Rheology and microstructures formation of immiscible model polymer blends under steady state and transient flows

Viscoelastic properties of model immiscible blend were studied here under steady state condition at different initial conditions and transient flow conditions. The flow‐induced microstructure has been studied on these model blends. For this system, the elastic properties of the blend are mainly governed by the interface. Measurement of the dynamic modulus and of the first normal stress difference, both reflecting this enhanced elasticity, have been used to prove the blend morphology. The dynamic moduli after cessation of shear flow, the mean diameter of the disperse phase as generated by the shear flow, have been calculated using the model of Palierne. A procedure based on a direct fitting of the dynamic moduli with the model is compared with the one that uses a weight relaxation spectrum. On the other hand, the steady state normal stress data have been related to the morphology of the blend by means of Doi and Ohta model. The specific interfacial area is found to be inversely proportional to the ratio of interfacial tension over shear stress for the blend. The flow behavior during transient shear flow was also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3519–3533, 2005     

Viscoelastic behavior of epoxy prepolymer/organophilic montmorillonite dispersions

Dispersions of a bisphenol A‐based epoxy resin with an organophilic montmorillonite (Nanofil 919) were studied by X‐ray diffraction and oscillatory shear rheometry. X‐ray studies reveal that the clay is intercalated by the epoxy and forms stable dispersions. The viscoelastic behavior of the nanodispersions was measured as a function of the Nanofil concentration and temperature. An increase in both G′ and G″ moduli was detected as the concentration increases. Furthermore, a transition from a liquid‐like behavior, at low temperatures, to a solid‐like behavior, at higher temperatures, was observed for all the samples. This transition is accounted for the formation of a percolated structure of interconnected tactoids through hydrophobic interactions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1837–1844, 2008     

Modeling the mechanical properties of highly oriented polymer films: A fiber/gel composite theory approach

Controlling the extent of orientation is of great interest in polymer processing and is effected by the choice of polymer, the fabrication technique and the processing conditions. Understanding the crystalline transitions that form highly oriented fibrils is necessary for modeling the changes in physical properties, relative to degree of orientation. A model is proposed to describe the mechanical properties of drawn semicrystalline polymer films based on structural transitions. With a minimal amount of experimental data (requiring testing on only two drawn films samples), this model can be used to predict film properties. These properties include the critical and maximum draw ratios, the moduli at the maximum draw ratio, the moduli of the fiber, the modulus of the nonfibrous gel relative to draw ratio, the volume fraction of fibers, and the rate of fibrillation. Where high degrees of uniaxial orientation are required, the polymer is typically drawn in the solid state, meaning the polymer is stretched in a single direction at temperatures below the melting point. During this process, pre‐existing crystallites are transformed into fiber‐like structures with large aspect ratios. The presence of these rigid asymmetric structures significantly enhances the moduli and break strength of the polymer. This work presents a model that describes the formation of fiber‐like structures. The volume fraction of fibers is predicted to be linear in draw ratio. The derived relationship between volume fraction of fibers and draw ratio can then be used for the prediction of the various properties of the oriented film. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 607–618, 2008     

Unexpectedly high young's moduli recorded for iPP/HDPE blends

Young's moduli of a series of quenched isotactic polypropylene/high‐density polyethylene blends were measured. The moduli of many of the blends exceeded the upper bound, calculated from the parallel model with the moduli of the two quenched homopolymers as those of the two components. In fact, both components crystallized at higher temperatures in the blends than they did on their own. It is argued that the higher crystallization temperatures of the components lead to higher component moduli and that this can explain the observation that the measured moduli of the blends apparently exceeded the upper bound. The implications of this work are discussed in light of other studies concerning the measurement and calculation of blend moduli. © 2001 John Wiley & Sons, Inc. J Polym Sci B Part B: Polym Phys 39: 1404–1414, 2001     

