Melt rheological properties of polypropylene–polyamide6 blends compatibilized with maleic anhydride‐grafted polypropylene

The melt rheological properties of binary uncompatibilized polypropylene–polyamide6 (PP–PA6) blends and ternary blends compatibilized with maleic anhydride‐grafted PP (PP–PP‐g‐MAH–PA6) were studied using a capillary rheometer. The experimental shear viscosities of blends were compared with those calculated from Utracki's relation. The deviation value δ between these two series of data was obtained. In binary PP–PA6 blends, when the compatibility between PP and PA6 was poor, the deformation recovery of dispersed PA6 particles played the dominant role during the capillary flow, the experimental values were smaller than those calculated, and δ was negative. The higher the dispersed phase content, the more deformed the droplets were and the lower the apparent shear viscosity. Also, the absolute value of δ increased with the dispersed phase composition. In ternary PP–PP‐g‐MAH–PA6 systems, when the compatibility between PP and PA6 was enhanced by PP‐g‐MAH, the elongation and break‐up of the dispersed particles played the dominant role, and the experimental values were higher than calculated. It was observed that the higher the dispersion of the PA6 phase, the higher the δ values of the ternary blends and the larger the positive deviation. Unlike uncompatibilized blends, under high shear stress with higher dispersed phase content, the PP‐g‐PA6 copolymer in compatibilized blends was pulled out from the interface and formed independent micelles in the matrix, which resulted in reduced total apparent shear viscosity. The δ value decreased with increasing shear stress. Copyright © 2006 Society of Chemical Industry     

Transient and steady-state deformations and breakup of dispersed-phase droplets of immiscible polymer blends in steady shear flow

Transient and steady-state deformations and breakup of viscoelastic polystyrene droplets dispersed in viscoelastic high-density polyethylene matrices were observed in a simple steady shear flow between two transparent parallel disks. By separately varying the elasticities of the individual blend components, the matrix shear viscosity, and the viscosity ratio, their effects on the transient deformation, steady-state droplet size, and the breakup sequence were determined. After the startup of a steady shear flow, the viscoelastic droplet initially exhibits oscillations of its length in the flow direction, but eventually stretches preferentially in the vorticity direction. We find that at fixed capillary number, the oscillation amplitude decreases with increasing droplet elasticity, while the oscillation period depends primarily on, and increases with, the viscosity ratio. At steady-state, the droplet length along the vorticity direction increases with increasing capillary number, viscosity ratio, and droplet elasticity. Remarkably, at a viscosity ratio of unity, the droplets remain in a nearly undeformed state as the capillary number is varied between 2 and 8, apparently because under these conditions a tendency for the droplets to widen in the vorticity direction counteracts their tendency to stretch in the flow direction. When a critical capillary number, Ca_c, is exceeded, the droplet finally stretches in the vorticity direction and forms a string which becomes thinner and finally breaks up, provided that the droplet elasticity is sufficiently high. For a fixed matrix shear stress and droplet elasticity, the steady-state deformation along the vorticity direction and the critical capillary number for breakup both increase with increasing viscosity ratio.     

Investigation of rheology and morphology to follow physical fibrillar network evolution through fiber spinning of PP/PA6 blend fiber

This work is aimed at investigating the influence of fibrillar morphology of deformed Polyamide 6 (PA6) droplets dispersed in Polypropylene (PP) matrix on the melt viscoelastic behavior of their blends. The blends of PP with various amounts of PA6 (1%, 6%, 10%, and 20%) were prepared by melt mixing in a co‐rotating twin screw extruder and fibrillated by fiber spinning process. Scanning Electron Microscopy revealed that the PA6 spherical droplets form fibrillar inclusions after fiber spinning. The steady and transient shear rheological responses of samples were evaluated in both linear and nonlinear ranges of deformation. Non‐terminal behavior of storage modulus at low frequency appeared as a typical characteristic of fibrillar morphology whose width and value depend on fibril growth. Storage modulus and complex viscosity of the blends containing PA6 fibrillated structure were remarkably enhanced compared to as‐extruded samples. The fibrillar‐induced elasticity of the fibers is a distinguishable behavior which was revealed by conducting transient stress and creep‐recovery measurements and upon appearing mature fibrils, elasticity of the polymer blend fibers increased significantly. POLYM. ENG. SCI., 58:1251–1260, 2018. © 2017 Society of Plastics Engineers     

