SPE Library
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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Rheology
CHAIN EXTENSION OF LOW VISCOUS PA 66 IN REACTIVE EXTRUSION PROCESS IN ORDER TO EXTRUDE THICK-WALLED PIPES
Dan Zhang, Hans-Gerhard Fritz, Christian Bonten,, May 2012
The aim of this study is to increase the complex viscosity of low viscous polyamide 66 (PA 66) by means of a chain extension process. The technical goal of the process is to extrude thick-walled pipes from chain extended PA 66 without the appearance of sagging problems. The influence of styrene maleic anhydride (SMA) and epoxide (EP) on chain extension of PA 66 were studied using a co-rotating twin- screw extruder. To evaluate the coupling effects of the different extenders on PA 66, the rheological and mechanical properties of the chain extended PA 66 were investigated. The extruded pipes, obtained from chain extended PA 66, featured a considerably improved wall-thickness distribution.
IN-SITU COMPATIBILIZATION OF HDPE-FUMED SILICA COMPOSITES: MORPHOLOGY, RHEOLOGY AND FILM BARRIER PROPERTIES
Sangita Nandi, Sanjukta Bose, Susanta Mitra, Anup K. Ghosh, May 2012
In the present study, HDPE-fumed silica (FS) composites were prepared by melt-mixing with different filler loading and in presence of PE-g-MA compatibilizer. Dynamic rheological properties and morphological analyses of the composites supported the plausible interfacial interaction between reactive groups of PE-g-MA and surface silanol groups of FS. Oxygen and water vapor permeability of the films made from composites were increased due to presence of FS as well as due to compatibilization.
NOUVEL NON-LINEAR RHEOLOGICAL PARAMETERS FOR POLYOLEFIN QUALITY CONTROL
S. Filipe, K. Klimke, Anh T. Tran, May 2012
The continuous demand of high performance materials with key properties requires the optimization of polymerization and post-reactor treatment processes. A multiscale characterization approach including techniques such as rheology, fractionation and NMR has proven to be essential to understand the links between polymerization conditions, molecular structural properties and end performance. Rheology is a preferred candidate for analytical characterization, since its use provides combined knowledge on molecular characteristics and processability. A key parameter for the performance of materials during processing is the so-called LCB. Rheology, in particular methods exploring the longest relaxation mechanisms, is known to provide a significant insight into the type and amount of longer chains incorporated during polymerization. Most of the existing rheological parameters used by Industry and Academia, to correlate molecular structure and processability, are based on techniques that are often time consuming and which, for most of the cases, are only applicable to a given class of materials. The increasing need to reduce “time to market” requires the development of more sophisticated and efficient characterization tools. The combination of different non-linear viscoelastic methods presented within this work will provide further insight into the links between molecular structural properties and polymerization conditions. The use of the Large Amplitude Oscillatory Shear (LAOS) together with uniaxial extensional flow measurements can bring new understanding on the nature of the non-linear viscoelastic response of LCB materials and its correlation with molecular characteristics.
A MULTIVARIATE IN-MOLD SENSOR DESIGN FOR MEASUREMENT OF MELT PRESSURE, TEMPERATURE, VELOCITY, AND VISCOSITY
David Kazmer, Stephen Johnston, Guthrie Gordon, Robert Gao, Zhaoyan Fan, Navid Asadiznajani, May 2012
A multivariate sensor is designed with a piezoelectric ring and an infrared detector for measurement of melt pressure and temperature. The infrared detector includes a thermistor for measurement of the mold temperature. The polymer melt velocity is estimated by inspecting the transient melt temperature signal. The melt viscosity is then estimated from rheological models as the slope of the melt pressure relative to the melt velocity. Experiments confirm the validity of the approach.