Melt rheology of polylactide/montmorillonite nanocomposites

In this article, the linear and nonlinear shear rheological behaviors of polylactide (PLA)/clay (organophilic‐montmorillonite) nanocomposites (PLACNs) were investigated by an Advanced Rheology Expanded System rheometer. The nanocomposites were prepared by master batch method using a twin‐screw extruder with poly(ε‐caprolactone) (PCL) as a compatibilizer. The presence of org‐MMT leads to obvious pseudo‐solid‐like behaviors of nanocomposite melts. The behaviors caused by the formation of a “percolating network” derived from the reciprocity among the strong related sheet particles. Therefore, the storage moduli, loss moduli, and dynamic viscosities of PLACNs show a monotonic increase with MMT content. Nonterminal behaviors exists in PLACNs nanocomposites. Besides the PLACNs melts show a greater shear thinning tendency than pure PLA melt because of the preferential orientation of the MMT layers. Therefore, PLACNs have higher moduli but better processibility compared with pure PLA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3189–3196, 2007     

Model filled rubber. II. Particle composition dependence of suspension rheology

Monodisperse size colloidal particles varying in chemical composition were synthesized by emulsifier‐free emulsion polymerization. Using a stress‐controlled rheometer, the rheological behavior of colloidal suspensions in a low molecular weight liquid polysulfide was investigated. All suspensions exhibited shear thinning behavior. The shear viscosity, dynamic moduli, and yield stress increased as interactions between particles and matrix increased. The rheological properties associated with network buildup in the suspensions were sensitively monitored by a kinetic recovery experiment. We propose that interfacial interactions by polar and hydrogen bonding between particles and matrix strongly promote affinity of matrix polymer to the filler particles, resulting in adsorption or entanglement of polymer chains on the filler surface. A network structure was formed consisting of particles with an immobilized polymer layer on the particle surface with each particle floc acting as a temporary physical crosslinking site. As the interfacial interaction increases, the adsorbed layer thickness on the filler particles, hence, the effective particle volume fraction, increases. As a result, the rheological properties were enhanced in the order PS < PMMA < PSVP. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 815–824, 1999     

Rheological and thermal properties of agarose aqueous solutions and hydrogels

In this article, we report on the rheological properties of agarose aqueous solutions and gels. Viscosity curves were determined for homogeneous agarose aqueous solutions at different temperatures (from 68 to 38 °C) to study the viscosity behavior as the systems undergo gelation. The gelation phenomenon of agarose solutions was also investigated by shear oscillation experiments and differential scanning calorimetry. The gelation and melting temperature as a function of agarose concentration were determined together with the gelation and melting enthalpies. The results obtained were interpreted using the two‐step model describing the gelation of agarose in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 322–328, 2008     

Rheological study of transient networks with junctions of limited multiplicity. II. Sol/gel transition and rheology

Viscoelastic and thermodynamic properties of transient gels formed by telechelic associating polymers are studied on the basis of the transient network theory that considers the correlation among polymer chains via network junctions. The global information of the gel is incorporated into the theory by introducing elastically effective chains defined according to the criterion of Scanlan [J. Polym. Sci. 43, 501 (1960)] and Case [J. Polym. Sci. 45, 397 (1960)]. We also consider the effects of superbridges whose backbone is formed by several chains connected in series and containing several breakable junctions. The dynamic shear moduli of this system are well described in terms of the Maxwell model characterized by a single relaxation time and high-frequency plateau modulus. Near the critical concentration at the sol/gel transition, superbridges become infinitely long along the backbone, thereby leading to a short relaxation time tau for the network. It is shown that tau is proportional to the concentration deviation Delta near the gelation point. The plateau modulus G(infinity) increases as the cube of Delta near the gelation point as a result of the mean-field treatment, and hence the zero-shear viscosity increases as eta(0) approximately G(infinity)tau approximately Delta(4). The present model can explain the concentration dependence of the dynamic moduli observed for aqueous solutions of telechelic poly(ethylene oxide).     

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) blend

The effect of phase‐separated morphology on the rheological properties of polystyrene/poly(vinyl methyl ether) (PS/PVME) blend was investigated by optical microscopy (OM), light scattering (LS) method, and rheology. The blend had a lower critical solution temperature (LCST) of 112°C obtained by turbidity experiment using LS at a heating rate of 1°C/h. Three different blend compositions (critical 30/70 PS/PVME by weight) and two off‐critical (50/50 and 10/90)) were prepared. The rheological properties of each composition were monitored with phase‐separation time after a temperature jump from a homogeneous state to the preset phase‐separation temperature. For the 30/70 and 50/50 blends, it was found that with phase‐separation time, the storage and loss moduli (G′ and G″) increased at shorter times due to the formation of co‐continuous structures resulting from spinodal decomposition. Under small oscillatory shearing, shear moduli gradually decreased with time at longer phase‐separation times due to the alignment of co‐continuous structures toward the flow direction, as verified by scanning electron microscopy. However, for the 10/90 PS/PVME blend, the rheological properties did not change with phase‐separation times. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 889–906, 1999     