Effect of selective localization of carbon nanotubes in PA6 dispersed phase of PP/PA6 blends on the morphology evolution with time,part 1: Droplet deformation under simple shear flows

The deformation of carbon nanotube (CNT)‐filled PA6 droplets in PP matrix was examined under simple shear flows. The morphology of blends with various CNT contents in PA6 were probed by FE‐SEM. Based on the wetting coefficient calculations and rheological measurements, it was noted that the majority of CNTs were selectively located in the PA6 phase for concentrations up to 2 wt%. TEM micrographs evidenced the results for a sample with 0.5 wt% CNT in PA6. Optical microscopy of the blends during simple shear flows revealed the reduced deformability and breakups for filled‐droplets. Such observations were ascribed to the increased viscosity ratio and gradual formation of an elastic structure within the droplets. Maffetone‐Minale transient droplet deformation model was coupled with a modified capillary number to account for the developed elastic forces. It was shown that the contribution of such forces to the total shape‐conserving forces could arise up to 99% in comparison with the well‐known interfacial forces. These resisting forces can be so strong that for blends with CNT concentrations above 0.5 wt% in PA6 almost no deformation was observed under the applied shear stresses in this work. POLYM. ENG. SCI., 55:1504–1519, 2015. © 2014 Society of Plastics Engineers     

物性对油滴剪切变形影响的模拟分析

以简单线性剪切流为背景,采用VOF模型及若干自定义子程序进行模拟分析,探讨物性对油滴变形和破碎的影响关系。模拟表明:粘度对变形起到抑制作用,粘度越大,变形越难,更能耐受剪切流动;表面张力越小,油滴越容易发生变形和破碎,稳定性越差,表面张力阻止了油滴的变形;油滴粒径越大,越易变形、破碎,越不稳定。     

Deformation of an oil droplet on a solid substrate in simple shear flow

Displacement of immiscible fluids is important in sub-surface processes such as enhanced oil recovery, oil sand processing and detergency. In this study, simulation of an oil droplet deformation on a solid substrate in simple shear flow has been carried out using computational fluid dynamics tool (Fluent 6.3) and the shape of the oil droplet is compared with that of the experimental observation. The dynamic behavior of a two-dimensional oil droplet subject to shear flow in a closed channel is considered under the condition of negligible inertial and gravitational forces. The volume of fluid method is used in Fluent to determine the dynamics of free surface of the oil droplet during the fluid flow. The oil droplet deformation increases with the increase in capillary number, Reynolds number and size of the oil droplet. The deformation of an oil droplet attached to channel surface in simple shear flow is studied experimentally in laminar flow through visual observation using microscope (Ziess, SV11 APO) with high speed camera (PCO). Aniline and isoquinoline was used to form oil droplet and distilled water was used as shearing fluid. The deformation of aniline and isoquinoline droplets was recorded using a high speed camera connected to a PC. The recorded image was replayed and the deformation of aniline and isoquinoline droplets was analyzed using Axio Vision software and compared with the results obtained from CFD simulation. The deformation of different sizes of aniline and isoquinoline droplets at different flow rates of shearing fluid and with time are well predicted by the CFD simulation.     

