Rheology of fiber filled polymer melts: Role of fiber‐fiber interactions and polymer‐fiber coupling

An experimental study and a numerical modeling analysis are carried out to examine the effects of fiber‐fiber interactions and coupling between fiber orientation and polymer chains conformation on the rheological properties of fiber suspensions. The experimental study allowed examination of large fiber volume fractions up to 35% over a range of shear rates that spans eight decades. This study confirmed already known results and led to new ones. In particular, a peak in the steady shear viscosity at the low shear rate region is observed at large volume fractions. Furthermore, new results regarding the applicability of the Cox‐Merz rule, the behavior of the damping factor, and the end pressure drops are reported, and physical interpretations are proposed. The results of the numerical modeling showed that it is necessary to account for the polymer‐fiber coupling factor to obtain a good fit between the model predictions and the experimental measurements. Comparisons between the model predictions and the experimental measurements allowed study of the variation of the parameters that govern the fiber‐fiber interactions and the polymer‐fiber coupling with the properties of the suspension and the flow. POLYM. ENG. SCI., 45:385–399, 2005. © 2005 Society of Plastics Engineers     

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.     

Shear and extensional rheology and flow‐induced orientation of carbon nanofiber/polystyrene melt composites

The rheological behavior and morphology of polystyrene/carbon nanofiber (PS/CNF) composites in their melt phase have been characterized through experimental measurements. Viscosity measurements of the PS/CNF composites in the linear viscoelastic regime show the ratio of the transient extensional viscosity to the transient shear viscosity to be greater than three, the Trouton ratio. This behavior is due to differences in the flow‐induced orientation of CNFs in shear and extensional flow. The orientation development of the CNFs in shear and extensional flow was analyzed through a method utilizing transmission electron microscopy and was used to explain observed rheological phenomena. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of shear‐thickening on the stability of slot‐die coating

Slot‐die coating is an economical roll‐to‐roll processing technique with potential to revolutionize the fabrication of nano‐patterned thin films at high throughput. In this study, the impact of shear‐thickening of the coating fluid on the stability of slot‐die coating was investigated. For the coating fluid, a model system fumed silica nanoparticles dispersed in polypropylene glycol was chosen. These dispersions exhibit shear and extensional thickening characterized through steady shear and capillary break‐up measurements. The critical web velocity for the onset of coating defect for different flow rates was measured, while the type of coating defect was visualized using a high speed camera. For the shear thickening particle dispersions, the coating failed through the onset of a ribbing instability. The critical web velocity for the onset of coating defect was found to decrease with increasing particle concentration and increasing fluid viscosity. The minimum wet thickness was studied as a function of capillary number for the particle dispersions and compared with a series of Newtonian fluids with similar viscosities. In all cases, shear‐thickening behavior was found to stabilize coating by reducing the minimum wet coating thickness when compared against a Newtonian fluid with similar viscosity at the same capillary number. Conversely, the shear‐thinning fluids tested destabilized the coating by increasing the minimum wet thickness when compared against a Newtonian at the same capillary number. The impact of shear‐thickening on slot‐die coating was further studied by quantifying the evolution of the ribbing instability with increasing web speed and by conducting tests over a wide range of coating gaps. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4536–4547, 2016     

Rheological behavior of noncompatibilized and compatibilized PP/PET blends with SEBS‐g‐MA

The rheological behaviors of noncompatibilized and compatibilized polypropylene/polyethylene terephthalate blends (80/20) in relation with their morphology were studied at two constant levels using maleic anhydride‐modified styrene‐ethylene‐butylene‐styrene polymer. By scanning electron microscopy of cryofractured surfaces, the morphology of the blends was examined after etching. The frequency sweep and step strain experiments were carried out for the blends. The frequency sweep results indicated that increasing the compatibilizer causes behavioral changes of the rheological properties, which could be related to the aggregation of the dispersed particles with rubbery shell. Also, the frequency sweep and step strain experiments in linear region, after cessation of simple steady shear flow with various preshear rates (higher shear stress values than G′_p), were done on compatibilized blend. The results showed that the morphology characteristics, defined by the aggregation of the dispersed particles based on rheological experimental data, were destroyed and replaced by an alignment in the flow direction for present imposed shear rates. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheological Characterization of Metalized and Non‐Metalized Ethanol Gel Propellants

