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     

Interfacial slip at the thermotropic liquid‐crystalline polymer/poly (ethylene naphthalate) interface

The unique rheological properties of a thermotropic liquid‐crystalline polymer (TLCP) were first studied. The thermal and shear history of the TLCP was found to play a critical role in its rheological properties. Crystallites were observed in the TLCP melt even above the melting temperature detected by differential scanning calorimetry. Because interfacial slip had long been suggested as an important reason for viscosity reduction in TLCP/thermoplastic blends, for the first time, interfacial slip at the TLCP/poly(ethylene naphthalate) (PEN) interface was investigated with an energy model. The model quantified the degree of interfacial slip at the TLCP/PEN interface by an energy factor. The calculated energy factors revealed a high degree of interfacial slip at the TLCP/PEN interface. It was proposed that the high rigidity of rodlike TLCP chains and their alignment parallel to the interface prevented mutual entanglements at the TLCP/PEN interface. The lack of mutual entanglements promoted the interfacial slip. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 302–315, 2004     

Equilibrium calculations of viscosity and thermal conductivity across a solid-liquid interface using boundary fluctuations

We calculate viscosity and thermal conductivity in systems of Lennard-Jones particles consisting of coexisting solid and liquid with different interface wetting properties using the recently developed equilibrium boundary fluctuation theory. We compare the slip length and equivalent liquid length obtained from these calculations with those obtained from nonequilibrium molecular dynamics. The equilibrium and nonequilibrium calculations of the slip length and the sum of the thermal equivalent lengths are in good agreement. We conclude that for both interfacial properties, the nonequilibrium simulations were probing the linear response. The significant dependence of the intrinsic equivalence length on the interfacial temperature difference used to generate the thermal gradient is explained as a consequence of the different thermodynamic states of the two interfaces.     

On the wall slip of polymer blends

The slip flow of the polypropylene (PP)/poly[ethylene‐co‐(vinyl acetate)] (EVA) system was studied in a capillary rheometer for shear rates of 40–1000 s^?1 at four temperatures. Three dies made of aluminum with a length/diameter (L/D) ratio of 15 and diameters of 1.59, 1.19, and 0.79 mm provided the flow data. Calculations of the slip velocity by the Mooney method showed power‐law behavior with the stress. Blends were prepared at various proportions of PP and EVA for observation of the variation of the slip velocity for different compositions and temperatures. Direct microscopic observations of the slip layer on extruded samples showed domains of the dispersed phase unevenly distributed between the slip layer and the core and provided estimates of the thickness of the layer adjacent to the capillary wall. Results showed that the viscosity in the slip layer was 10–100 times lower than that in the bulk for the same value of the shear stress. In terms of the extrapolation length, the development of the slip layer was the result of different disentanglement dynamics of the molecules in the slip layer in comparison with those in the bulk. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 303–316, 2002     

Rheological properties and interfacial slip of a multilayer structure under dynamic shear

Interfacial slip between polymer melt under steady shear has been studied using a simplified multilayer structure. In this investigation, interfacial slip under dynamic shear was studied by calculating the angular displacements of the multilayer structure and its component layers. On the basis of the angular displacements, a slip index was defined to quantify the degree of interfacial slip. A relationship governing the rheological behavior of the multilayer structure under slip and nonslip condition was established. These results were correlated with equations derived from consideration of energy equilibrium in the multilayer structure. Polymer multilayer structures of high‐density polyethylene/polystyrene and liquid crystal polymer(LCP)/poly ethylene naphthalate(PEN) were investigated. Of all the polymers investigated, large interfacial slip was found at LCP/PEN interface under dynamic shear. The high rigidity and alignment along the interface of LCP molecules was believed to prevent chain entanglement in the interfacial layer and therefore promote interfacial slip at the interface. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2683–2693, 2005     

Peeling of polydimethylsiloxane adhesives at low velocities: Cohesive failure

This work presents results obtained in 90‐degree peeling tests at low velocities in the case of Newtonian adhesives, when failure is cohesive. Peeling experiments are described and consider the influence of the thickness, viscosity, and surface tension of the adhesive, as well as the backing rigidity. A simple model, based on lubrication effects in thin films, is considered and compared with the measurements, when peeling is a two‐dimensional phenomenon. Furthermore, a criterion for predicting the transition between the two‐dimensional regime and the three‐dimensional regime at higher velocities is proposed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 145–157, 2005     

Mobility of permeable fractal agglomerates in slip regime

Hydrodynamic drag and mobility of fractal aggregates in the slip creeping flow regime are calculated. A theoretical continuum model of the gas slip flow past and within agglomerates is developed. It accounts for effects of flow rarefaction and porous fractal structure upon the molecular mean free path, apparent viscosity, and effective permeability of agglomerates. It is shown that flow rarefaction significantly diminishes the aggregates' drag to an extent that cannot be predicted by the Cunningham's drag correction factor. The developed model allows calculation the agglomerates' transport properties in a wide range of fractal dimensions. For low D(f) agglomerates the drag force agrees with the Friedlander's expression based on the Epstein's single sphere drag in the free molecular regime.     

