Stratified morphology of a polypropylene/elastomer blend following channel flow

A thermoplastic olefin blend consisting of isotactic polypropylene (PP) and an ethylene‐butene copolymer (EBR) impact modifier (25 wt % EBR) was subjected to a short, high‐shear pulse within the flow channel of a pressure‐driven microextruder following low‐shear channel filling from a reservoir of the melt. The resulting morphology was examined by laser scanning confocal fluorescence microscopy (LSCFM), with contrast provided by a fluorescent tracer in the EBR minor phase. Shear experiments were performed under isothermal conditions with a known wall shear stress for a specified duration, providing a well‐defined thermal and flow history. Low‐shear channel filling produces small droplets across the central region of the channel and large droplets, consistent with steady‐state shear, in the regions near the channel walls. After cooling the molten blend to a crystallization temperature of 153 °C, a brief interval (5 s ～ 1/2000 of the quiescent crystallization time) of high shear (wall shear stress: 0.1 MPa) induces rapid, highly oriented crystallization and a stratified morphology. Ex situ LSCFM reveals a “skin” at the channel walls (～70 μm) in which greatly elongated fiberlike droplets, oriented along the flow direction, are embedded in highly oriented crystalline PP. Further from the walls but directly beside the skin layers are surprising zones in which EBR domains show no deformation or orientation. Several zones of intermediate deformation and orientation at an angle to the flow direction are located closer to the center of the channel. At the center of the channel, EBR droplets are spherical, as expected for channel flow. The various strata are explained by the interplay of droplet deformation, breakup, and coalescence with the shear‐induced crystallization kinetics of the matrix. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2842–2859, 2002     

Studies on fracture behaviors of immiscible polypropylene/ethylene‐co‐vinyl acetate blends with multiwalled carbon nanotubes

Immiscible polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) blends with two different compositions, one (PP/EVA = 80/20) exhibits the typical sea‐island morphology and the other (PP/EVA = 60/40) exhibits the cocontinuous morphology, were prepared with different contents of f‐MWCNTs. The fracture behaviors, including notched Izod impact fracture and single‐edge notched tensile (SENT) fracture, were comparatively studied to establish the role of f‐MWCNTs in influencing the fracture toughness of PP/EVA blends. Our results showed that, for PP/EVA (80/20) system, f‐MWCNTs do not induce the fracture behavior change apparently. However, for PP/EVA (60/40) system, the fracture toughness of the blend increases dramatically with the increasing of f‐MWCNTs content. More severe plastic deformation accompanied by the fibrillar structure formation was observed during the SENT test. Furthermore, SENT test shows that the significant improvement in fracture toughness of PP/EVA (60/40) with f‐MWCNTs is contributed to the simultaneous enhancement of crack initiation energy and crack propagation energy, but largely dominated by crack propagation stage. Further results based on crystalline structures and morphologies of the blends showed that a so‐called dual‐network structure of EVA and f‐MWCNTs forms in cocontinuous PP/EVA blends, which is thought to be the main reason for the largely improved fracture toughness of the sample. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1331–1344, 2009     

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     

Effects of slip on the viscosity of polymer melts

We use existing scaling theories by de Gennes, Brochard, and Ajdari to calculate the apparent viscosity of multilayer blends with weakly entangled interfaces. The lowering of the apparent viscosity with respect to the bulk is a manifestation of interfacial slip. The theoretical predictions are compared with the recent experimental data of Zhao and Macosko. The theory is able to describe a continuous transition from a low-slip regime to a high-slip regime when the bulk rheology is still Newtonian, in agreement with experiments. However, the dependence of the apparent viscosity on the shear rate and layer thicknesses is much stronger than what is observed experimentally. The apparent viscosity is also calculated for dilute polymer emulsions. We modify a theory of Palierne, which is valid in the linear viscoelastic regime for the bulk, to include the effects of interfacial slip. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1888–1904, 2004     

