Effect of compatibilization on the deformation and breakup of drops in step-wise increasing shear flow

Drop deformation and breakup were investigated in the presence of a block copolymer in step-wise simple shear flow using a home-made Couette cell connected to an Anton Paar MCR500 rheometer. Polyisobutylene (PIB) was used as the matrix, while five different molecular weights of polydimethylsiloxane (PDMS) were selected to provide drops with a relatively wide range of viscosity ratio. A block copolymer made of PDMS-PIB was used for interfacial modification of the drop-matrix system. The copolymer concentration was 2 wt% based on the drop phase. The experiments consisted in analyzing the drop shape and measuring the variation of the length to diameter ratio, L/D, both in steady state and in transient regimes till breakup. This allowed revising of the classical Grace curve that reports the variation of the critical capillary number for breakup as a function of viscosity ratio and providing also a new one for blends compatibilized with an interfacial active agent with a given molecular weight.     

Effects of matrix viscoelasticity on drop deformation in dilute polymer blends under slow shear flow

The deformation of a single drop in a flowing dilute polymer blend is here investigated for slow steady shear, through video-enhanced microscopy and image analysis. The data are interpreted in terms of a perturbative solution of the fluidodynamic problem for small drop deformations, where effects of matrix viscoelasticity are taken into account. It is found that drop orientation towards the shear direction is directly linked to normal stresses in the matrix fluid.     

Polypropylene/polyamide 6/polyethylene-octene elastomer blends. Part 3. Mechanisms of volume dilatation during plastic deformation under uniaxial tension

It has been shown in a previous paper in this series that important dilatation is produced by plastic deformation under tension of neat PP and PP/PA6/POE blends, for which the POE to PA6 concentration ratio equals 1/2. In this work, the detailed mechanisms of this volume change are investigated from electron micrographs (SEM and TEM) obtained in the deformed state. At low alloy content, it is thus observed that dilatation results from decohesion of the PA6 particles from the PP matrix. As the amount of PA6 and POE increases, voids are nucleated preferentially in the thicker POE interphase making a shell around the PA6 particles, and secondarily in isolated POE particles. Unexpectedly, it has been found that the overall volume dilatation decreases with total alloying content. This is interpreted by: (i) the increasing contribution of PA6 that intrinsically deforms with less cavitation than PP, (ii) the post-cavitation rubber-like stretching of POE particles and, (iii) the early formation of a percolating network of shear bands from the diffuse array of voids formed after the yield point. These mechanisms explain the gradual increase of the resistance to impact of the PP/PA6/POE as their alloying content is increased.     

The role of organically modified layered silicate in the breakup and coalescence of droplets in PBT/PE blends

In this study, we investigated the effect of organically modified nanoclay (organoclay) on the morphology of immiscible polymer blends (PBT/PE) with various compositions of PBT ranging from 1 to 90 wt%. When a small amount of organoclay between 1 and 3 phr is added to the blend, the thin clay tactoids of the thickness of the order of 10 nm are located at the interface between PBT and PE phase. As its content is increased, the additional organoclay positions in a specific component depending on its affinity with the component. The addition of a small amount of organoclay results in the effective size reduction for PBT/PE blend. The organoclay located at the interface forms the interfacial phase with a non-homogeneous distribution of clay along the interface and changes the interfacial tension, which result in the coalescence suppression of the droplets. Rigid organoclay with a high aspect ratio allows the blend morphology with long-term thermal stability by suppressing the Brownian motion. This ability of the organoclay to suppress the coalescence of the droplets effectively reduces the droplet size. On the other hand, additional organoclay results in the rheological properties of particular component being increased, which means the change in the viscosity ratio. The change in the viscosity ratio, together with the coalescence suppression effect, affects the determination of the droplet size, depending on the location of the organoclay. Therefore, the organoclay suppresses the coalescence of the droplets at the interface, while simultaneously influencing the breakup of the droplets due to the change of viscosity ratio.     

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.     