Rheological studies of the interactions in cellulose/ethylene diamine/salt systems

Degree of polymerization (DP) of cellulose was measured to confirm that aging time and salt concentration did not cause cellulose degradation. Dynamic rheological studies of cellulose solutions were carried out to probe the evolving interactions between cellulose and ethylene diamine (EDA)/salt solvent system. Potassium thiocyanate (KSCN) was used as the salt in these studies. Steady shear studies indicated that all solutions exhibited shear‐thinning behavior. The empirical Cox‐Merz rule did not hold true for the cellulose system with weak gel microstructure. The shear viscosities at the shear rates explored decreased with aging time. The zero‐shear viscosity, however, increased with increasing salt concentration. Oscillatory shear studies were investigated and the time temperature superposition (TTS) method was used to extend the experimental frequency range of the instrument. The results showed that the average relaxation time of the cellulose system decreased as the sample aged and increased with increasing salt concentration, indicative of dynamic interactions between cellulose and the solvent system in solution. The conformations of cellulose chains were constantly changing over time. The system gelled when the salt concentration was increased to a critical point. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2326–2334, 2008     

The effect of interfacial viscosity on the droplet dynamics under flow field

The effects of interfacial viscosity on the droplet dynamics in simple shear flow and planar hyperbolic flow are investigated by numerical simulation with diffuse interface model. The change of interfacial viscosity results in an apparent slip of interfacial velocity. Interfacial viscosity has been found to have different influence on droplet deformation and coalescence. Smaller interfacial viscosity can stabilize droplet shape in flow field, while larger interfacial viscosity will increase droplet deformation, or even make droplet breakup faster. Different behavior is found in droplet coalescence, where smaller interfacial viscosity speeds up film drainage and droplet coalescence, but larger interfacial viscosity postpones the film drainage process. This is due to the change of film shape from flat‐like for smaller interfacial viscosity to dimple‐like for larger interfacial viscosity. The film drainage time still scales as Ca⁰ at smaller capillary number (Ca), and Ca^1.5 at higher capillary number when the interfacial viscosity changes. The interfacial viscosity only affects the transition between these limiting scaling relationships. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1505–1514, 2008     

Morphology evolution of nanocomposites based on poly(phenylene sulfide)/poly(butylene terephthalate) blend

Poly(phenylene sulfide) (PPS)/poly(butylene terephthalate) (PBT) (60/40 w/w) blend nanocomposites (PPS/PBTs) were prepared by direct melt compounding of PPS, PBT, and organoclay. The morphology and rheology of PPS/PBTs were investigated using scanning electron microscope and transmission electron microscope as well as parallel plate rheometer. The intercalated clay tactoids are selectively located in the continuous PBT phase due to their nice affinity. A novel morphology evolution of the immiscible blend matrices is observed with increase of clay loadings. Small addition of clay increases the discrete PPS spherulite domain size. With increasing loading levels, the PPS phase transform to the fibrous structure and finally, to the partial laminar structure at the high loading levels, in which shows a characteristic of large‐scaled phase separation. The presence of clay, however, does not impede the coalescence of the PPS phase because the phase size increases with increasing clay loadings. The elasticity and blend ratio of two matrices are proposed as the important roles on the morphological evolution. Moreover, the laminar structure of PPS phase is very sensitive to the steady shear flow and is easy to be broken down to spherulite droplet at the low shear rate. However, high shear level is likely to facilitate the coalescence of those PPS phase and finally to phase inversion, both contributing to increases of the dynamic modulus after steady shear flow. In conclusion, the morphology of the immiscible polymer blend nanocomposites depends strongly on both the clay loadings and shear history. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1265–1279, 2008     

Investigating time–temperature superpositioning in crosslinked polymers using the tube‐junction model