Cavitation of polyethylene during extrusion processing instabilities

We present observations of cavitation that occur inside a capillary die during extrusion of polyethylene. This phenomenon was observed over the last 1.5 mm of the capillary tube immediately upstream of the exit. We observed spontaneous formation of voids near the wall that grew to a typical length and width of 150 μm, and then shrank and disappeared over a time frame of approximately 20 ms. From velocity measurements of these structures, we concluded that their width in the radial direction was smaller than in the axial and lateral directions, and they were near the wall. The shape of the cavities was highly irregular. We assessed the roles of extensional stress and shear stress at the exit region and concluded that they were not the direct cause of cavitation. Rather, cavitation occurs in conjunction with an upstream rupture of the polymer that occurs in the contraction region leading into the capillary tube (gross melt fracture). We argue that the exit region does, however, serve as the initiation point of the cavitation because of a combination of the reduced pressure and extensional stress. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2791–2799, 2002     

Migration of nanosilica particles in polymer blends

Hydrophilic pyrogenic silica melt mixed in immiscible polypropylene/poly (ethylene‐co‐vinyl acetate) (PP/EVA) blend was found to migrate from the PP matrix to the EVA dispersed domains and remained confined inside them. Surprisingly, it was shown than silica was also able to migrate from a dispersed PP phase to an EVA matrix but this transfer was slower and not complete. The same silica with a hydrophobic surface treatment moved and accumulated to the blend interface and in PP. The mechanisms from which this migration proceeds are discussed. Whereas self diffusion of the particles was shown to have almost no effect, shear induced movements and collisions with dispersed drops is believed to be the most efficient mechanism. The possible trapping of silica aggregates during droplet–droplet coalescence was impossible to observe but is thought to be a possible additional mechanism. No quantification on the relative importance of the latter phenomenon can be drawn at the moment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1976–1983, 2008     

Numerical Analysis of 3‐D Flow Past a Stationary Sphere with Slip Condition at Low and Moderate Reynolds Numbers

Computations are performed to determine the steady 3‐D viscous fluid flow forces acting on the stationary spherical suspended particle at low and moderate Reynolds numbers in the range of 0.1≤Re≤200. A slip is supposed on the boundary so that the slip velocity becomes proportional to the shear stress. This model possesses a single parameter to account for the slip coefficient λ (Pa.s/m), which is made dimensionless and is called Trostel number (Tr=λ a/μ). Decreasing slip, increases drag in all Reynolds limits, but slip has smaller effects on drag coefficient at lower Reynolds number regimes. Increasing slip at known Reynolds number causes to delay of flow separation and inflect point creation in velocity profiles. At full slip conditions, shear drag coefficient will be zero and radial drag coefficient reaches to its maximum values. Flow around of sphere at full‐slip condition is not equal to potential flow around a sphere. Present numerical results corresponding to full slip (Tr→0) are in complete accord with certain results of flow around of inviscid bubbles, and the results corresponding to no‐slip (Tr→∞) have excellent agreement with the results predicted by the no‐slip boundary condition.     

Ductile–brittle‐transition phenomenon in polypropylene/ethylene‐propylene‐diene rubber blends obtained by dynamic packing injection molding: A new understanding of the rubber‐toughening mechanism

For a more complete understanding of the toughening mechanism of polypropylene (PP)/ethylene‐propylene‐diene rubber (EPDM) blends, dynamic packing injection molding was used to control the phase morphology and rubber particle orientation in the matrix. The relative impact strength of the blends increased at low EPDM contents, and then a definite ductile–brittle (D–B) transition was observed when the EPDM content reached 25 wt %, at which point blends should fail in the ductile mode with conventional molding. Wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) were used to investigate the shear‐induced crystal structure, morphology, orientation, and phase separation of the blends. WAXD results showed that the observed D–B transition took place mainly for a constant crystal structure (α form). Also, no remarkable changes in the crystallinity and melting point of PP were observed by DSC. The highly oriented and elongated rubber particles were seen via SEM at high EPDM contents. Our results suggest that Wu's criterion is no longer valid when dispersed rubber particles are elongated and oriented. The possible fracture mechanism is discussed on the basis of the stress concentration in a filler‐dispersed matrix. It can be concluded that not only the interparticle distance but also the stress fields around individual particles play an important role in polymer toughening. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2086–2097, 2002     

