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The SPE Library contains thousands of papers, presentations, journal briefs and recorded webinars from the best minds in the Plastics Industry. Spanning almost two decades, this collection of published research and development work in polymer science and plastics technology is a wealth of knowledge and information for anyone involved in plastics.

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Conference Proceedings

Oxidized Polypropylene and Ionomers Thereof as Compatibilizers for Polypropylene/Nylon-6 Blends
V. Dang, C. Shu, D. Dong, T. Phan, May 2004

Oxidized polypropylene and ionomers thereof were evaluated as compatiblizers for polypropylene/ nylon-6 (PP/PA-6) blends. For these blends, the ionomer of oxidized PP provided better morphology and physical properties than the oxidized PP. The change in morphology was also reflected in the rheological behaviors that the compatibilized blends showed an increase in melt elasticity. With improvement in flowability and yellowing resistance, the ionomer of oxidized PP also, for the most part, yielded mechanical properties comparable to commercially available maleated PP.

Oxidized Polypropylene as Compatibilizer/Dispersion Agent for Flame Retardants
V. Dang, C. Shu, D. Dong, May 2004

Oxidized polypropylene has been produced with a controlled level of functionality. Applications of this new polymer in both halogenated and non-halogenated flame retardant (FR) formulations were studied. Benefits include enhancement of flame retardance performance and improvement in mechanical properties, processability, and surface appearance. In the melt stage, rheological measurements of G’ indicate that relaxation time decreases significantly when adding oxidized PP, confirming the improvements in PP-FR interfacial interaction and FR dispersion in the PP matrix.

New Miscible Blends of Nylon 6 and Polyhydroxyaminoether Resins
Kris Akkapeddi, Clark Brown, Darnell Worley, May 2004

Nylon 6 (PA-6) was found to form fairly miscible blends with certain types of polyhydroxyaminoether (PHAE) resins as evidenced by microscopy and DSC techniques. Such miscibility between a nylon and a non-nylon polymer is rather rare and novel. However, the observed miscibility and phase behavior was found to depend on both the nylon and the PHAE resin structures. For PA-6, the miscibility was found to occur only when the PHAE contained sufficient amounts of resorcinol moieties and ethanol amine moieties. Other nylons such as PA-66, PA-6I/6T, PA-MXD6 and PA-12 showed an increasing tendency for phase separation and immiscibility.

In Situ Block Copolymer Formation during Solid-State Shear Pulverization: An Explanation for Blend Compatibilization via Interpolymer Radical Reactions
Andrew H. Lebovitz, John M. Torkelson, May 2004

Interpolymer radical coupling leading to block copolymer formation is demonstrated for the first time in the solid state and in the absence of diffusion using solid-state shear pulverization. Fluorescence-detection gel permeation chromatography detected interpolymer reaction in high-molecular weight polystyrene (PS)/pyrene-labeled PS and high-MW poly(methyl methacrylate) (PMMA)/pyrene-labeled PS blends. Proof of interpolymer radical coupling supports prior pulverization studies demonstrating compatibilization, i.e., stability of dispersed-phase to long-time annealing, of PS/high density polyethylene and PS/PMMA blends.

Stabilization of Dispersed Phase to Static Coarsening: Polymer Blend Compatibilization via Solid-State Shear Pulverization
Andrew H. Lebovitz, John M. Torkelson, May 2004

Absolute compatibilization of immiscible polymer blends via a novel, continuous process, solid-state shear pulverization, and without addition of compatibilizing agents is quantitatively shown for the first time by stability of number-average dispersed-phase domain size to longterm annealing. Compatibilization via pulverization is due to in situ chain scission that is supported by molecular weight analysis of PS before and after pulverization, resulting in polymer radicals that can lead to in situ interfacial block copolymer formation.