Morphology of PEO/PDMS blends during shear: Coexistence of two droplet/matrix structures and additive effects

The morphologies of blends of polyethyleneoxide (PEO 37) and poly(dimethylsiloxane)s (PDSM), with viscosity ratios, λ, of approximately one (PDMS 230) or 2.8 (PDMS 314, being the component of higher viscosity) and interfacial tensions on the order of 10 mN/m, were investigated at 70 °C as a function of shear rate (up to 10 s⁻¹) and of time. For the system PEO 37/PDMS 230 we have also studied the influence of the compatibilizer dimethyl-ethyleneoxide-copolymer (PDMS-co-PEO), which is only reasonably soluble in PEO. To investigate the morphologies we have used an optical shear cell in combination with a light microscope. The most important observation consists in the formation of two coexisting droplet/matrix structures for volume fractions of PDMS ranging from 0.4 to 0.6 for both λ values; the presence of the copolymer extends this region to 0.7. In the case of λ≈1 the average droplet radii are within experimental error independent of composition and morphology; for λ=2.8 they depend on the matrix phase in which they are contained and do again not vary with composition. The reduction in drop size caused by the copolymer is markedly larger if PEO forms the matrix. The present morphological observations suggest that the two coexisting droplet/matrix phases develop out of a single droplet/matrix structure via coalescence processes.     

Jet breakup and droplet formation in near-critical regime of carbon dioxide-dichloromethane system

The jet breakup and droplet formation mechanism of a liquid in the near-critical conditions of a solvent-antisolvent system is examined with high-speed visualization experiments and simulated using a front tracking/finite volume method. The size of droplets formed under varying system pressure at various jet breakup regimes is measured with a Global Sizing Velocimetry, using the shadow sizing method. A stainless steel nozzle with 0.25 mm I.D and 1.6 mm O.D was used in this study. Experiments were performed at fixed temperature of 35 °C and system pressure in the range from 61 to 76 bar in the near-critical regime of the DCM-CO₂. At the near mixture critical regime for DCM-CO₂ mixture, the miscibility between the two fluid phases increases and the interfacial tension diminishes. This phase behavior has important applications in particle formation using gas antisolvent (GAS) and supercritical antisolvent (SAS) processes. The jet breakup and droplet formation in the near-critical regime is strongly dependent on the changes in interface tension and velocity of the liquid phase. An understanding of the droplet formation and jet breakup behavior of DCM-CO₂ in this regime is useful in experimental design for particle fabrication using SAS method.     

Ruthenium staining for morphological assessment and patterns formation in block copolymer films

The selective staining by ruthenium tetroxide (RuO₄) was used in combination with Atomic Force Microscopy and calcination to discriminate and assign microphases at the surfaces of films of complex polymer systems. This paper evaluates this technique on thin films of polystyrene-b-polylactide (PS-b-PLA) and polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) and demonstrates its efficiency on complex thin film of binary blend of PS-b-PMMA and PLA. This method overcomes difficulties in the interpretation of AFM images by assigning PS microphase. In addition we show that this methodology could yield nanostructured inorganic materials with tunable structures such as perforated layers or nanowires that could find potential applications in the fabrication of high specific surface area Ru oxide-based materials.     

Transition between stratified and non-stratified horizontal oil-water flows. Part II: Mechanism of drop formation

The conditions and mechanism of drop formation at the interface of oil-water wavy stratified flows that lead to the onset of drop entrainment and the transition to dual continuous flow pattern were investigated both experimentally and theoretically. Experimentally, high-speed video imaging was used to capture the mechanism of drop detachment from waves during oil and water stratified flow in a diameter horizontal acrylic pipe. The visual observations revealed that the faster phase undercuts the other one while the waves present in both phases deform until drops are detached. The wave deformation was attributed to the drag force, that originates from the relative movement between the two phases, exceeding the stabilising surface tension force. Based on this force balance an equation was developed that related the wavelength to the amplitude that can lead to drop detachment. This drop entrainment equation and the wave stability equation suggested in part I of the paper [Al-Wahaibi, T., Angeli, P., 2007. Transition between stratified and non-stratified horizontal oil-water flows. Part I: Stability analysis. Chemical Engineering Science, in press, doi:10.1016/j.ces.2007.01.024 ], defined three regions in a wave amplitude versus length graph, namely the stable waves, the unstable waves and the drop entrainment region. The intersection of the lines produced by these two equations gives the critical minimum wave characteristics for drop formation. These agreed well with experimental data when a new correlation for the drag coefficient on the waves was used, suitable for liquid-liquid flows. Also the characteristics of waves that were experimentally found to form drops fell within the predicted entrainment region.     