Crystal and phase morphology of dynamic-packing-injection-molded high-density polyethylene/ethylene vinyl acetate blends

The effect of shear stress, provided by so-called dynamic-packing injection molding, on crystal morphology and phase behavior was investigated for high-density polyethylene (HDPE) in blends with ethylene vinyl acetate (EVA) of various viscosities and vinyl acetate (VA) contents, with the aid of differential scanning calorimetry, two-dimensional small-angle X-ray scattering (2D SAXS), and scanning electron microscopy (SEM). A shish-kebab pattern was found in the oriented zones of dynamic samples, and the ratio of shish to kebab increased as a function of the EVA content in the blends up to 20 wt %, regardless of the VA content. This showed that molecules of HDPE could easily be stretched to form a shish structure in the presence of EVA. Moreover, a large increase in the long spacing, characterized by 2D SAXS measurements, was achieved because of the presence of EVA. The SEM results showed an obvious decrease in the domain size of the EVA phase under the effect of shear stress. All these results suggested shear-induced mixing between HDPE and EVA, in that ethylene segments of EVA molecules could be forged in the shish structure during shear and the other fractions of EVA were located in the amorphous regions between the adjacent lamellae of HDPE. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1831–1840, 2004     

Effects of functionalized multiwalled carbon nanotubes on the morphologies and mechanical properties of PP/EVA blend

The maleic anhydride‐grafted multiwalled carbon nanotubes (MWCNTs‐g‐MA) have been introduced into polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) blend. To clearly describe the effects of MWCNTs‐g‐MA on the morphology and mechanical properties of PP/EVA blends, the selective distribution of MWCNTs‐g‐MA in the blends is realized through different sample preparation methods, namely, MWCNTs‐g‐MA disperse in EVA phase and MWCNTs‐g‐MA disperse in PP matrix. The results show that the distribution of MWCNTs‐g‐MA has an important effect on the final morphology of EVA and the crystallization structure of PP matrix. Compared with PP/EVA binary blend, distribution of MWCNTs‐g‐MA in PP matrix induces the aggregation of EVA phase at high EVA content and the decrease of spherulite diameters of PP matrix simultaneously. However, when MWCNTs‐g‐MA are dispersed in the EVA phase, they induce more homogeneous distribution of EVA, and the crystallization behavior of PP is slightly affected by MWCNTs‐g‐MA. The corresponding mechanical properties including impact strength and tensile strength are tested and analyzed in the work. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1481–1491, 2009     

Analysis of rheology and wall depletion of microfibrillated cellulose suspension using optical coherence tomography

A rheometric method based on velocity profiling by optical coherence tomography (OCT) was used in the analysis of rheological and boundary layer flow properties of a 0.5% microfibrillated cellulose (MFC) suspension. The suspension showed typical shear thinning behaviour of MFC in the interior part of the tube, but the measured shear viscosities followed interestingly two successive power laws with an identical flow index (exponent) and a different consistency index. This kind of viscous behaviour, which has not been reported earlier for MFC, is likely related to a sudden structural change of the suspension. The near-wall flow showed existence of a slip layer of 2–12 μm thickness depending on the flow rate. Both the velocity profile measurement and the amplitude data obtained with OCT indicated that the slip layer was related to a concentration gradient appearing near the tube wall. Close to the wall the fluid appeared nearly Newtonian with high shear rates, and the viscosity approached almost that of pure water with decreasing distance from the wall. The flow rates given by a simple model that included the measured yield stress, viscous behavior, and slip behavior, was found to give the measured flow rates with a good accuracy.     