Compatibilization of PC-SAN Blends by Ultrasound-Assisted Melt Mixing
Hyungsu Kim, Joung Gul Ryu, Hyunsuk Yang, Jae Wook Lee, May 2004

In this study, high intensity ultrasound was employed to induce mechano-chemical degradation during melt processing of polymeric materials. It was expected that generation of macroradicals in polymer mixture can lead to in-situ copolymer formation by their mutual combination, which should be an efficient path to compatibilize immiscible polymer blends and stabilize their phase morphology in the absence of other chemical agents.Ultrasound-aided degradation of PC and SAN was practiced during melt processing of the polymer in a sonicated mixer. We investigated the changes in the morphology of PC/SAN blends for various viscosity ratios of PC and SAN and improvement of mechanical properties of sonicated blends was evaluated.

Simulation of Droplet Breakup Using a Lattice Boltzmann Method
F.R. Phelan Jr., N.S. Martys, May 2004

Droplet breakup in homogeneous shear flow at super critical Capillary numbers and a viscosity ratio of unity is studied using a lattice Boltzmann method. We find that the total number of child drops that form from an isolated super critical drop scales according to a power law relation (n = 3.5). The child drops that form are all below critical, but not wholly uniform in size, and the distribution appears to be log-normal at high drop numbers. It is also found that for large ratios of the Capillary number to its critical value, the total strain required to break up a drop into N sub-critical entities tends to a constant value.

Drop Breakup Mechanisms in Polymer-Polymer Systems
Bin Lin, Uttandaraman Sundararaj, Frej Mighri, Michel A. Huneault, May 2004

The deformation and breakup of a single viscoelastic polymer drop inside a viscoelastic polymer matrix at high temperatures under simple shear was visualized in a specially designed transparent Couette mixer. The polymer systems studied were polyethylene matrix/polycarbonate drop (PE/PC) with viscosity ratios between 2 and 8. Aside from the “erosion” mechanism, which has already been reported (1, 2), three other distinct breakup modes were observed: (a) “parallel breakup” – the drop breaks after being stretched into a thin sheet or sausage parallel to the flow direction; (b) “tip streaming” – streams of small droplets are released from the tips of a pointed drop in the flow direction; and (c) “perpendicular breakup” – the drop breaks after being elongated in the vorticity direction.

Polymer Dispersion Visualization in a Couette Flow Cell
Frej Mighri, Michel A. Huneault, May 2004

Dispersion mechanisms in high viscosity ratio polystyrene/polyethylene (PS/PE) and ethylene propylene rubber/polypropylene (EPR/PP) systems under relatively high shear rates and temperatures up to 230°C have been investigated in a transparent Couette setup. Through the in situ visualization, two non-Newtonian breakup mechanisms were revealed. The first one was the droplet elongation perpendicular to the flow direction followed by droplet shattering when the ends of the elongated droplets get slightly off axis with the stationary plane. The initial elongation has been associated to elastic normal force buildup in the droplet. The second non-Newtonian mechanism consisted in erosion at the drop surface.

Time-Scales of Coalescence in Polymer Processing: Study on Polypropylene/Polyamide-6 Blends
Jairo E. Perilla, Sadhan C. Jana, May 2004

The effects of shearing time, volume fraction, shear rate, and viscosity ratio on coalescence of isotactic polypropylene (PP) and polyamide-6 (PA6) blends were studied in simple shear flow. A simple model for coalescence developed to provide characteristic times in coalescence in polymer processing operations was used to analyze experimental results. The pre-coalescence droplet morphology was created by melt blending the polymers in a twin-screw extruder at several compositions and was subjected to a simple shear flow in a cone and plate rheometer at low shear rates (0.1 and 0.5 s-1). The rheological data was analyzed after removing the effects of viscosity mismatch to leave only the interfacial effects on coalescence.

Morphology Transitions in Multilayer Polymer Melts Due to Growth and Interaction of Holes
A.S. Joshi, D.A. Zumbrunnen, N. Coutris, May 2004

Chaotic advection has been used in prior work to create melts containing a large numbers of very thin individual layers among polymer components. Morphology changes in the layers occurred due to hole growth and interaction. Because the process was amenable to control, a wide variety of blend morphologies were obtained in extrusions. Modeling of these morphological transitions has been carried out with the aim of improving process control in envisioned smart blending machines where blend morphology can be specified via a computer keyboard. The lattice Boltzmann method (LBM) was used to study the interactive growth of various hole patterns in layers in a periodic three-dimensional domain. It was demonstrated computationally that hole growth can lead to numerous thin and oriented fibers, single and dual phase continuous morphologies, and very fine droplets. The advantages of obtaining these and other structures via controllable multilayer formation and breakup are discussed.

