement was found to be related to the shear‐induced structural development of the solution.     

Operating window of solution casting,part I: Newtonian fluids

An experimental study was carried out to investigate the fluid mechanics of solution casting. Newtonian glycerol solutions were used as test fluids and were casted on the polyethylene terephthalate films. The focus of this study is on the evaluation of the operating window, i.e., a region for stable and uniform processing. Different types of defects such as stable or unstable poolings, vibrating edges, and air entrainment outside the operating windows were observed. The effects of two different start‐up approaches on the operating window were studied. One of the key operating parameters is the maximum casting velocity V_max for stable operation. The fluid viscosity is the most critical parameter on V_max. It was found that if the gap between the slot die exit and the moving film substrate is smaller than 600 μm, V_max might go down and then go up as the fluid viscosity increases. On the other hand, if the gap is larger than 600 μm, V_max will decrease as the fluid viscosity increases. Competition of two different types of defects, i.e., unstable pooling and air entrainment, can decide V_max, as evidenced by the observation on the fluid motion and dynamic contact angles of different cases. The importance of different forces on V_max was also analyzed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparative studies of rheological properties of polyacrylamide and partially hydrolyzed polyacrylamide solutions

The present work is concerned with experimental results of rheological characteristics of polyacrylamide (PAM) and of partially hydrolyzed polyacrylamide (HPAM) (degree of hydrolysis up to 80%) in aqueous and aqueous/sodium chloride solutions with changing experimental conditions such as polymer concentration, temperature, solvent quality, and shear rate applied. It has been observed that the all‐aqueous and aqueous/NaCl solution of PAM and of HPAM exhibited the non‐Newtonian behavior with shear‐thinning and shear‐thickening areas. The onset of shear‐thickening at depends mainly on the degree of HPAM hydrolysis, as well as on solution concentration, temperature, solvent quality, and polymer molecular weight. Rheological parameters from power law (Ostwald de Waele model) and activation energy of viscous flow (E_a) are determined and discussed. The changes in apparent shear viscosity during aging of solutions of PAM and HPAM are also described. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2235–2241, 2007     

Rheological properties of new polymer compositions for sand consolidation and water shutoff in oil wells

The rheological properties of some newly developed polymer compositions have been investigated with and without crosslinking. These polymer compositions were developed as a water shutoff and sand consolidation treatment agents for producing oil and gas wells. The effects of several variables on the rheology of the compositions were evaluated over a wide range of temperatures (25–110°C), shear rates (0–500 s^?1), brine percentages (0–15%), crosslinker types and concentrations (0–3%), and polymer concentrations (6–50%). It was found that increasing the shear rate from 0 s^?1 to 100 s^?1 caused shear thinning and reduction of the viscosity of the dilute solutions (6–13%) from 25 cP to ～ 3 cP at 80°C. In contrast, for the concentrated solutions (20–50%), the viscosity dropped slightly in the shear rate range 0–10 s^?1, and subsequently decreased more slowly up to shear rates of 500 s^?1. The viscosities of all polymer solutions dropped by a factor of 2 as the brine concentration increased from 0% to 15%. Finally, aging time coupled with shear rates and higher percentages of crosslinkers accelerate the buildup of viscosity and gelation time of the polymer compositions. For concentrated solutions, shear rates ranging within 0–200 s^?1 accelerated gelation time from 9.75 h to 2–3 h, when they were sheared at 80°C. The polymeric solutions exhibited Newtonian, shear‐thinning (pseudo‐plastic), and shear‐thickening (dilatant) behavior, depending on the concentration, shear rate, and other constituents. In most cases, the rheological behavior could be described by the power law. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

The viscoelastic behavior of concentrated polyacrylonitrile/1‐butyl‐3‐methylimidazolium chloride from solution to gel

The viscoelastic behavior of concentrated polyacrylonitrile (PAN) /1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) solutions at different concentrations and temperatures has been investigated by rheology. For concentrated polymer solutions at low temperature (40°C), the shear viscosity was found to show a raid decrease from the ending of Newtonian plateau. At relatively high shear rate or frequency for the concentrated PAN/[BMIM]Cl solutions, the deviation from the empirical Cox–Merz rule was quite evident, which suggested the formation of heterogeneous structures within these solutions. However, the dependence of G′ and G″ on angular frequency presented approximate linearity with similar slope at some temperatures between 100°C and 20°C. All the results lead us to the fact that the gelation has occurred within the concentrated solutions during cooling and the process was found to be thermoreversible. The gelation temperatures of the solutions have exhibited strong concentration dependence. It may be suggested that the microphase separation may be the major reason for the gelation of the concentrated PAN/[BMIM]Cl solutions during cooling process. POLYM. ENG. SCI., 54:598–606, 2014. © 2013 Society of Plastics Engineers     