The role of interfacial modifier in toughening of nylon 6 with a core‐shell toughener

The effects of nylon 6 matrix viscosity and a multifunctional epoxy interfacial modifier on the notched impact strength of the blends of nylon 6 with a maleic anhydride modified polyethylene‐octene elastomer/semi‐crystalline polyolefin blend (TPEg) were studied by means of morphological observation, and mechanical and rheological tests. Because the viscosity of the TPEg is much higher than that of nylon 6, an increase in the viscosity of nylon 6 reduces the viscosity mismatch between the dispersed phase and the matrix, and increases notched impact strength of the blends. Moreover, addition of 0.3 to 0.9 phr of the interfacial modifier leads to a finer dispersion of the TPEg and greatly improves the notched impact strength of the nylon 6/TPEg blends. This is because the multi‐epoxy interfacial modifier can react with nylon 6 and the maleated TPEg. The reaction with nylon 6 increases the viscosity of the matrix while the coupling reaction at the interface between nylon 6 and the maleated TPEg leads to better compatibilization. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2664–2672, 1999     

Local hydrodynamics of solvent near diffusing dendrimers: A test of the new Stokes–Einstein relation

We have reported a new Stokes–Einstein relation (SER) for size determination and tested it by different nanoparticles. We assumed that the breakdown for SER results from local increases in viscosity. Here we investigate hydrodynamics of solvent near dendrimers to further test generality of our new theory. We discuss simulations of dendrimers in comparison to nanoparticles, experimental data on dendrimers from literature, and our theory. Local viscosity and local diffusivity of solvent near dendrimers are estimated by persistence times and exchange times, respectively. We find that the local dynamics of solvent near dendrimers of low density stay almost the same as that of bulk solvent. While the motions of solvent particles slow down near dendrimers of high density. This is similar with changes in local dynamics of solvent near nanoparticles. According to the causes we proposed for the deviation of SER, this is consistent with our findings that the SER works for the dendrimers of low density, while it fails for the dendrimers of high density. The new SER is then tested to predict size of the dendrimers accurately. Taking this together with the results for the nanoparticles, we believe that the new theory is general. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1380–1392     

Effects of poly(N‐isopropylacrylamide) on the solution properties of hydrophobically modified acrylamide copolymer

The hydrophobic interaction between hydrophobically modified acrylamide copolymer (HMPAM) and poly(N‐isopropylacrylamide) (PNIPAM) in aqueous solutions was investigated. The results show that the solution properties of HMPAM are significantly influenced by the addition of PNIPAM. In dilute regime, the intrinsic viscosity of HMPAM in 0.025 wt % PNIPAM/0.1 M NaCl mixed solution is 17.52 dL g^?1, about 2 times 8.66 dL g^?1, that in 0.1 M NaCl solution, which is due to the attractive interaction between the hydrophobic parts of PNIPAM and HMPAM molecules. In semidilute regime, below the saturation concentration, the addition of PNIPAM can lead to both the apparent viscosity and the modulus of HMPAM solutions increasing, which is attributed to the number of aggregation junctions increasing, responsible for the increase of the contribution of the reversible network to the viscosity increase, the β value. In addition, a thermothickening behavior for the HMPAM/PNIPAM mixed solution is observed with increasing temperature over 15–30 °C, which is consistent with the large increase of the Huggins coefficient of HMPAM in the presence of PNIPAM from 1.95 to 7.59 as temperature increases from 25 to 30 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 709–715, 2005     

Phase behavior of the polybutadiene–polystyrene diblock copolymer with the addition of the nonselective solvent dichlorobenzene in temperature and pressure fields

Thermal composition fluctuations were measured in a polybutadiene–polystyrene diblock copolymer with small-angle neutron scattering as a function of the temperature, pressure, and solvent content. The solvent was dichlorobenzene. In particular, we determined the phase diagram, the Flory–Huggins parameter, and the Ginzburg parameter. The two latter parameters were determined in terms of a theory by Fredrickson and Helfand from the susceptibility at an elevated temperature in the disordered regime. These parameters showed an overall linear decrease with pressure and a minimum at a 10% solvent content. The ordering temperature could be sufficiently well described by the theory of concentrated solutions. These results were consistent with corresponding experiments on a polybutadiene–polystyrene blend, for which the compensation of the free volume was observed by the solvent molecules. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3179–3190, 2004     