The mechanism and a slip model for the initial plastic deformation of amorphous polyethylene under uniaxial tension

The mechanical behaviors of a polyethylene (PE) bulk consisting of amorphous molecular chains under uniaxial tension have been explored using molecular simulations. The stress–strain relationship and the plastic deformations of the PE bulk have been analyzed. Two deformation stages were found in the stress–strain curve, the elastic stage with a straight linear part of the curve and the plastic stage with a flat sawtooth‐like part. The Young's modulus calculated from the elastic part is in good agreement with experimental results. Some key parameters such as the energy variations in different terms reveal that the interchain slip should be chiefly responsible for the initial plastic deformations of amorphous PE under uniaxial tension. In order to address how this slip influences the plastic deformations, the mechanical details of a single chain have been elucidated when it was pulled out from two PE clusters consisting of regular and amorphous chains, respectively. The interchain slip, found as the basic movement style, is responsible for the movement of the stretched chain. Both the critical slip force and the critical slip length have been found in these two cases. For the straight chain pulled out from the cluster with regular chains, the critical slip force is about 1.81 nN and the critical slip length is about 40 polymerization degrees. While for the chain in the amorphous cluster, the critical force is about 0.86 nN and the critical length is almost the same. Based on the simulation results, a meso slip model has been deduced to explain the behaviors of the amorphous PE bulk under uniaxial tension. With reference to the slip model of single crystals and polycrystals a constitutive relation was obtained by considering the Young's modulus, the equivalent slip stress and the average orientation parameters of each chain. The comparison of the results from the constitutive relation and the simulations proves that this model does well in predicting the mechanical behaviors of amorphous PE under uniaxial tension in general. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 986–998     

Shear‐induced change of exfoliation and orientation in polypropylene/montmorillonite nanocomposites

For the improved dispersion of montmorillonite (MMT) in a polypropylene (PP) matrix, PP/MMT nanocomposites prepared via direct melt intercalation were further subjected to oscillating stress achieved by dynamic packing injection molding. The shear‐induced morphological changes were investigated with an Instron machine, wide‐angle X‐ray diffraction, scanning electron microscopy, and transmission electron microscopy. The original nanocomposites possessed a partly intercalated and partly exfoliated morphology. A transformation of the intercalated structure into an exfoliated structure occurred after shearing, and a more homogeneous dispersion of MMT in the PP matrix was obtained. However, the increase of the exfoliated structure was accompanied by the scarifying of the orientation of MMT layers along the shear direction. Some bended or curved MMT layers were found for the first time by TEM after shearing. However, the orientation of PP chains in the PP/MMT nanocomposites became very difficult under an external shear force; this indicated that the molecular motion of PP chains intercalated between MMT layers was highly confined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1–10, 2003     

Mechanical hysteresis,interface and filler–filler structural breakdowns in ethylene vinyl acetate organoclay composites internally lubricated via radiolytically degraded PTFE microparticles

Inclusion of two or more distinct fillers (hybrid fillers) in a matrix is envisaged to entail synergetic advantages. This study reports synthesis and property evaluation of a novel hybrid filler‐based polymer composite containing two types of fillers with distinct attributes namely mechanical reinforcement and internal lubrication. Poly(tetrafluoroethylene) micro‐particles (PTFEMP) were synthesized via radiolytic‐mechanical degradation and used as an internal lubricant for organoclay (OC) reinforced ethylene vinyl acetate (EVA) matrix. Mechanical hysteresis, nonlinear and linear small amplitude oscillatory shear rheology, morphology, small angle X‐ray scattering (SAXS), dynamic coefficient of friction (DCoF), surface wetting and thermoxidative stability of binary and ternary composites were investigated. In EVA/OC composites, PTFEMP acted as an internal lubricant and reduced DCoF in a volume fraction‐dependent fashion. OC and PTFEMP both increased the mechanical hysteresis of EVA; though the magnitude of hysteresis was much less in PTFEMP. Intriguingly, PTFEMP reduced mechanical hysteresis of EVA/OC composites that is work done during loading and unloading stress–strain cycles was considerably reduced with the inclusion of PTFEMP in EVA/OC composites. SAXS results revealed mass fractals and the presence of an interfacial layer in EVA/OC composites but not in EVA/PTFEMP composites. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 509–519     