EFFECT OF CLAY CONCENTRATION ON THE RHEOLOGICAL PROPERTIES OF TRIBLOCK COPOLYMERS NANOCOMPOSITES
Leice G. Amurin, Danilo J. Carastan, , Nicole R. Demarquette, May 2012
Block copolymers are materials with many applications in the field of thermoplastic elastomers. Their properties can be further improved by the addition of nanoclays. However, the morphological and rheological properties of these hybrid materials are not very well known. In this work, the effects of clay concentration on the evolution of morphology of two block copolymers, (SEBS and SEBS-MA), presenting an aligned cylindrical morphology, when submitted to elongational flows was studied. The elongational test was performed using a Sentmanat elongational rheometer and the morphology of the clay-containing block copolymers was studied using small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM).
SUREFLO®: A NEW AND HIGHLY EFFECTIVE PROCESS ADDITIVE FOR THERMOPLASTICS
Xiaofan Luo, Brian P. Sarvas, John D. Jungjohann, Aaron Puhala, May 2012
In this paper, we explore the effects of a new process additive, SureFlo®, on the rheological and crystallization behavior of semi-crystalline polyolefins. It was found that SureFlo® can dramatically lower melt viscosities and delay crystallization, resulting in improved processability of the polymer. As we show in a finite-element simulation of a typical injection molding process, the use of 7 wt- % SureFlo® results in significant decrease in fill time and increases productivity by ~20%.
MORPHOLOGY OF POLY(LACTIC ACID)/POLY(BUTYLENE ADIPATE-CO-TEREPHTHALATE) BLENDS AND ITS COMPOSITE WITH SPHERICAL SILICA PARTICLES
Ebrahim Jalili Dil, Pierre Carreau, Sepehr Ravati, Basil Favis, May 2012
In this work the detailed morphology of poly(lactic acid)/ poly (butylene adipate-co-terephthalate) has been carried out for the first time. The morphology of PLA/PBAT blends with different compositions was studied and limits of the co-continuity region were determined using rheological measurements and image analysis. Particle size analysis and breaking thread experiments showed that PLA/PBAT is a very low interfacial tension polymer blend. Moreover, composites of PLA/PBAT/spherical silica particles were prepared and the localization of silica particles in this blend was studied.
RHEOLOGICAL CHARACTERIZATION OF INJECTION MOULDING GRADE THERMOTROPIC LIQUID CRYSTAL POLYMERS (LCPS)
Ahmed Rahman, Rahul K Gupta, Sati N. Bhattacharya, Shishir Ray, Franco Costa, May 2012
Liquid Crystal Polymers (LCPs) are advanced high temperature processing polymers with unique physical properties. It contains rigid rod like molecules, which exhibit structural orientation during the flow process at one or two dimensional level. Rheological behaviour of unfilled LCPs and filled (glass fibre) LCPs were characterized with ARES and Capillary rheometer at low and high shear rates. The complex viscosities (h*) as well as shear viscosities (h) showed a typical shear- thinning behaviour. LCPs exhibit anomalous rheological behaviour with shear and temperature. Viscosity reduced at low shear rate region because of the tumbling nature of rod like molecules. The abnormal temperature dependence of the viscosities can be explained by the transition of anisotropic rod-like molecules to isotropic molecules with increase in temperature. In steady shear flow, it was observed that rotational transformation occur from direction of flow to surface direction, which leads to first negative normal stress difference (N1) with shear rate. Stress relaxation conducted after cessation of shear flow to prove the molecular dynamics. Multiple overshoot observed due to tumbling, which was varying with temperature and shear rate.
INVESTIGATION OF PROCESSING AND RHEOLOGICAL PARAMETERS EFFECT ON FILM BLOWING PROCESS STABILITY BY USING VARIATIONAL PRINCIPLES
Martin Zatloukal, Roman Kolarik, May 2012
In this study, a numerical stability analysis of the film blowing process is performed considering non- isothermal processing conditions, non-Newtonian behavior of the polymer and physically limiting criteria (maximum tensile and/or hoop stress) in order to investigate the complex relationship between processing conditions (internal bubble pressure, heat transfer coefficient, mass flow rate, cooling air temperature, melt/die temperature), material parameters (extensional viscosity, rupture stress, Newtonian viscosity, flow activation energy, power law index) and film blowing stability.