Analysis of phase morphology and dynamics of immiscible PP/PA1010 blends and its partial-miscible blends during melt mixing from SEM patterns

The formation and evolution of the phase morphology of polypropylene (PP) with Nylon1010 (PA1010) blends before and after adding the compatibilizer, polypropylene grafted maleic anhydride (PP-g-MAH), during melt mixing are investigated by the pattern analysis of scanning electron microscope (SEM). The average particle diameter DP_AV, characteristic length Λ and the average characteristic length Λm are calculated to discuss the melt mixing process. It is proved, by the figure-estimation theory, that the distribution of Λ is log-normal distribution. Furthermore, the phase morphology during melt mixing is discussed in depth by the parameters of the log-normal distribution. The results demonstrate that the structure of the dispersed phase during melt mixing evolves with dynamical self-similarity through the competition of break-up and coalescence of dispersed phase. A fractal dimension, based on the probability density of the character length, is calculated in this study. The results show that the fractal dimension is an effective parameter to characterize the melt mixing process of polymer blends.     

Dispersion, agglomeration, and network formation of multiwalled carbon nanotubes in polycarbonate melts

Three different industrially available multiwalled carbon nanotube (MWNT) materials were directly incorporated into polycarbonate by melt mixing using a small-scale compounder. Despite of similar aspect ratios the electrical percolation behaviour was different. TEM investigations reveal significant differences in the nanotube dispersion which can be attributed to different dispersability of the raw MWNT materials. It is shown that the investigation of the sedimentation behaviour of aqueous MWNT dispersions is a simple method to estimate the nanotube dispersability.The relationships between melt processing conditions and MWNT dispersion and distribution were studied on polycarbonate samples containing 0.875 wt% MWNT prepared by masterbatch dilution. During melt mixing only high shear forces can provide suitable MWNT dispersion because firstly the MWNT disentanglement is facilitated and secondly secondary agglomeration is prevented. At low shear agglomeration of formerly well dispersed MWNT could be observed. During hot pressing the network or MWNT arrangement and the resulting electrical conductivity can be manipulated by the processing conditions like melt temperature and pressing speed. A certain nanotube agglomeration can enhance the development of an electrical percolated network as shown by dielectric spectroscopy.     

Characteristics of subzero startup and water/ice formation on the catalyst layer in a polymer electrolyte fuel cell

This work experimentally explores the fundamental characteristics of a polymer electrolyte fuel cell (PEFC) during subzero startup, which encompasses gas purge, cool down, startup from a subfreezing temperature, and finally warm up. In addition to the temperature, high-frequency resistance (HFR) and voltage measurements, direct observations of water or ice formation on the catalyst layer (CL) surface have been carried out for the key steps of cold start using carbon paper punched with microholes and a transparent cell fixture. It is found that purge time significantly influences water content of the membrane after purge and subsequently cold-start performance. Gas purge for less than 30 s appears to be insufficient, and that between 90 and 120 s is most useful. After gas purge, however, the cell HFR relaxation occurs for longer than 30 min due to water redistribution in the membrane-electrode assembly (MEA). Cold-start performance following gas purge and cool down strongly depends on the purge time and startup temperature. The cumulative product water measuring the isothermal cold-start performance increases dramatically with the startup temperature. The state of water on the CL surface has been studied during startup from ambient temperatures ranging from −20 to −1 °C. It is found that the freezing-point depression of water in the cathode CL is 1.0 ± 0.5 °C and its effect on PEFC cold start under automotive conditions is negligible.     