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     

Capillary extrusion of polypropylene/high-density polyethylene immiscible blends as studied by rheo-particle image velocimetry

The capillary extrusion of polypropylene (PP) and high-density polyethylene (HDPE) immiscible blends was studied in this work by rheo-particle image velocimetry (Rheo-PIV). The PP/HDPE blends were prepared by single screw extrusion and extruded through a transparent capillary die at a temperature of 200 °C and concentrations of 80/20, 60/40, 40/60 and 20/80 wt%, respectively. PIV measurements described accurately the flow behavior of PP/HDPE blends and revealed continuous velocity profiles in the die, without macroscopic phase separation, for all the blends in the resolution range of the PIV technique. The flow behavior of all the blends was shear-thinning (power-law) type and their viscosities laid in between the values corresponding to the neat polymers and increased in an exponential way along with the concentration of the highest viscosity component in the blend (HDPE). Also, it was found that the extruded blends acquired a stratified morphology and that HDPE mitigates extrudate distortions in PP, meanwhile PP eliminates slip and flow instabilities in HDPE by migrating to the region of highest shear stresses in the die. Migration of PP to the capillary wall was corroborated by Raman spectroscopy measurements on the periphery of solid extrudates. Finally, via calculations of the density of the molten blends under flow using the velocity profiles in the die, we show that the homopolymers are compatible in the molten state and follow a simple inverse relation for their density, and an exponential one for their viscosity.     

Selective distribution,reinforcement, and toughening roles of MWCNTs in immiscible polypropylene/ethylene‐co‐vinyl acetate blends

Polypropylene/ethylene‐co‐vinyl acetate (PP/EVA) nanocomposites with functionalized multiwalled carbon nanotubes (FMWCNTs) have been prepared. The dissolution experiment, transmission electronic microscope, and scanning electronic microscope characterizations prove that, in the nanocomposites with sea–island morphology, although some FMWCNTs are observed in both PP and EVA phases, most of FMWCNTs distribute at the interface; however, in the nanocomposites with cocontinuous morphology, FMWCNTs mainly distribute in EVA phase. Further results based on (differential scanning calorimetry) measurements show that the different dispersion states of FMWCNTs, which are resulted by the different melt blending sequences, result in the different crystallization behaviors of PP matrix. The mechanical measurements show that FMWCNTs exhibit apparent reinforcement and toughening effects for immiscible PP/EVA blends, and such effects are greatly dependent upon the blending sequences. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1882–1892, 2010     

Synthesis and characterization of aromatic polyamides containing alkylphthalimido pendent groups

A series of polyisophthalamides containing pendent phthalimido groups and flexible side spacers were prepared from four novel diacids and three commercial aromatic diamines. These polyamides were prepared in high yields and with high molecular weights by direct polycondensation with triphenyl phosphite and pyridine as condensing agents. The weight‐average and number‐average molecular weights, measured by gel permeation chromatography, were 70,000–137,000 and 47,000–86,000 g/mol, respectively. The novel polyamides were amorphous and readily soluble and showed glass‐transition temperatures of 150–240 °C, as measured by differential scanning calorimetry. Thermogravimetric analysis showed that the 10% weight‐loss temperatures in nitrogen were 355–430 °C, a significant improvement in thermal stability having been observed with the increase in the side‐chain length. A theoretical quantum mechanical study was successfully carried out to explain these results. Flexible and tough films, cast from polymer solutions, showed tensile strengths of 50–125 MPa. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3711–3724, 2002     

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