The gellation of metalized and non‐metalized ethanol with a methylcellulose gelling agent and its effect on the rheological properties (flow and dynamic study) of these gels is reported herein. The rheological study shows that increasing the shear rate reduces the apparent viscosity for a given yield stress (for a shear rate range of 1 to 12 s⁻¹) for both shear rate ranges (1 to 12 and 1 to 1000 s⁻¹) covered in present experiment. The gellant and metal particle concentrations significantly influence the gel apparent viscosity. Distinct changes in thixotropic behavior were observed, while decreasing the concentration of MC gellant and Al metal particles in the ethanol gels. The dynamic study showed that all of the linear viscoelastic regions (LVE) of the gel samples were independent of strain percentage (1 to 10). The G′ values depended on the frequency and exceeded the G′′ values, which indicated a gel‐like highly structured material. The tanδ values showed that all of the ethanol gels were elastic and weak physical gels with a high degree of cross‐linking.     

Effect of steady shear on the morphology of biodegradable poly(ϵ‐caprolactone)/polylactide blend

The biodegradable polymer blend containing 70/30 weight ratio of poly(ε‐caprolactone) (PCL) and polylactide (PLA) was prepared by means of melt mixing. The evolution of the “sea‐island” phase structure in the steady shear flow was studied using scanning electron microscope (SEM) and parallel‐plate rheometer. The results show that the morphological evolution induced by steady shear follows different mechanisms at various flow rates. The lower shear rates (Newtonian flow) promote coalescence of the discrete PLA droplets, whereas higher shear rates (non‐Newtonian flow) promote break‐up of the droplets. The dynamic rheological responses of PCL/PLA blend before and after steady preshear were then analyzed using emulsion model and Taylor equation. The results show that the evolution approaches of the morphology highly depend on changed level of the critical effective interfacial tension in the steady shear flow, which are further confirmed by the transient rheological measurements. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Melt‐rheological behavior of high‐solid cement‐in‐polymer dispersions

The rheological behavior of a series of poly(ethylene oxide) melts containing nonhydrated cement is investigated using stress‐sweep measurements. The influence of the polymer end‐group—diol, monomethyl ether, and dimethyl ether—, molecular weight, and the particle volume fraction is examined. The data suggests that monomethyl ethers adsorb with their single OH group head‐on on the cement surface, which reduces the interparticle friction and the viscosity, but mixtures based on monomethyl ethers exhibit shear‐thickening behavior. The diols cause the formation of hydrogen‐bonded particle networks leading to high viscosities, but these mixtures exhibit shear‐thinning behavior due to the collapse of the network upon shearing. On increasing the particle volume fraction, the samples feature a nonlinear increase in viscosity. Fitting these data indicated that the maximum particle volume fraction is close to the random packing density of spheres and decreases with decreasing shear stress. As coating for glass rovings, the mixtures match the reinforcing performance of solvent‐based systems despite lower cement content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and rheological studies on the molecular composition and structure of metallocene‐ and Ziegler–Natta‐catalyzed ethylene–α‐olefin copolymers

The relationship between the molecular structure and the thermal and rheological behaviors of metallocene‐ and Ziegler–Natta (ZN)‐catalyzed ethylene copolymers and high‐density polyethylenes was studied. Of special interest in this work were the differences and similarities of the metallocene‐catalyzed (homogeneous) polymers with conventional coordination‐catalyzed (heterogeneous) polyethylenes and low‐density polyethylenes. The short‐chain branching distribution was analyzed with stepwise crystallization by differential scanning calorimetry and by dynamic mechanical analysis. The metallocene copolymers exhibited much more effective comonomer incorporation in the chain than the ZN copolymers; they also exhibited narrower lamellar thickness distributions. Homogeneous, vanadium‐catalyzed ZN copolymers displayed a very similar comonomer incorporation to metallocene copolymers at the same density level. The small amplitude rheological measurements revealed the expected trend of increasing viscosity with weight‐average molecular weight and shear‐thinning tendency with polydispersity for the heterogeneous linear low‐density polyethylene and very‐low‐density polyethylene resins. The high activation energy values (34–53 kJ/mol) and elevated elasticity found for some of our experimental metallocene polymers suggest the presence of long‐chain branching in these polymers. This was also supported by the comparison of the relationship between low shear rate viscosity and molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1140–1156, 2002     

Flow behavior of polypropylenes with different molecular structures in a coat‐hanger die