Laminar Morphology of Extruded HDPE/PA-6 Blends Controlled by Flow Fields
Han-Xiong Huang, You-Fa Huang, Shu-Lin Yang, May 2004

Ribbons were extruded from two high-density polyethylene (HDPE)/polyamide-6 (PA-6) blends with different melt shear viscosity ratios (VRs) of PA-6 to HDPE. Three different screw configurations, one metering and two mixing screws, and three screw speeds were evaluated to investigated their effects on the morphology of extruded ribbons. The scanning electron microscopy (SEM) observation showed that the blends with different VRs need different screw shearing intensity to yield a thin, overlapping, and discontinuous laminar PA-6 phase, which results in enhancing permeability barrier properties. The screw speed also played a distinct role in controlling the morphology of the blend. By controlling the flow fields, through appropriately combining the screw configuration with screw speed in this study, a well-developed laminar PA-6 phase with an aspect ratio of about 100 was obtained.

Interfacial Chemistry and Morphology of Blends of Polybutyleneterephthalate and Epoxide-Containing Rubber
Martin van Duin, Philippe Martin, Ana Vera Machado, Roger Legras, Marnix van Gurp, May 2004

Of the various ways in which polybutyleneterephthalate (PBT) can be toughened, the addition of epoxidecontaining rubbers is one of the most effective. The interfacial chemistry (dissolution and fractionation experiments) and morphology (transmission electron microscopy) development in blends of PBT with ethylene-(methyl acrylate)-(glycidyl methacrylate) rubber (E-MA-GMA) has been studied as a function of the mixing time for batch kneaders and of the length along the axis of a co-rotating twin-screw extruder. First, a physics-controlled mixing regime occurs with a very fast dispersion of the rubber to the ?m level. Subsequently, a chemistry-controlled regime occurs, where the interfacial area is covered with PBT/E-MA-GMA graft copolymer, which prevents coalescence and, thus, results in further refinement of the morphology to sub-?m level. The occurrence of cross-linking of the rubber phase in some cases limits optimum blend dispersion.

Interfacial Area and Rheological Measurements of Cocontinuous Poly(Ethylene Oxide)/Polystyrene Blends
Jeffrey A. Galloway, Christopher W. Macosko, May 2004

Blends of poly(ethylene oxide) and polystyrene were analyzed using scanning electron microscopy with image analysis and rheological measurements to determine the region of cocontinuity. Local maxima in the amount of interface in the blends and in the elastic modulus at low frequency correspond to the boundaries of the region of cocontinuity. Annealing of the samples caused some blends near the boundaries of the region of cocontinuity to break up into dispersed morphologies, while other blends remained cocontinuous, despite dramatic increases in the size scale.

Morphological Phase Behavior of PMMA and PC in PMMA/PC Binary and PP/PMMA/PC Ternary Blends
Minhee Lee, Seohwa Kim, Bong-Keun Lee, May 2004

The morphological phase behavior of polycarbonate and poly(methyl methacrylate) was studied in PMMA/PC binary and PP/PMMA/PC ternary blends prepared in a Haake batch mixer. Even though extensive research on the PMMA/PC blends has been performed, the miscibility between two polymers has not been clearly understood to date. The phase separation between two polymers has been consistently observed specifically the blends were prepared in molten state. In this paper, immiscible and miscible PMMA/PC phases were observed in PMMA/PC binary blends and PP/PMMA/PC ternary blends, respectively. Therefore, effects of the PP-matrix on the PMMA/PC miscibility were proposed in this study. In order to clarify the effects of the PP-matrix, various analyzing techniques including NMR, GPC, ICP and SEM were utilized. It was also found that the miscibility of PMMA and PC is highly affected by the processing parameters such as mixing temperature and mixing time in the presence of the PPmatrix.

