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.
Michail K. Dolgovskij, Paula D. Fasulo, Frédéric Lortie, Christopher W. Macosko, Robert A. Ottaviani, William R. Rodgers, May 2004
Polypropylene/organoclay nanocomposites have been prepared by melt blending in five different mixers: an internal mixer, two lab-scale, co-rotating vertical twin-screw mixers, a 30 mm co-rotating twin-screw extruder, and a multilayer extrusion system. The effectiveness of these mixers toward the dispersion of the clay into the polymer matrix was evaluated by TEM, X-ray diffraction, and melt rheology. Mechanical properties and coefficients of linear thermal expansion (CLTE) were also evaluated for these blends. The vertical twin-screw mixer at lower shear rate appears to provide the best mixing in terms of dispersion efficiency and modulus improvement. The combination of shear rate and residence time in the mixer is discussed in order to rationalize our results.
Mark A. Barger, Robert L. Sammler, Craig J. Carriere, May 2004
It has been long recognized that properties of multiphase polymer systems are strongly dependent upon supramolecular structure. Examples of controlling supramolecular structure for property enhancement during fabrication include (a) control of molecular orientation and/or crystallization, and (b) establishing optimum morphology in multiphase polymer systems.Interfacial tension strongly influences multiphase polymer blend morphology, and compatablizers are frequently employed to manage interfacial tension in order to encourage the formation of a specifically desired morphology. Interfacial tension has also been found to affect the flow stability of certain multilayer flows.This paper will discus interfacial tension effects in ternary biphasic blends of bisphenol-A polycarbonate, poly(methyl methacrylate), and poly(vinylidene fluoride). PMMA and PVdF are thermodynamically miscible and form one phase of the biphasic blend. The Imbedded Fiber Retraction method was used to probe interfacial tension of the blends with polycarbonate. The interfacial tension function was found to be non-linear with respect to PMMA/PVdF phase composition, and this result will be rationalized by applying surface thermodynamic theory.
Reactive extrusion of maleic anhydride functionalized polyethylene (PE-MA) and amine-terminated polyamide-6 (PA-6) was carried out in a twin-screw extruder with the injection of supercritical CO2 (scCO2). The extent of the interfacial reaction was quantified by measuring the amount of unreacted maleic anhydride (MA) by means of FTIR. It was found that the final MA conversion increases with CO2 concentration. The increase of MA conversion was explained from the mechanism of interfacial reactions between two melt phases. Dissolution of CO2 into polymer melts increases the free volume, thus enhancing the segmental chain mobility, promoting the reorientation of chain configuration and facilitating contact of reactive functional groups. It was also found that, with the increase of polyamide-6 content in the blend, the effect of CO2 on the MA conversion is less pronounced. At high concentration of polyamide-6 (70%), the MA conversion is very high (80 %) even without using CO2 and injection of CO2 into the polymer melts seems to have no effect on the MA conversion. This is most likely due to the development of a cross-linked interfacial region or the saturation of copolymers at the interface.
In this study, the effect of supercritical CO2 (scCO2) on the interfacial tension between polystyrene (PS) and low density polyethylene (LDPE) was studied using the pendant drop method at temperatures from 200 to 240 °C and CO2 pressures up to 18 MPa. The LDPE melt was prepared in a high pressure optical cell and the PS pendant drop was injected into the LDPE melt with a special high pressure syringe. The interfacial tension measurement was taken after saturation of CO2 into both polymer melts. It was found that the interfacial tension between PS and LDPE decreases by as much as 30% at CO2 pressures just above its critical pressure. Further increase of CO2 pressure seems to have small effect on the interfacial tension.
I. Pesneau, M.F. Champagne, M.A. Huneault, May 2004
LLDPE-g-GMAs were synthesized in a twin-screw extruder by free radical grafting of GMA on LLDPE. The grafted GMA content was varied between 0 and 1.8wt% by changing the initial GMA and peroxide concentrations and the viscosity of the LLDPE. The double cantilever beam (DCB) test was then used to measure the adhesion of these materials with PETG. The effect of the grafting level, the presence of unbound GMA and the viscosity of the material was investigated. Good adhesive strength was developed, in particular when the material was purified to remove unbound GMA monomer and oligomers.
The impact behaviors of nanoclay filled Nylon 6 (Nano-Nylon 6) blended with poly (acrylonitirile-butadiene-styrene) terpolymers (ABS) prepared through a twin screw mixing process were investigated here using metallocene polyethylene grafted maleic anhydride (POE-g-MA) as compatibilizer. It is found that impact strength increases slightly for Nano-Nylon 6/ABS blend system with the addition of compatibilizer, but increases remarkably for the conventional Nylon 6/ABS case. These discrepancies could be attributed to a different degree of available reaction sites from amine group on Nano-Nylon 6 and Nylon 6.