An experimental investigation of the flow behavior of three polypropylene melts with different molecular structures during extrusion through a coat‐hanger die is presented. Two linear and one long‐chain branched material, rheologically characterized in shear and elongation, were investigated. Using laser–Doppler velocimeter measurements of the velocity profiles across the gap height were performed at five various locations along the die. The uniformity of the velocity distribution along the die has been assessed using the maximum velocities v₀ of the corresponding velocity profiles across the gap. The velocity distribution along the die changes with throughput and temperature. Regarding the rheological properties, it was found that the power‐law index of the viscosity as a function of shear rate has a decisive influence on the uniformity of flow but that the pronounced strain hardening in elongation typical of the long‐chain branched polypropylene is not reflected by the velocity distribution along the die. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Linear and nonlinear melt‐state viscoelastic properties of polypropylene/organoclay nanocomposites

Rheological behavior of polypropylene (PP)/organoclay nanocomposites varying in compatibilizer (PP‐g‐MA) and organoclay concentration was investigated. The samples were prepared by melt intercalation method in an internal mixer. The wide angle X‐ray diffraction patterns and results of rheological measurements showed that the compatibilizer had strong influence in increasing the interlayer spacing. The observed low frequency liquid‐like to solid‐like transition and apparent yield stress in simple shear flows, along with convergence of transient shear stress to nonzero values in stress relaxation after the cessation of flow experiments, were found to be consistent with formation of a physical network in quiescent conditions which could be easily ruptured with applying low shear rates. The values of stress overshoot strain in flow reversal experiments were independent of shear rate, organoclay, and compatibilizer content. From the results of frequency sweep experiments in different nonlinear strain amplitudes it was shown that extended Cox‐Merz analogy was valid in nonlinear dynamic deformations while the shear viscosity showed positive deviation from this analogy with higher deviations at lower shear rates. Results of storage modulus recovery and flow reversal experiments at different shear rates suggested that network structure is reformed with a much slower rate compared to the rotational relaxation of organoclay platelets. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

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,flow visualization and extrudate swell of NR compound by rotating‐die rheometer

An experimental apparatus coupled with a rotating die system was especially designed and manufactured to study the rheological properties, flow patterns and swelling behavior of natural rubber (NR) compound for different shear rates and die rotating speeds at a test temperature of 110°C, the results being compared with those by the static capillary die. It was found that NR compound used exhibited psuedoplastic non‐Newtonian behavior. The rotation of the capillary die could reduce the extrusion load. The wall shear stress for any given shear rates increased with increasing die rotating speed. The fluctuation of the entrance pressure drop increased with increasing die rotating speed. The flow pattern development in the rotating‐die rheometer was different from that observed in the static die. The flow patterns in the rotating die were clearly unstable and contained two flow components which included axial flow along the barrel and circumferential flow at the die entrance. The size and shape of the axial and circumferential flows were more dependent on the piston displacement. It was found that the swelling ratio of the NR compound decreased with increasing die rotating speed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Measurements of slip velocity and frictional heating in the capillary extrusion of linear‐low‐density polyethylene with a fluoropolymer processing aid

The slip velocity and frictional or slip heating of linear‐low density polyethylene with a fluoropolymer processing aid in capillary flow were measured by rheo‐particle image velocimetry and thermal imaging. The pure polymer did not show slip before the stick‐slip regime but exhibited strong slip when blended with the processing additive. However, for shear stresses beyond the stick‐slip regime, the pure polymer and the blend exhibited the same flow behavior with slip. The slip velocity increased with the shear stress at two different rates before and after the stick‐slip and the contribution of slip to the total flow rate exhibited a minimum. Significant rises in temperature were measured under slip and no slip conditions, being these much higher than the values predicted by the adiabatic flow assumption. Clear difference was made between viscous and frictional heating before the stick‐slip regime, even though they could not be distinguished from one another at higher stresses. Overall, in the presence of slip, frictional and viscous heating act synergistically producing higher temperature rises in the melt. Finally, in contrast to predictions by numerical simulations of viscous heating, measured velocity profiles did not evidence the heating effects in the shear stress range analyzed in this work. POLYM. ENG. SCI., 56:837–845, 2016. © 2016 Society of Plastics Engineers     

Percolation network formation in poly(4‐vinylpyridine)/aluminum nitride nanocomposites: Rheological,dielectric, and thermal investigations