An In-Situ Process for the Production of Electrically Conductive Polyaniline Fibres from a Polymer Blend
Ricardo Herbé Cruz-Estrada, May 2004

The feasibility of using an in-situ deformation process for producing electro-conductive polyaniline (PANI) fibres embedded in the bulk of a filament-like composite and longitudinally oriented along its axial direction is evinced. Blends of a PANI complex and polystyrene-polybutadinepolystyrene (SBS) were capillary extruded into filaments. The extrudates’ microstructure consisted of elongated domains of the PANI complex embedded in the SBS, displaying a considerable degree of uniformity and continuity, and preferentially oriented in the extrusion direction.

Blends of Ethylene-Methyl Acrylate-Acrylic Acid Terpolymers with Ethylene-Acrylic Acid Copolymers
Nutthakan Pongrakananon, Nathaporn Somrang, Nathaporn Somrang, Pitt Supaphol, Manit Nithitanakul, Brian P. Grady, May 2004

The effect of methyl acrylate composition in ethylene-methyl acrylate-acrylic acid (E-MA-AA) terpolymers and acrylic acid content in ethylene-acrylic acid (E-AA) copolymers was investigated in blends of these two materials. The E-MA-AA terpolymer with 8 mole percent methyl acrylate was not miscible with any E-AA material no matter what the AA content, while the terpolymer with only 2 mole percent methyl acrylate was miscible, at least to some extent, with the E-AA copolymer at high acrylic acid contents. For the E-AA polymer material with the highest acid content, there was a synergistic effect for some properties at low E-MA-AA contents; the tensile strength was 10% higher than the value for the E-AA copolymer, even though the E-AA copolymer was much more stiff.

Study on Mechanical Properties of Dynamically Cured PP/Epoxy Resin Blends
Xueliang Jiang, Hua Huang, Yong Zhang, Yinxi Zhang, May 2004

In this paper, dynamical vulcanization process which usually used for preparation of thermoplastic elastomers was applied to PP/epoxy resin blend systems. Products of crosslinked epoxy resin particles finely dispersed in PP matrix were obtained, and were named as dynamically cured PP/epoxy resin blends. Maleic anhydride grafted PP (PP-MA) was used as a compatilizer. The influences of PP-MA content, epoxy content and reaction conditions on mechanical properties of dynamically cured PP/epoxy resin blends were investigated. Experimental results show that dynamically cured PP/epoxy resin blends have better mechanical properties than that of the PP/epoxy and PP/PP-MA/epoxy blends. By increasing epoxy resin content, flexural modulus increased significantly, while the elongation at break dramatically deceased. Impact strength was slightly affected by the presence of the epoxy resin.

The Processing and Performance of Polyvinyl Chloride / Ethyl-Vinyl Acetate Copolymer Blends
D.C. McConnell, G.M. McNally, W.R. Murphy, May 2004

Two grades of ethyl-vinyl acetate (EVA), each containing 26% (modified with 1.2% methacrylic acid) and 27% vinyl acetate (VAc) respectively, were blended at various compositions, with two grades of PVC. Mechanical analysis of these blends showed that the tensile and flexural modulus decreased and impact strength increased, with increasing EVA content. Rheological analysis for the blends showed only slight changes in shear viscosity with increasing EVA content, even at lower shear rates. DMTA showed a shift in glass transition temperatures of the PVC and EVA components within the blends, suggesting partial miscibility over the range of concentrations studied.

The Effects of Coupling Agents on the Mechanical Properties of Wood-Polymer Composites
P. Douglas, W.R. Murphy, G. McNally, M. Billham, May 2004

A range of wood-polymer blends, containing 40% w/w MDF sawdust (90-150 microns) was prepared using polypropylene (MFI 1.7 g/10min) and LDPE (MFI 2.2 g/10min). The blends were melt compounded using a Killion single screw extruder with a barrier type screw design. Two different coupling agents, maleic anhydride and a titanate compound, were incorporated into the blends during compounding at concentrations of 1 and 2%. Tensile, flexural and impact specimens from these blends were prepared using injection moulding. Mechanical analysis showed improved impact strength, tensile modulus and break strength for polypropylene-wood and polyethylene-wood blends containing 1% maleic anhydride.










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