Recent developments in the formation, characterization, and simulation of micron and nano-scale droplets of amorphous polymer blends and semi-crystalline polymers

Polymer micro- and nano-particles are fundamental to a number of modern technological applications, including polymer blends or alloys, biomaterials for drug delivery systems, electro-optic and luminescent devices, coatings, polymer powder impregnation of inorganic fibers in composites, and are also critical in polymer-supported heterogeneous catalysis. In this article, we review some of our recent progress in experimental and simulation methods for generating, characterizing, and modeling polymer micro- and nano-particles in a number of polymer and polymer blend systems. By using instrumentation developed for probing single fluorescent molecules in micron-sized liquid droplets, we have shown that polymer particles of nearly arbitrary size and composition can be made with a size dispersion that is ultimately limited by the chain length and number distribution within the droplets. Depending on the time scale for solvent evaporation—a tunable parameter in our experiments—phase separation of otherwise immiscible polymers can be avoided by confinement effects, producing homogeneous polymer blend micro- or nano-particles. These particles have tunable properties that can be controlled simply by adjusting the size of the particle, or the relative mass fractions of the polymer components in solution. Physical, optical, and mechanical properties of a variety of micro and nano-particles, differing in size and composition, have been examined using extensive classical molecular dynamics calculations in conjunction with experiments to gain deeper insights into fundamental nature of their structure, dynamics, and properties.     

Compatibilising action of random and triblock copolymers of poly(styrene-butadiene) in polystyrene/polybutadiene blends: A study by electron microscopy, solid state NMR spectroscopy and mechanical measurements

Scanning electron microscopy, solid-state proton NMR spectroscopy and static mechanical analysis have been performed in order to evaluate the compatibilising action of random copolymers of polystyrene and polybutadiene and triblock copolymers of poly(styrene-butadiene-styrene) in incompatible polystyrene/polybutadiene (PS/PB) blends. Scanning electron microscopic examination of the cryofractured and etched surfaces showed high degree of compatibilising action of the triblock copolymers as evidenced by the very sharp decrease of the domain size of the dispersed phase followed by an increase at higher concentrations. This is a clear indication of interfacial saturation. These results were in agreement with the theoretical predictions of Noolandi and Hong. The random copolymer was not effective in compatibilising the system. Solid-state proton NMR experiments were performed on the uncompatibilised and compatibilised blends. The proton spin-lattice relaxation times in the laboratory frame, T₁(H), and in the rotating frame, T_1ρ(H), and spin-spin relaxation times, T₂(H), were carefully measured for the systems. Significant changes were observed for the systems compatibilised with triblock copolymers due to the preferential localisation of the copolymers at the PS/PB interface. However, the random copolymer did not have any compositional drift and is not an effective interface modifier in agreement with microscopy study. The static mechanical properties of the blends have also been analysed. The addition of triblock copolymers increased the mechanical properties of the blends. Finally, attempts have been made to correlate the NMR results with the microstructure and mechanical properties of the blends.     

Phase continuity and inversion in polystyrene/poly(methyl methacrylate) blends

Dual-phase continuity and phase inversion of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends processed in a twin-screw extruder was investigated using a selective extraction technique and scanning electron microscopy. Emphasis was placed on investigating the effects of viscosity ratio, blend composition, processing variables (mixing time and annealing) and diblock copolymer addition on the formation of bi-continuous phase structure (BPS) in PS/PMMA blends. The experimental results were compared with the volume fraction of phase inversion calculated with various semi-empirical models. The results showed that the formation of a BPS strongly depends on the blend composition and the viscosity ratio of the constituent components. Furthermore, BPS was found in a wide volume fraction interval. Increasing the mixing time and the addition of diblock copolymer, both led to a narrowing range of volume fraction in which BPS exists. Quiescent annealing coarsened the structure but indicated no qualitative changes. Some model predictions for phase inversion could predict qualitative aspects of the observed windows of co-continuity but none of the models could account quantitatively for the observed data.     

Investigation of the degree of homogeneity and hydrogen bonding in PEG/PVP blends prepared in supercritical CO2: Comparison with ethanol-cast blends and physical mixtures

The degree of homogeneity and H-bond interaction in blends of low-molecular-mass poly(ethylene glycols) (PEG, M_w = 400, 600, 1000) and poly(vinylpyrrolidone) (PVP, M_w = 9 × 10³) prepared in supercritical CO₂, ethanol and as physical mixtures were studied by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy and dynamic mechanical analysis (DMA) techniques. Homogeneity of samples prepared in supercritical CO₂ were greater than physically mixed samples, but slightly less than ethanol-cast samples. PEG-PVP H-bond interaction was higher for ethanol-cast blends when compared to blends prepared in supercritical CO₂. This reduced interaction was attributed to a combination of: (1) shielding of PEG-PVP H-bond interactions when CO₂ is dissolved in the blend; (2) rapidly reduced PEG and PVP chain mobility upon CO₂ venting, delaying rearrangement for optimum PEG-PVP H-bond interaction.     