Fluctuating Interfaces in Liquid Crystals

Summary: We review and compare recent work on the properties of fluctuating interfaces between isotropic and nematic liquid-crystalline phases. Molecular dynamics and Monte Carlo simulations have been carried out for systems of ellipsoids and hard rods with aspect ratio 15:1, and the fluctuation spectrum of interface positions (the capillary wave spectrum) has been analyzed. In addition, the capillary wave spectrum has been calculated analytically within the Landau-de Gennes theory. The theory predicts that the interfacial fluctuations can be described in terms of a wave vector dependent interfacial tension, which is anisotropic at small wavelengths (stiff director regime) and becomes isotropic at large wavelengths (flexible director regime). After determining the elastic constants in the nematic phase, theory and simulation can be compared quantitatively. We obtain good agreement for the stiff director regime. The crossover to the flexible director regime is expected at wavelengths of the order of several thousand particle diameters, which was not accessible to our simulations.     

Effect of the particle size distribution on the low shear viscosity of high‐solid‐content latexes

The production of high‐solid‐content, low‐viscosity latexes is an active field in both industry and academia. The viscosity of polymer dispersions has a clear dependence on the particle size distribution (PSD). An example is the rule of thumb that a bimodal PSD enables the reduction of the viscosity with respect to monomodal systems. Despite important progress in theoretical work, not much has been done to quantitatively predict the low shear viscosity of aqueous polymer dispersions as a function of the complex PSD. In this work, the capability of a low‐shear‐viscosity equation to quantitatively account for the influence of both the PSD and the physicochemical characteristics of the dispersions is experimentally assessed. An analysis, consistent with theoretical concepts, of the data with semiempirical correlations is proposed. Next, with values of the parameters of the viscosity equation obtained experimentally, the effect of a latex with a 70% solid content on the low shear viscosity is examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3936–3946, 2004     

Adhesive bonding of glassy polymer surfaces by an ultrathin layer of a semicrystalline polymer

To develop a greater understanding of interfacial interactions between a semicrystalline polymer and a glassy polymer, adhesion tests were performed on very thin layers of poly(ethylene oxide) (PEO) sandwiched between two layers of poly(tetramethyl bisphenol A polycarbonate) (TMPC). The tests were designed to provide intimate contact between the surfaces while they were heated above the melting point of the PEO and cooled back to room temperature. A contact mechanics approach, based on the Johnson, Kendall, and Roberts theory, was used to determine values of the energy release rate describing the energetic driving force for crack propagation within the interfacial region. The ability to measure crack propagation at large values of the energy release rate was limited by rupture of the silicone elastomer that was used to provide a sufficiently compliant matrix for the adhesion experiment. By cycling the tensile stress at relatively low loading levels, we were able to measure fatigue crack propagation at values of the energy release rate that did not result in failure of the elastomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3809–3821, 2004     

Erosion‐dependant continuity development in high viscosity ratio blends of very low interfacial tension

This work studies continuity development and cocontinuity in high viscosity ratio EPDM/PP blends. A very low interfacial tension (0.3 mN/m) between the blend components together with high viscosity ratios (11 and 17) result in a variety of unusual morphological features, including isolated nanometer diameter fibers, very large particles, partially coalesced particles, and numerous particles interconnected by fibers. This unique combination of morphologies leads the blend to a novel and stable cocontinuous structure of partially coalesced particles and particles interconnected by fibers. Compared with low to medium viscosity ratio EPDM/PP blends, these cocontinuous networks demonstrate early percolation thresholds, rapid continuity development, and attain cocontinuity at lower compositions of minor phase. The slow surface erosion of the high viscosity EPDM phase during melt blending is shown to be responsible for the generation of these unusual morphological structures. Typically the timescale for erosion phenomena are so small that they have defied study in the mixing environment itself and typical blend morphology studies almost always examine the final steady‐state morphology obtained after several minutes of mixing. The combination of very low interfacial tension and very high viscosity ratios of these EPDM/PP systems provide a unique opportunity to examine erosion phenomena persisting over longer time scales during melt mixing. We propose a new concentration‐dependant erosion mechanism that is based on particle collision–coalescence–separation dynamics. The proposed conceptual mechanism is shown to dramatically accelerate the erosion process and maintain cocontinuity over prolonged periods of mixing. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1919–1929, 2006     