This article examines the application of time–temperature superpositioning (TTS) in certain thermorheologically complex polymers using a recently developed phenomenological model that describes crosslinked polymer viscoelasticity based on fundamental physical considerations. The model's capability to calculate both isochronal temperature sweeps and isothermal frequency sweeps of storage and loss moduli allows us to simulate conditions typical of certain thermorheologically complex polymers. We use the model to generate modulus frequency sweeps over the limited range of frequencies that are typically accessible to experiments. We apply TTS to shift these sweeps along the frequency axis to construct master curves. The model master curves are then compared with the model's “true” moduli curves over the full frequency domain at the reference temperature. This comparison suggests that nonsuperposability may go unnoticed if we only rely on the smoothness of the storage modulus master curve. Superpositioning to achieve a smooth loss modulus master curve tends to be more reliable. This has serious implications for assessing the reliability of relaxation moduli and creep compliance master curves that have no associated loss component that can be used to assess the quality of superpositioning. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 127–142, 1999     

Brownian dynamics simulation of two‐dimensional nanosheets under biaxial extensional flow

The morphology dynamics of two‐dimensional nanosheets under extensional flow are investigated using a coarse‐grained model. Nanosheets (graphene, BNNS, MX₂) are promising materials for a variety of materials and electronics applications. Extensional flow fields are often present during dispersion processing, such as spin coating. Both nanosheet properties (e.g., moduli, size) and processing parameters (e.g., extension rate) can have a significant impact on the nanosheet morphology and thus, the structure and properties of the bulk material. Our previously developed dimensionless Brownian dynamics methodology is used to explore biaxial extensional flow. Nanosheets exhibit a flat conformation under extensional flow for high bending moduli and an extended “washrag” conformation for low bending moduli. Intrinsic extensional viscosity increases with strain before reaching a plateau. The intrinsic viscosity exhibits a weak power law with nanosheet molecular weight. These simulation results allow for experimental control over morphology as a function of nanosheet properties and flow type and strength. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1247–1253     

Melt rheology of polypropylene containing small amounts of high molecular weight chain. I. Shear flow

Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of high molecular weight polyethylene (PE) into PP. The viscoelastic properties of the high‐melt‐strength PP melts under shear flow were investigated. It was found that the rheological properties of the high‐melt‐strength PP were distinctly different from those of conventional PP. The elastic response at low frequencies was significantly enhanced in comparison with the conventional PP, implying a presence of a long relaxation time mode that was not revealed in conventional PP. In step‐shear measurements, the fast and slow relaxation processes that characterized the linear viscoelastic properties were observed also for nonlinear relaxation moduli. The dependence of the damping for the slow process of the high‐melt‐strength PP on shear strain was much weaker than that of the fast process. These rheological behaviors characterizing the long relaxation time mode were further enhanced with the increasing concentration of high molecular mass PE. The unusual shear rheological behaviors were discussed in view of the role of high molecular weight PE as a long relaxation time mode within PP. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2692–2704, 2001     

Viscoelastic behavior of semicrystalline polymers at elevated temperatures on the basis of a two‐process model for stress relaxation

Viscoelastic behavior at elevated temperatures of high‐density polyethylene and isotactic polypropylene was investigated by using the stress relaxation method. The results are interpreted from the view of an established two‐process model for stress relaxation in semicrystalline polymers. This model is based on the assumption that the stress relaxation can be represented as a superposition of two thermally activated processes acting in parallel. Each process is associated either with the crystal or amorphous phase of a polymer sample. It was found that the temperature dependence of viscosity coefficients and elastic moduli of these two fractions are similar in the two materials. The experimental data was correlated with literature data of α and β processes in polyethylene and polypropylene obtained from dynamic mechanical thermal analysis. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3239–3246, 2000     

Shear‐induced clay dispersion in HDPE/PEgMA/organoclay composites as studied via real‐time rheological method