RHEOLOGICAL PROPERTIES AND FOAMING BEHAVIOR OF COAGENT-MODIFIED POLYPROPYLENE
Ying Zhang, Marianna Kontopoulou, J.Scott Parent, Savvas G. Hatzikiriakos, Chul B. Park, May 2012
Reactive modification of linear PP by radical mediated grafting in the melt state is investigated as a means of increasing its melt strength, thus resulting in improved foam processing characteristics. A tri-functional coagent, triallyl trimesate (TAM) is used to introduce long chain branching to the linear PP homopolymer. Rheological characterization is conducted to relate the rheological properties to the modified PP chain architecture. The foaming behaviour of the linear and branched PPs is investigated using a batch foaming apparatus with N2 as a blowing agent.
NUMERICAL VERIFICATION OF RHEOLOGICAL CHARACTERIZATION OF POLYSTYRENE DURING MICROCELLULAR INJECTION MOLDING
Shia-Chung Chen, Kuan-Hua Lee, Yu-Wan Lin, Tai-Yi Shiu, Chuan-Wei Chang, Jimmy C. Chien, May 2012
The purpose of this study is to investigate the rheological behavior of Polystyrene melt with dissolved SCF of nitrogen during Microcellular Injection Molding process applied with Gas Counter Pressure (GCP) technology; also, rheological behavior is compared with independent theoretical simulation using moldex3D. A slit cavity is designed to measure the pressure drop of polystyrene mixed with 0.4wt% supercritical nitrogen fluid under different mould temperatures (185°C, 195°C, and 205°C), injection speeds (5, 10, and 15 mm/s) as well as counter pressures (0, 150, 300 bars). It was found that the melt viscosity is reduced by up to 30% when GCP is increased from 50 to 150 bar as compared to conventional injection molding. The simulation results of pressure history well agrees with the experiments and provide a theoretical point of view on process design.
MEASUREMENT AND MODELING OF PLANAR AND UNIAXIAL EXTENSIONAL VISCOSITIES FOR LDPE POLYMER MELT
Martin Zatlouka, May 2012
In this work, novel patent pending rectangle and circular orifice dies have been used in order to determine planar and uniaxial extensional viscosities for extrusion coating LDPE through entrance pressure drop determination on conventional twin bore capillary rheometr. It has been revealed that the uniaxial extensional viscosity/uniaxial extensional strain hardening is higher in comparison with the planar extensional viscosity and recently proposed non-Newtonian fluid model can described the measured rheological data reasonably well.
HIGH-SHEAR-RATE RHEOLOGY OF POLYSTYRENE MELTS
Wei Sheng Guan, Han Xiong Huang, May 2012
This work presents a systematic analysis on the capillary rheology of polystyrene melts under high shear rates ranging from 103 to 106 s-1. The precise Bagley correction was achieved by means of the enhanced exit pressure technique. The end pressure drop was found to predominate over the Bagley-corrected capillary pressure drop in the high shear rate range. Furthermore, the dissipation heating, pressure dependence, and compressibility effects were quantitatively evaluated. Results implied that the apparent nonlinearity of the Bagley-corrected capillary pressure drop versus apparent shear rate profile, which occurred at the shear rates of above 105 s-1, mainly resulted from the dissipation heating. In the shear rate ranges investigated, the corrected rheological behavior could be adequately described by the power law.
PROGRESS ON SIMULATING LONG-GLASS FIBER ORIENTATION IN COMPLEX MOLDING GEOMETRIES
Kevin J. Meyer, Donald G. Baird, May 2012
The mechanical properties of fiber reinforced materials are highly dependent on fiber orientation generated within the composite during molding operations. Rheologically obtained parameters for fiber suspensions are applied to current models to predict fiber orientation in complex geometries independent of experimental considerations. This method provides an a priori pathway to determine fiber orientation based solely on rheological testing of the suspension and independent of the mold geometry. Furthermore, predictions for fiber orientation are carried out using the traditional rigid fiber Folgar-Tucker model as well as the semi-flexible Bead-Rod model which allows for the inclusion of fiber bending to be taken into account often witnessed in long-glass fiber (LGF) systems. Computations for fiber orientation are performed for center-gated disks and predictions with the two above models are compared to experimental data.