F. Gribben, G.M. McNally, W.R. Murphy, T. McNally, May 2004
Polymer blends of polyamides and polyethylenes are immiscible and highly incompatible. These blends are characterised by high interfacial tension, a two-phase morphology and poor physical characteristics due to reduced interaction across the phase boundaries. The compatibilising agent, maleic anhydride-grafted-LLDPE, is physically miscible with the polyethylene phase and has a chemical functionality with the polyamide phase. The use of a new generation mLLDPE (ENGAGE ™ by Dupont) was studied to investigate its suitability as a modifier for the polyamide grade. The influence of the composition of the blends and the effect of the addition of the compatibiliser were both investigated for their effect on the mechanical properties. Increased mLLDPE content was shown to slightly decrease the impact values but significantly increase the modulus values. The addition of the compatibiliser improved the properties of the blends.
A nanocomposite consisting of rectangular prism-shaped liquid crystalline polymer nano-crystals dispersed in a thermoplastic polymer matrix was produced by melt mixing blends of a thermotropic liquid crystalline polyester (TLCP) and the zinc salt of lightly sulfonated polystyrene ionomers at 300 °C. The conversion of a macroscopically dispersed LCP phase to nano-particles during melt mixing was analyzed directly by torque measurements during melt-mixing and indirectly by wide angle X-ray diffraction and transmission electron microscopy of the resulting blends. Salts other than zinc did not induce the formation of the TLCP nano-particles, so it appears that the formation of the nano-crystals involved a specific interaction of the zinc sulfonate groups with the TLCP. The specific nature of the interaction, e.g., physical or chemical is not yet known.
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 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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Kim McLoughlin Senior Research Engineer, Global Materials Science Braskem
A Resin Supplier’s Perspective on Partnerships for the Circular Economy
About the Speaker
Kim drives technology programs at Braskem to develop advanced polyolefins with improved recyclability and sustainability. As Principal Investigator on a REMADE-funded collaboration, Kim leads a diverse industry-academic team that is developing a process to recycle elastomers as secondary feedstock. Kim has a PhD in Chemical Engineering from Cornell. She is an inventor on more than 25 patents and applications for novel polyolefin technologies. Kim is on the Board of Directors of SPE’s Thermoplastic Materials & Foams Division, where she has served as Education Chair and Councilor.
A Resin Supplier’s Perspective on Partnerships for the Circular Economy
About the Speaker
Gamini has a BS and PhD from Purdue University in Materials Engineering and Sustainability. He joined Penn State as a Post Doctorate Scholar in 2020 prior to his professorship appointment. He works closely with PA plastics manufacturers to implement sustainability programs in their plants.
A Resin Supplier’s Perspective on Partnerships for the Circular Economy
About the Speaker
Tom Giovannetti holds a Degree in Mechanical Engineering from The University of Tulsa and for the last 26 years has worked for Chevron Phillips Chemical Company. Tom started his plastics career by designing various injection molded products for the chemical industry including explosion proof plugs and receptacles, panel boards and detonation arrestors for 24 inch pipelines. Tom also holds a patent for design of a polyphenylene sulfide sleeve in a nylon coolant cross-over of an air intake manifold and is a Certified Plastic Technologist through the Society of Plastic Engineers. Tom serves on the Oklahoma Section Board as Councilor, is also the past president of the local Oklahoma SPE Section, and as well serves on the SPE Injection Molding Division board.
Joseph Lawrence, Ph.D. Senior Director and Research Professor University of Toledo
A Resin Supplier’s Perspective on Partnerships for the Circular Economy
About the Speaker
Dr. Joseph Lawrence is a Research Professor and Senior Director of the Polymer Institute and the Center for Materials and Sensor Characterization at the University of Toledo. He is a Chemical Engineer by training and after working in the process industry, he has been engaged in polymers and composites research for 18+ years. In the Polymer Institute he leads research on renewably sourced polymers, plastics recycling, and additive manufacturing. He is also the lead investigator of the Polyesters and Barrier Materials Research Consortium funded by industry. Dr. Lawrence has advised 20 graduate students, mentored 8 staff scientists and several undergraduate students. He is a peer reviewer in several journals, has authored 30+ peer-reviewed publications and serves on the board of the Injection Molding Division of SPE.
Matt Hammernik Northeast Account Manager Hasco America
A Resin Supplier’s Perspective on Partnerships for the Circular Economy
About the Speaker
Matt Hammernik serves as Hasco America’s Northeast Area Account Manager covering the states Michigan, Ohio, Indiana, and Kentucky. He started with Hasco America at the beginning of March 2022. Matt started in the Injection Mold Industry roughly 10 years ago as an estimator quoting injection mold base steel, components and machining. He advanced into outside sales and has been serving molders, mold builders and mold makers for about 7 years.
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