Viscosity effects in cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates

The effect of bulk viscosity on the cobaloxime‐mediated catalytic chain‐transfer polymerization of methacrylates at 60 °C was investigated by both the addition of high molecular weight poly(methyl methacrylate) to methyl methacrylate polymerization and the dilution of benzyl methacrylate polymerization by toluene. The results indicate that the bulk viscosity is not directly linked to the chain‐transfer activity. The previously measured relationship between chain‐transfer‐rate coefficient and monomer viscosity therefore probably reflects changes at the molecular level. However, the results in this article do not necessarily disprove a diffusion‐controlled reaction rate because cobaloxime diffusion is expected to scale with the monomer friction coefficient rather than bulk viscosity. Considering the published data, to date we are not able to distinguish between a diffusion‐controlled reaction rate or a mechanism directly affected by the methacrylate substituent. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 782–792, 2002; DOI 10.1002/pola.10152     

Investigation of shear failure mechanisms of pressure‐sensitive adhesives

We report new experiments investigating the failure mechanisms in shear, of thin layers of acrylic pressure‐sensitive adhesives (PSA). We have developed a novel experimental device able to shear a soft adhesive layer confined between a rigid hemispherical lens and a rigid glass substrate. Using the resources of in situ contact visualization, the nonhomogeneous deformation of the layer and the shear failure processes were observed optically. Depending on the rheological properties of the adhesive, ratios of the contact radius over the layer thickness of 10–30 were achieved, mimicking well the contact conditions encountered in a thin adhesive layer within a joint. When the adhesive was weakly crosslinked, we observed a fluid‐like behavior and could measure a reasonable value for the viscosity of the PSA, implying that flow can occur in the layer and failure will occur by creep. On the other hand, for a more crosslinked adhesive, closer to what is used in applications, a stick‐slip peeling behavior was observed, which involves a coupling between peeling mechanisms at the leading edge of the contact and interfacial slippage. Such a process suggests a failure by fracture rather than by creep. Interestingly, the peeling mechanisms and the associated stress levels change significantly when the layer becomes as thin as 20 μm, implying a fracture process that is controlled by a critical energy release rate in shear G_IIc rather than by a critical shear stress causing failure of the interfacial bonds. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3316–3330, 2005     

Tunable nanopatterning by diblock copolymers in small confinements*

Here we study the effects of confinement on the self‐assembly of diblock copolymers. Specifically, we study the hexagonal cylindrical phase as it self‐assembles within a narrow confinement. We quantify the structural deformation of the cylindrical morphology that arises from the frustration that the narrow confinements exert on the system when the confinement width is incompatible with the lattice structure of the bulk mesophase. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3695–3700, 2004     

Interfacial tension in a lower critical solution temperature blend: Effect of temperature,blend composition,and deformation of the interphase

Interfacial tension is a very important material parameter in two‐phase polymer blends. It determines the morphology development during processing, which is crucial for the end‐use properties of the material. Although different techniques for interfacial tension measurement give comparable results for immiscible polymers, the determination of the interfacial tension in lower critical solution temperature blends is not straightforward. This is illustrated for poly(α‐methyl styrene acrylonitrile)/poly(methyl methacrylate)(PαMSAN/PMMA), a slightly incompatible polymer pair. Interfacial tension has been measured with three different techniques: small‐amplitude oscillatory shear, recovery after elongation, and elongation of a multilayer sample. The large differences in these results can be attributed to the fact that most experimental techniques determine an apparent value, rather than the thermodynamic equilibrium value, of the interfacial tension. The latter is only obtained if the measurement is performed under quiescent conditions on a system that is composed of the coexisting PαMSAN‐rich and PMMA‐rich phases. The apparent interfacial tension depends on the actual composition of the phases and on the deformation of the interface. An order of magnitude approximation for such effects has been derived from theoretical considerations. Finally, each of these apparent values can be of practical importance. If a blend is prepared by melt mixing of the pure polymers, a high apparent value of interfacial tension should be considered. If, however, a blend is prepared by phase separation of a homogeneous mixture, the thermodynamic value is important. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 679–690, 2002     

Hydrophilicity and the viscosity of interfacial water

We measure the viscosity of nanometer-thick water films at the interface with an amorphous silica surface. We obtain viscosity values from three different measurements: friction force in a water meniscus formed between an oxide-terminated W tip and the silica surface under ambient conditions; similar measurements for these interfaces under water; and the repulsive "drainage" force as the two surfaces approach at various speeds in water. In all three cases, we obtain effective viscosities that are approximately 10(6) times greater than that of bulk water for nanometer-scale interfacial separations. This enhanced viscosity is not observed when we degrade the hydrophilicity of the surface by terminating it with -H or -CH3. In view of recent results from other interfaces, we conclude that the criterion for the formation of a viscous interphase is the degree of hydrophilicity of the interfacial pair.