FUNCTIONALITY IN MULTILAYER FILMS FOR PACKAGING
F. Sadeghi, R. Silverwood, A. Housni, A. Ajji, May 2012
During the last decades, the food, pharmaceutical and many other industries have seen several changes in packaging technology and applications because of new consumer demands and market trends. These drivers can be summarized as requirements for high quality, freshness and extended shelf-life of products, with easy-to-use and resistant packaging made with lighter, cheaper and recyclable materials. On the other hand, public demand and awareness for food safety has become a significant concern. This has even intensified on the recent regular outbreak of Listeria and Salmonella bacteria in various area of the world, following the consumption of contaminated meat and cheese products. The outbreak has prompted the public awareness to question food quality in stores and technological solutions that could prevent contamination and/or alert consumers may provide better public protection. Finally, the global market for materials and films used in packaging is very large. When decomposed into various segments such as controlled, active, and smart or barrier packaging, the volumes used and annual growth rates are significant in addition to other concerns such as sustainability. The performance of polymer films and multilayer packages are the result of the microstructure that is imparted to the material as a result of complex interactions between the resin and the thermo- mechanical history that it experiences during processing. This microstructure is strongly influenced by molecular parameters of the resins used (molecular weight, molecular weight distribution, branching, co-monomer type and content, etc.), their layout in multilayer structures and the additives used as well as the rheological, thermodynamic, thermal properties and the crystallization kinetics under the processing conditions. In the past, most of the studies were directed to the improvement of structural properties of films and multilayer structures (mainly mechanical: strength, tear, toughness etc...) and muc
IMPROVING THERMAL EFFICIENCY OF SINGLE SCREW EXTRUSION
Adrian Kelly, Javier Vera Sorroche, Elaine Brown, Phil Coates, May 2012
Thermal issues associated with polymer melt extrusion are complex. The process efficiency associated with melting and conveying polymers using a rotating screw inside a barrel is highly dependent upon the frictional, thermal and rheological properties of the polymer, the selected screw geometry, and designated extruder operating conditions including machine set temperatures and screw speed. Melting of the polymer is attained through a combination of thermal conduction and viscous shearing. This process is energy intensive but optimisation cannot be simply indicated by the energy used per kilogram of product. The quality of the extrudate is also of paramount importance. Melt quality can be defined in terms of the value and homogeneity of melt temperature. In this work, in- process monitoring techniques incorporating thermocouple grid sensors, infra-red thermometers and an energy meter have enabled real-time characterisation of thermal dynamics in single screw extrusion, for a 63.5mm diameter extruder. Operation of this extruder has also been simulated using commercial CAE software. Two commercial grades of polyethylene have been investigated using three extruder screw geometries at different extrusion operating conditions to gather evidence relating to process thermal efficiency. Extruder screw geometry, screw rotation speed, extruder set temperatures and material properties were each found to have a significant effect on the thermal homogeneity of the melt and on process energy consumed.
THE EFFECT OF POLYHYDROXYBUTYRATE-CO-VALERATE (PHBV) CONTENT ON THERMAL, RHEOLOGICAL, MECHANICAL PROPERTIES AND FOAMING BEHAVIOR OF POLYLACTIC ACID (PLA)
Qi Guan, Reza Rizvi, Hani E. Naguib, May 2012
This paper examines the effect of PHBV content on the properties of PLA-PHBV blends and their foams. PLA and PHBV blends were manufactured in various compositions via compounding, and their tensile, thermal and rheological properties and their foam morphologies were characterized. The results indicated that although PLA and PHBV are immiscible, the addition of small quantities of PHBV (up to 30 wt%) lead to a finer and more homogenous cellular morphology.