Preparation and properties of self-reinforced polypropylene/liquid crystalline polymer blends

The mechanical properties of self-reinforced liquid crystalline polymer/polypropylene (LCP/PP) blends strongly depend on the viscosity ratio of the blend components in the melt. This ratio was determined for PP blends with different commercial LCPs (Vectra A950 and Vectra B950), by means of capillary rheometry, under conditions representative for the blending process during extrusion. It was found that optimal mechanical properties were achieved when the LCP/PP viscosity ratio at 285°C ranges between 2 and 4 at a shear rate of 800–1000s⁻¹. The LCP/PP viscosity ratio appears to be shear stress dependent. This creates the option of fine tuning the LCP droplet deformation process by means of the extrusion rate. This shear stress dependence is more pronounced for PP blends with Vectra B950 than for blends with Vectra A950.     

Morphology in Immiscible Polymer Blends During Solidification of an Amorphous Dispersed Phase under Shearing

Solidification under shear of dispersed polycarbonate (PC) fibers in copolymer polyethylene‐methyl acrylate matrix (EMA) was investigated using a hot optical shear device. First, the deformation of PC droplets and its modeling under isothermal conditions were studied for comprehension purposes. Overall agreement with literature models was found and the main influence of the viscosity ratio has been stressed. Second, the morphology control through dynamic quenching was experimented. It consists of solidifying the amorphous PC dispersed phase under shear flow. Break‐up times of PC fibers were taken into account. Shear rate and quenching‐time balance was demonstrated. Thus, during dynamic solidification, a fibrillar morphology could be obtained through rapid quenching. Long quenching times allow nodular morphology, whose size depends on the shear rate used. PC rods can be obtained by adjusting the shear rate during dynamic quenching.     

Drop Deformation and Breakup Mechanisms in Viscoelastic Model Fluid Systems and Polymer Blends

This paper reviews the dispersion mechanisms in viscoelastic systems under relatively high shear rate conditions. In particular, two non‐Newtonian deformation and breakup mechanisms were revealed by flow visualization in a transparent Couette shearing setup. The first one is the dispersed droplet elongation perpendicular to the flow direction. This was observed only for viscoelastic drops and had been associated to normal force buildup in the droplet. The second deformation/breakup mechanism was observed in very high viscosity ratio polymer systems. It consists in erosion at the drop surface. Clouds of very small ribbons and sheets were developed around the drop then stretched and finally broken into very small droplets, rapidly distributed in the matrix.     

Studying the formation mechanism of in situ poly(butylene terephthalate) microfibrils prepared by one‐step direct extrusion via orthogonal experimental design

Polypropylene/poly(butylene terephthalate) (PP/PBT) microfibrillar composites (MFCs) were prepared through in situ one‐step direct extrusion using a triangle‐arrayed triple‐screw extruder (TTSE) at a processing temperature between the melting points of two components. The orthogonal experimental method was designed to assess the effects of the PBT content and processing parameters (temperature, screw speed, and feed rate) on the morphology of PBT fibrils. It can be found that the most important influence factor on the fibril formation is the PBT content, followed by temperature, feed rate, and screw speed. Furthermore, the morphological evolution procedures of the dispersed phase started from spherical pellets to ellipsoids or ribbons, forming short fibrils, and consequently high‐aspect‐ratio fibrils appeared under the alternating shear‐extensional flow field. Moreover, the rheological properties of linear PP incorporating fibrillated PBT were thoroughly investigated. The relaxation time of blends with various fibrous PBT was linearly proportional to the aspect ratio of fibrils. Strain‐hardening in extensional flow was observed for blends with long fibrils, and the strain‐hardening factor grew with the fibrillar aspect ratio, indicating the formation of a physical entanglement network between fibrils and matrix. POLYM. ENG. SCI., 58:1166–1173, 2018. © 2017 Society of Plastics Engineers     

Reactive compatibilization and in‐line morphological analysis of blends of PET and a thermotropic liquid crystalline polymer

The reactive extrusion of a compatibilized polyethylene terephthlate and thermotropic liquid crystalline copolyester blend system is investigated via in‐line optical microscopy and light scattering. The reactivity, morphology, rheological behavior and mechanical properties were studied. It was found that a droplet‐fiber transition in the liquid crystalline polymer can occur, and this transition is dependent upon the reactivity, the viscosity ratio of the blend components and the shear fields. The fibers are strongly oriented along the flow direction when specific processing conditions are met. An enhancement in the mechanical properties correlates with the morphology. The formation, deformation and stability of the fiber microstructure under different flow conditions are discussed.     