In current study, a real‐time rheological method was used to investigate the intercalation and exfoliation process of clay in high‐density polyethylene/organoclay (HDPE/OMMT) nanocomposites using maleic anhydride grafted polyethylene (PEgMA) as compatibilizer. To do this, a steady shear was applied to the original nonintercalated or slightly intercalated composites prepared via simple mixing. The moduli of the composites were recorded as a function of time. The effect of matrix molecular weight and the content of compatibilizer on the modulus were studied. The role of the compatibilizer is to enhance the interaction between OMMT and polymer matrix, which facilitates the dispersion, intercalation, and exfoliation of OMMT. The matrix molecular weight determines the melt viscosity and affects the shear stress applied to OMMT platelets. Based on the experimental results, different exfoliation processes of OMMT in composites with different matrix molecular weight were demonstrated. The slippage of OMMT layers is suggested in low‐molecular weight matrix, whereas a gradual intercalation process under shear is suggested in high‐molecular weight matrix. Current study demonstrates that real‐time rheological measurement is an effective way to investigate the dispersion, intercalation, and exfoliation of OMMT as well as the structural change of the matrix. Moreover, it also provides a deep understanding for the role of polymer matrix and compatibilizer in the clay intercalation process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 302–312, 2010     

Mechanical properties of polymers containing fillers

The addition of fillers can significantly change the mechanical characteristics of a material. In this paper, a general, mechanistic model is established to determine the moduli, relaxation moduli, break strengths, and break strains for polymer films containing liquid and solid micro fillers. Based on rigorous continuum mechanics principles, this model considers the filler/filler interactions, incorporates the nonlinear synergistic effects of fillers, and provides accurate predictions in comparison with experimental data. The analytical model developed provides information that is not available or extremely difficult to obtain experimentally. The model can be applied to determine the filler/matrix adhesion and filler modulus using measured modulus of a filled polymer film (a filled polymer is a polymer containing fillers). It is found that the compression moduli of polymer films containing liquid fillers differ significantly from the tension moduli, especially when the volume fraction of the filler is high. The difference in compression and tension Young's moduli normalized by the tension Young's modulus is as high as 35%. The relative error in maximum pressure calculation during Hertzian contact caused by using the tension moduli is as high as 48%. The relaxation modulus of a filled polymer film is determined through inverse Laplace transforms of its composite modulus in the s‐space. For a filled polymer film containing liquid phase fillers, a closed form solution for its relaxation modulus has been obtained. It is found that the composite relaxation modulus of the filled polymer is proportional to the relaxation modulus of the matrix polymer multiplied by a factor related to the volume fraction of the liquid filler. The break strength of the filled polymer is found to be proportional to the break strength of the polymer matrix material multiplied by a power function of the modulus ratio of filled polymer to polymer matrix, R. The break strain of the filled polymer is proportional to the break strain of the polymer matrix multiplied by a power function of 1/R. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 155–172, 1999     

Self‐ and cross‐associations in two‐component mixed polymer gels

The gel properties of two‐component mixed polymer gels are investigated using a cascade model, which assumes that the gel network is formed via the self‐association of one of the two components and the cross‐association of the two components. The effects of the model parameters, such as the equilibrium constants and the functionalities for cross‐associations and self‐associations, on the composition dependence of the modulus and gel point curves are examined to elucidate the contribution of self‐associations to the gel network. The results show that the characteristics of self‐associations become pronounced when the equilibrium constant or the functionality for self‐associations is comparable to that for cross‐associations. The model is applied to analyze the critical gelling concentration data for xanthan/locust bean gum mixed gels, which shows significant self‐associations at high xanthan compositions. The resulting model curves agree well with the experimental data at all temperatures. The analysis of the temperature dependence of the best‐fit equilibrium constant yields values of enthalpy change that are consistent with previous findings. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 80–91, 2008     

Bulk and shear rheology of silica/polystyrene nanocomposite: Reinforcement and dynamics

Bulk and shear rheological studies were performed on a 10 wt % silica nanoparticle‐filled polystyrene nanocomposite. The limiting moduli in glassy and rubbery states are higher for the nanocomposite than for the neat polymer; the increase is consistent with hydrodynamic reinforcement and is slightly higher than the lower bound of the rule of mixtures prediction. All evidence indicates that the presence of nanoparticles does not significantly change the polymer dynamics associated with glass transition, except to increase the T_g by 3 K. Comparison of the bulk and shear retardation spectra suggests that the underlying mechanisms for both responses are similar at short times and that the long‐time chain modes available to the shear are not available to the bulk, consistent with Plazek's earlier findings. In addition, T ? T_g and TV^γ scaling, along with the findings of thermorheological complexity, are discussed. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 621–632