ELONGATIONAL RHEOLOGY AND MECHANICAL PROPERTIES OF BIODEGRADABLE PLA/PBSA BLENDS
Hassan Eslami, Musa R. Kamal, May 2012
Blends of poly(lactic acid) (PLA) and poly[(butylene succinate)-co-adipate] (PBSA) were prepared using a twin screw extruder. The morphology of the blends was examined using scanning electron microscopy (SEM). Elongational flow properties of the blends and pure components were studied. A strong strain hardening behavior was observed for PLA/PBSA blends, in which PBSA forms the continuous phase (PBSA wt% ? 50). The results of tensile test showed that even for blends containing only 10wt% PBSA, elongation at break increased significantly. By the addition of PBSA to PLA, a transition from brittle behavior (observed for pure PLA) to ductile behavior was observed.
POLYMER PARTICLE INTERACTIONS IN NANOCOLLOIDS
Burcu Ozel, Mehmet Yildiz, Yusuf Z. Menceloglu, May 2012
The rheological properties of complex fluids has been one of the interesting research subject due to the macroscopic behaviour (namely shear thinning and shear thickening) exhibited when they are subject to shear force. All concentrated suspensions under right conditions can exhibit the non-Newtonian flow behaviour, however, the required conditions and the underlying mechanism are not well understood in literature. To this respect, this study systematically investigates the effects of physicochemical parameters on the flow behavior of colloidal nanoparticle suspension (CNS) to shed a light on the mechanism behind the shear thickening behavior of CNS. We have also presented the outcomes of experimental studies of CNS with a low particle volume fraction, and anisotropic and flocculated microstructures through measuring their viscosity and electrical resistance under various shear forces together with utilizing several relevant characterization methods (i.e., Dynamic Light Scattering, Transmission Electron Microscopy and Capacitance Measurement). It is observed that studied CNS display shear thickening/thinning flow behavior depending on their microstructure forms due to the interaction forces among particles and associated changes in floc sizes, which are controlled by the shear induced hydrodynamical forces. The detailed valuation of the experimental results indicates that the shear thickening phenomena in low volume fraction, anisotropic and flocculated systems is mainly attributed to the increase in the total surface area and the effective volume fraction of particles due to both hydrodynamic and interparticle forces.
ON-LINE SENSORING IN EXTRUSION-BASED PROCESSES: PAST, PRESENT AND FUTURE
João M. Maia, May 2012
The challenges materials processing and compounding face nowadays are related not only with the design and control of better and more efficient machines but, essentially, with the manipulation of the molecular structure of the materials, with a view to obtaining innovative high performing products. Extruders are a fundamental part of any extrusion process and intermeshing co-rotating twin-screw extruders, in particular, have special application niches, being the equipment of choice for blending and compounding operations, mainly because of their good distributive and dispersive mixing capabilities. In fact, they are used in most important modern polymer applications such as compounding of filled polymer systems and masterbatches, polymer melt homogenization, polymer modification and the polymer blending. Very often, the last two operations involve, apart from polymer processing, chemical reactions, classical examples of which are the peroxide induced degradation of polypropylene to prepare grades with controlled rheology, and the grafting of maleic anhydride onto polyolefins to improve their compatibility with other polymers. Although these are widespread value-added processes in the polymer industry, there is often a gap in the fundamental knowledge of the properties and physical and chemical composition of the materials being processed during the extrusion process because the extruders are “black boxes” in which the properties of the initial materials, as well as those of the final product, are known, but not the kinetics of the transformation process. This poses severe limitations to current operations because without this knowledge any optimization effort of material structure and/or properties is done by trial- and-error and, thus, is very time consuming and offers no guarantees that the final product is, in fact, optimal. In this work, we present a review of recent developments in on-line sensors that allow for the monitoring of the rheological, chemical and s
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