Effect of selective localization of carbon nanotubes in pa6 dispersed phase of PP/PA6 blends on the morphology evolution with time,part 2: Relaxation of deformed droplets after cessation of flow

The relaxation of carbon nanotube (CNT)‐filled PA6 droplets in PP matrix was studied after cessation of simple shear flows. The morphology evolutions of blends with various CNT contents in PA6 were probed by optical microcopy over time. It was shown that the retraction of deformed droplets accelerates with increasing CNT content in PA6. As evidenced by linear rheological measurements, gradual formation of elastic structures within the droplets was found responsible for such observations. The pre‐shearing flow was varied to investigate the effects of different flow histories on the kinetics of relaxation. By increasing the shear‐rate of the flow prior to relaxation, the relaxation kinetics slowed down to some extent. The slowed‐down kinetics was attributed to the partial rupture of the elastic structures within PA6. This idea was evidenced by performing the startup of steady shear flow experiments on PA6/CNT nanocomposites. The final morphology of the blends after the melt blending process was analyzed. The average droplet size was found to increase with increasing the CNT content. Also, the distribution of the droplet sizes became broader as a result of the increased viscosity and elasticity ratios. POLYM. ENG. SCI., 56:51–60, 2016. © 2015 Society of Plastics Engineers     

Numerical investigation of the evaporation of two-component droplets

A numerical model for the complete thermo-fluid-dynamic and phase-change transport processes of two-component hydrocarbon liquid droplets consisting of n-heptane, n-decane and mixture of the two in various compositions is presented and validated against experimental data. The Navier-Stokes equations are solved numerically together with the VOF methodology for tracking the droplet interface, using an adaptive local grid refinement technique. The energy and concentration equations inside the liquid and the gaseous phases for both liquid species and their vapor components are additionally solved, coupled together with a model predicting the local vaporization rate at the cells forming the interface between the liquid and the surrounding gas. The model is validated against experimental data available for droplets suspended on a small diameter pipe in a hot air environment under convective flow conditions; these refer to droplet’s surface temperature and size regression with time. An extended investigation of the flow field is presented along with the temperature and concentration fields. The equilibrium position of droplets is estimated together with the deformation process of the droplet. Finally, extensive parametric studies are presented revealing the nature of multi-component droplet evaporation on the details of the flow, the temperature and concentration fields.     

Thixotropic Behavior of Oil‐in‐Water Emulsions Stabilized with Ethoxylated Amines at Low Shear Rates

Oil‐in‐water (O/W) emulsification is a lubricating pipeline method based on the reduction of the energy frictional loss produced during viscous flow. The flow behavior of heavy O/W emulsions formulated with nonionic surfactants is described. The effects of pH and salinity of the aqueous phase on droplet diameter, stability, and apparent viscosity of O/W emulsions were evaluated. The low‐shear Couette flow of O/W emulsions displayed intense shear‐thinning and thixotropic behavior. Thixotropy was associated to the droplet deformation energy caused by shear rate changes. The droplet deformation and alignment led to the apparent viscosity reduction compared to the fluid at rest. Thixotropic behavior is supposed to balance between the breakdown and recovery of droplet ordered structures. Emulsion formulation parameters were influenced by the aqueous phase pH, enabling to manage the emulsion properties. The droplet mean diameter of < 18 µm resulted in very stable emulsions.     

Modeling droplet deformation in melt spinning of polymer blends

We report the results of a study of droplet deformation in uniaxial elongational flow under nonisothermal conditions. A mathematical model is developed that simulates deformation conditions in fiber spinning. To test our model, a blend of polypropylene and polystyrene was spun into fibers. The blend morphology of the fibers is accurately predicted by the proposed model. Morphological studies have shown that immiscible additives remain dispersed in the matrix as suspended droplets and that the droplets are elongated into fibrils under the action of shear or extensional forces during processing.     