Large scale formation of various highly oriented structures in polyethylene/polycarbonate microfibril blends subjected to secondary melt flow

A strong shear flow was imposed on the melt of polycarbonate (PC) microfibril reinforced high density Polyethylene (HDPE) during a secondary melt flow process, i.e. gas assisted injection molding (GAIM). Classic shish-kebabs and typical transcrystallinity were simultaneously observed in the entire thickness of the GAIM HDPE/PC microfibril composites, which were closely related to the strong shear flow that was further amplified and distributed by incorporated PC microfibrils. Interestingly, some nano-sized ultrafine PC microfibril inclined to absorb extended chain bundles to form shish nuclei on its surface first, which subsequently evolved into hybrid shish-kebab superstructures. It was deemed that the induced formation of hybrid shish-kebab superstructures on nano-sized ultrafine PC microfibril was due to the absorbing of extended chain bundles for hybrid shish nuclei with the strong shear flow serving as the driving force. Importantly, large scale formation of these highly oriented crystalline superstructures can bring significant mechanical reinforcement in GAIM HDPE/PC microfibril composite. For GAIM HDPE/PC microfibril composites, its yield strength is increased by 68% and 66%, compared to the GAIM HDPE parts and the common injection molded (CIM) HDPE/PC composites, respectively; meanwhile, the Young's modulus is enhanced by 253% and 17%, compared to the GAIM HDPE parts and the CIM HDPE/PC composites, respectively.     

Structure development and property changes in high‐density polyethylene/calcium carbonate blends during pan‐milling

A new self‐designed mechanochemical reactor, inlaid pan‐mill, was used in studying high density polyethylene (HDPE) and calcium carbonate (CaCO₃) blends. The effects of CaCO₃ on the crushing and structure of HDPE matrix and the properties of HDPE/CaCO₃ blends were investigated. Scanning electron microscopy, Fourier transformed IR spectroscopy, dynamical mechanical testing analysis, capillary rheometer, and Instron material testing system were used to characterize the structure of HDPE and evaluate the properties of HDPE/CaCO₃ blends. The introduction of calcium carbonate during milling improved milling efficiency, and time needed for each cycle was greatly reduced. Oxygen‐containing groups on HDPE chains, which were produced during milling, increased interfacial interactions and improved the dispersion and distribution of calcium carbonate particles in HDPE/CaCO₃ blends. Rheological, thermal, and mechanical properties were also improved. The elongation at break of milled blends with high concentrations of calcium carbonate was significantly higher than that of unmilled blends. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1459–1464, 1999     

Miscibility of Polycarbonate/Polyvinylpyrrolidone and Polycarbonate/Polyethylene Oxide in Chloroform by Viscosity,Ultrasonic and Refractometric Methods

Abstract

Miscibility studies of polycarbonate/polyvinylpyrrolidone (PC/PVP) and polycarbonate/ polyethylene oxide (PC/PEO) in common solvent chloroform were carried out in different percentages of the blend compositions. The viscosity, ultrasonic velocity, refractive index and density were measured at 30[ddot]C. The interaction parameters were obtained using the viscosity data to probe the miscibility. The obtained results were confirmed by the ultrasonic velocity, density and refractive index measurements.     

Decoration of multi-walled carbon nanotubes by polymer wrapping and its application in MWCNT/polyethylene composites

ABSTRACT: We dispersed the non-covalent functionalization of multi-walled carbon nanotubes (CNTs) with a polymer dispersant and obtained a powder of polymer-wrapped CNTs. The UV-vis absorption spectrum was used to investigate the optimal weight ratio of the CNTs and polymer dispersant. The powder of polymer-wrapped CNTs had improved the drawbacks of CNTs of being lightweight and difficult to process, and it can re-disperse in a solvent. Then, we blended the polymer-wrapped CNTs and polyethylene (PE) by melt-mixing and produced a conductive masterbatch and CNT/PE composites. The polymer-wrapped CNTs showed lower surface resistivity in composites than the raw CNTs. The scanning electron microscopy images also showed that the polymer-wrapped CNTs can disperse well in composites than the raw CNTs.