Rheological behaviour of some amphiphilic β‐cyclodextrin‐based azo aromatic polyurethanes in N,N‐dimethylformamide solutions

Amphiphilic β‐cyclodextrin‐based azo aromatic poly(ether urethane)s with different soft segment lengths have been synthesized and characterized. Hydrogen bonding in these systems was demonstrated by Fourier transform infrared spectroscopy analysis (carbonyl stretching region). A rheological study was performed on solutions of the synthesized poly(ether urethane)s in N,N‐dimethylformamide at various concentrations and temperatures by employing parallel plate geometry, and a comparative evaluation of the influence of the structural components on the viscometric responses was performed. The rheological behaviour was found to be strongly dependent on the chemical composition of the synthesized polyurethanes which promotes self‐assembly and structuring in solution. Hard segment content and polymer concentration influence pseudoplastic shear‐thinning flow behaviour. The rheology can be interpreted in terms of hydrophobic associations and chain entanglements and a hydrogen bonding network occurring in solution. The start‐up flow of the polymer solutions is determined by the lifetime of the associative polymer segments. Shear stress plateaux indicative of ‘shear banding’ behaviour explained by the structuring of the polymer solutions at increased temperatures were obtained. The studied amphiphilic polyurethane solutions are thermoresponsive systems exhibiting viscosity increase with increasing temperature contrary to the usual Arrhenius thermo‐thinning behaviour. At constant shear rate viscosity was found to increase with increasing temperature due to thermo‐association. © 2014 Society of Chemical Industry     

Stability of Newtonian-PTT coextrusion fiber spinning

Linear stability analysis has been applied to a coextrusion fiber spinning flow that consists of a Newtonian fluid as a core layer and a Phan-Thien/Tanner (PTT) fluid as a skin layer. These two chosen fluids show entirely different rheological behaviors. The stability of this coextrusion system was affected by the choice of three characteristic parameters: the skin layer fraction (f), the extensional parameter (ϵ), and the shear thinning parameter (ξ) in the Phan-Thien/Tanner model. The linear stability results indicate that the viscoelastic skin layer (PTT fluid) has a stabilizing effect that delays the onset of draw resonance. Under fixed compositions (f is fixed), the stability envelopes changed from upturned curves to flattened ones as extensional force dominated the system. The neutral stable curves closed to the horizontal line at a critical draw ratio of around 20, showing similar behavior to a Newtonian fluid where the system has a very high Deborah number or it is dominated by shear thinning effects.     

Solution properties of ionic hydrophobically associating polyacrylamide with an arylalkyl group

Copolymers of acrylamide, 2‐acrylamide‐2‐methylpropanesulfate (AMPS), and hydrophobic monomer N‐arylalkylacrylamide (BAAM) were synthesized by free‐radical micellar copolymerization. The effects of the copolymer, BAAM, AMPS, and NaCl concentrations and the pH value on the apparent viscosity of the copolymers were studied. The solution viscosities increased sharply when the copolymer concentration was higher than the critical associating concentration. The apparent viscosities of aqueous solutions of poly(N‐arylalkylacrylamide‐co‐acrylamide‐co‐2‐acrylamide‐2‐methylpropanesulfate) (PBAMS) increased with increasing BAAM and AMPS concentrations. PBAMS exhibited good salt resistance. With increasing pH, the apparent viscosities first increased and then decreased. Dilute PBAMS solutions exhibited Newtonian behavior, whereas semidilute aqueous and salt solutions exhibited shear‐thickening behavior at a lower shear rate and pseudoplastic behavior at a higher rate. Upon the removal of shear, the aqueous solution viscosities recovered and became even greater than the original viscosity, but the salt solution viscosities could not recover instantaneously. The elastic properties of PBAMS solutions were more dominant than the viscous properties, and this suggested a significant buildup of a network structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 316–321, 2005     

Viscoelastic sol–gel state of the chitosan and alginate solution mixture

The rheological behavior of chitosan/alginate solutions was investigated in relation to gelation and polyelectrolyte complex (PEC) formation. Before mixing, the chitosan and the alginate solutions were both homogeneous fluids. However, heterogeneity developed after mixing, accompanied by a serious increase of viscosity. To determine the sol–gel state of the solutions, the viscoelastic variables, such as the dynamic storage modulus (G′) and loss modulus (G″), the loss tangent, and the viscoelastic exponents for G′ and G″, were obtained. Depending on the concentration, the chitosan/alginate solutions revealed unexpected rheological behavior. At a polymer concentration of 1.0 wt %, the chitosan/alginate solution was in a viscoelastic gel state, whereas, at higher concentrations, viscoelastic sol properties were dominant. A viscoelastic gel state for the chitosan/alginate solution was induced based on the weak formation of fiber‐shaped precipitates of a PEC at a low polymer concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1408–1414, 2007