Melt rheology and morphology of PP/SEBS/PC ternary blend

Melt rheological properties of the ternary blend of isotactic polypropylene (PP), styreneethylene–butylene–styrene terpolymer (SEBS), and polycarbonate (PC), PP/SEBS/PC, are studied in a wide range of composition, such that PP is the matrix and SEBS and PC are the minor components, with the proportion of one varying from 0 to 30% at various fixed compositions of the other. The respective binary blends, PP/SEBS and PP/PC, studied as the reference systems for interpretation of results on the ternary blends yielded interesting new information about the morphology development and its correlation with melt rheological properties of these binary blends. The studies include the measurement of melt rheological properties on a capillary rheometer in the shear rate range 10¹–10⁴ s^?1 at a fixed temperature of 240°C. The data presented as conventional flow curves are analyzed for the effect of blend composition and shear rate on pseudoplasticity, melt viscosity, and melt elasticity, and role of each individual component is identified. Morphology of dispersed phases of these blends is studied through scanning electron microscopy of the cryogenically fractured and suitably etched surfaces. Variations of morphology with blend composition and shear rate showed interesting correlation with melt rheological properties, which are discussed in detail. An important finding of the morphological studies is that in the PP/SEBS/PC ternary blend the SEBS phase forms two types of morphologies depending on the blend composition and shear rate: (i) simple droplets and (ii) boundary layer at the surface of the PC droplets. © 1993 John Wiley & Sons, Inc.     

Droplet deformation in confined shear and extensional flow

This work describes the direct observation of deforming water droplets in castor oil, undergoing combined shear and extensional flows in a transparent horizontal annular Couette flow cell, over a wide range of straining fields. This study is motivated by the recognition that many mixing devices of practical importance rely for their effective function on a complex, strongly time-dependent combination of these fundamental straining fields and interactions of the fluid with the confining surfaces. Photographic studies of droplet deformation have identified different modes of breakup and complex droplet structures. This study emphasises the significance of droplet size, constraining geometry and flow history on the dynamic response of droplets within shear and extensional flows.     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

电场作用下液滴的变形及库仑分裂模式

基于高速成像技术,本文对电场作用下甲醇液滴的显微形貌特征进行了可视化研究,精确捕捉了两相流体系中不同生长阶段的荷电液滴基于时间分辨特性的变形及库仑分裂演变行为,得到不同工况下荷电液滴的变形分裂过程及行为演化细节。基于液滴所受库仑力和介电泳力与周围流域的耦合作用,揭示了电场作用下不同生长阶段的液滴库仑分裂形成机理。结果表明,电场强度和液滴粒径是决定液滴变形及库仑分裂模式的主要因素,荷电液滴的变形及库仑分裂模式可以分为推压变形、顶部破碎、顶部-边端破碎、伞状破碎。结合量纲为1参数对液滴的变形及破碎特征进行了定量分析,随着电场强度的增大及液滴粒径的减小,液滴变形及顶部破碎的程度更加剧烈,液滴临界伞状破碎长度减小。     

Hydrodynamic Instabilities of Adhering Droplets Due to a Shear Flow in a Rectangular Channel

This paper reports on the hydrodynamic droplet instabilities of different sizes and viscosities due to shear forces in a rectangular channel. Water‐glycerine droplets of different volumes are investigated. A new and nonambiguous definition for the critical velocity of droplet detachment and a new mathematical correlation between the critical velocity v_crit and the fluid properties are presented. The measurements show that v_crit decreases with the droplet volume but at the same time the contour deformation increases. With increasing viscosity of the liquid droplet, i.e., higher glycerine mass fraction, the contour deformation becomes more prominent and an increase in v_crit can be observed. With respect to the fluid properties and droplet volumes, three different motion patterns are detected.