This work is concerned with several issues related to the rheological behavior of poly(4‐vinylpyridine)/aluminum nitride (AlN) nanocomposites. The composites are prepared by solution processing combined with ultrasonication and magnetic stirring. To understand the percolated structure, the nanocomposites are characterized via a set of rheological, dielectric, and thermal conductivity analyses. The nanoparticle networks are sensitive to the steady shear deformation particularly at low shear rates, where a shear‐thinning domain is observed. The rheological measurements revealed also that the activation energy is significantly lower at high nanofiller loadings suggesting stronger AlN interactions. The changes in the terminal behavior of shear moduli are the result of variations in composite elasticity determined by the percolation network. The flocculation and percolation thresholds estimated from the rheological moduli dependence on AlN loading are correlated with the dielectric constant values. Thermal conductivity is determined from a new theoretical model involving, besides the contribution of each phase, both percolation processes and the shape of the nanofiller. POLYM. COMPOS., 35:1543–1552, 2014. © 2013 Society of Plastics Engineers     

Synthesis in inverse emulsion and properties of water‐soluble associating polymers

An inverse, free‐radical emulsion polymerization technique was designed for the preparation of copolymers of acrylamide and sodium acrylate modified with low amounts (<0.5 mol %) of a series of amphiphilic comonomers, the isooctylphenoxy–poly(oxyethylene)(n) methacrylates (1 ≤ n ≤ 12). The products of the reaction were hydrophobically modified water‐soluble polymers (HMWSPs) of high molecular weight encapsulated within water droplets dispersed in an organic medium. Kinetic studies showed that the full‐conversion samples were rather homogeneous in composition because of the specificity of the process. A mechanistic scheme is proposed that accounts for the incorporation level of the amphiphilic comonomer as a function of its hydrophile–lipophile balance and the nature of the redox initiator (hydrophilic or lipophilic). The rheological properties of the HMWSPs in aqueous solutions were investigated as a function of the comonomer content and the nature of the initiator with steady‐flow experiments. The thickening properties were directly correlated to the conditions of synthesis and were optimal when the initiator and the amphiphilic comonomer were located in two distinct phases. A maximum in viscosity was observed for a hydrophobe content of about 0.3 mol %. An examination of the viscosity as a function of the shear rate and time showed that these solutions had all the characteristics of associating polymers. The complex rheological behavior was the result of the balance between interchain and intrachain hydrophobic liaisons and the kinetics of disorganization and reorganization of the network structure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1418–1430, 2002; DOI 10.1002/app.10337     

Rheological characterization of cellulose solutions in N‐methyl morpholine N‐oxide monohydrate

Three different modes of rheological properties were measured on 11 and 13 wt % solutions of cellulose in N‐methyl morpholine N‐oxide (NMMO) monohydrate, in which concentration range lyocell fibers of much reduced fibrillation are preferably produced. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions. Both cellulose solutions showed a shear thinning behavior over the shear rate measured at 85, 95, 105, and 115°C. However, 13 wt % solution gave rise to yield behavior at 85ºC. The power law index ranged from 0.36 to 0.58. First normal stress difference (N₁) was increased with lowering temperature and with increasing concentration as expected. Plotting N₁ vs shear stress (τ_ω) gave almost a master curve independent of temperature and concentration, whose slope was about 0.93 for both cellulose solutions over the shear rate range observed (τ_ω > 500 Pa). In addition, the cellulose solutions gave high values of recoverable shear strain (S_R), ranging from 60 to 100. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 216–222, 2002     

Hybrid rheological model for non‐Newtonian turbulent pipe flow

Many slurry rheograms do not follow the Bingham model, but are curved (convex upwards) at low‐strain rates. Alternate models such as the yield‐power law (YPL), provide a good fit to the low‐strain rate data, but they tend to underestimate apparent viscosities at high‐strain rates. The current paper considers a hybrid rheological model consisting of a cubic‐spline fit to the low‐strain rate data merging into a Bingham linear model above a limiting strain rate. This model predicts turbulent flow well, depending only on the area difference between the Bingham rheogram and the cubic spline.     

On the non‐newtonian viscous behavior of polymer melts in terms of temperature and pressure‐dependent hole fraction

A new theoretical non‐Newtonian viscosity model is developed by taking the fractional series expansion of Eyring's shearing strain rate. A broad range of experimental rheological data of various polymer melts including polyethylenes, polypropylene, polystyrene, poly (methyl methacrylate), and polycarbonate are fitted well using the proposed model. From the model; zero shear, constant shear‐stress and constant shear‐rate viscosities are derived as a linear function of viscosity related quantity, Y_h, called “thermo‐occupancy function” and their coefficients are discussed in detail. The thermo‐occupancy function is expressed in terms of temperature and structural vacancies such as hole fraction computed from the Simha‐Somcynsky Hole Theory (SS). In addition, the derivative of the logarithm of viscosities with respect to the hole fraction, named as viscoholibility, is observed decreases with the increasing hole fraction. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40540.