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Conference Proceedings
Polypropylene/Clay Nanocomposites: Characterization and Interpretation of Structure - Property Relationships
Anita Vaxman, Gershon Lidor, Rotem Shalom, Moshe Narkis, Arnon Siegmann, Aliza Tzur, May 2004
Polypropylene (PP) nanocomposites were obtained by melt compounding of PP and organoclays in the presence of maleic anhydride grafted polyolefin compatibilizer. The effects of compatibilizer type and content and the mixing sequence on the morphology and properties of the PP/clay nanocomposites were investigated. PP nanocomposites exhibit enhanced mechanical properties compared with neat PP and they also are thermally more stable. Rheological properties are sensitive to the composite structure and thus are a valuable indication of the degree of exfoliation.
Novel Nanostructured Polymer Blends with Enhanced Benefits
Jing Teng, Joshua U. Otaigbe, Eric Taylor, May 2004
Molecular-level blending of reactive polymers can provide an alternative and economical route to producing new polymers with special structures and improved properties. In this paper, we report results of our experimental efforts to generate compatibilized polypropylene (PP)/polyamide 6 (PA6) blend via in situ polymerization and in situ compatibilization of polypropylene, ? -caprolactam and maleic anhydride grafted PP that is impossible to achieve using conventional polymer blending methods reported in the literature. The intrinsic molecular-level blending and compatibilization of the preparation method allowed formation of nanostructured PP/PA6 blends with interesting stable interpenetrating or co-continuous morphologies that can be controlled during processing. Thermal and morphological measurements revealed that the compatibilization effect of the blend is significantly better than that obtained from conventional reactive blending of premade polymers. With proper control of the thermodynamics, interfacial tension (through use of chemically modified functional polymer) and deformation rates, particle coalescence could be suppressed, making it possible to generate the polymer blends with very small (< 100 nm) polydispersities. These blends could find applications in a number of high-end uses such as optics, drug delivery, tissue engineering, and permeable membranes for separation phenomena.
PBT and PET Ionomer Based Clay Nanocomposites
Grant D. Barber, Sean P. Bellman, Robert B. Moore, May 2004
Poly(butylene terephthalate), poly(ethylene terephthalate) and their respective ionomers were utilized as matrices in the formation of organically-modified montmorillonite clay nanocomposites. These materials were prepared using melt extrusion with a variety of clay concentrations. The small angle x-ray scattering and transmission electron microscopy data revealed that low levels of sulfonation in the polyester ionomers resulted in exfoliated clay nanocomposites. Moreover, the orientation of the clay platelets within injection molded dogbones was found to increase with increasing sulfonation level of the ionomers. The affect of clay dispersion on the thermal and mechanical properties of the nanocomposites was investigated. The enhancements in mechanical properties produced by the ionic functionality were attributed to an increase in the number of interactions between the clay platelets and the matrix via electrostatic interactions involving the sodium sulfonate groups. In addition, a tentative model of how the negatively charged, sulfonate groups along the polymer chains interact with the montmorillonite clay platelets to improve the exfoliation of the clay platelets was provided.
Performance Enhancing Crosslinked SBR Masterbatches for Thermoplastic Elastomers
Manoj Ajbani, Chris Kiehl, May 2004
Masterbatches of crosslinked solution-polymerized styrene-butadiene random elastomers (XL-SBR) and polypropylene (PP) were prepared and used for enhancing the oil resistance, compression stress relaxation performance, lowering gloss, and compression set of styrene-ethylene/butylene-styrene (SEBS)-based thermoplastic elastomer (TPE) compounds. Enhanced performance was achieved when SBR partly or substantially replaced the SEBS component. Modification of SEBS compounds in the Shore A range of 45-85 with the crosslinked SBR is discussed.
New Soft EPDM Rubber Concentrate for Toll Compounding to Produce High Flow Thermoplastic Vulcanizates (TPVs) for Injection Molding Applications
Yundong Wang, Ryszard Brzoskowski, May 2004
New soft EPDM rubber concentrate can be used to produce thermoplastic vulcanizates (TPVs) with improved flow properties by toll compounding processes for injection molding applications. By adding various amounts of polyolefin plastics such as polypropylene homo polymer or copolymers, TPVs with different durometers and properties can be made easily using compounding equipment such as twin screw extruders or other mixing equipment with sufficient mixing capability.
New Thermoplastic Vulcanizates (TPVs) with Improved Processibility for Injection Molding Applications
Yundong Wang, Hua Cai, Ryszard Brzoskowski, May 2004
A new line of thermoplastic vulcanizates (TPVs) has been introduced by DSM Thermoplastic Elastomers for injection molding applications where UV resistance is critical. This new line of products, consisting of several grades with hardness ranging from 50 to 85 shore A in black color, shows superior flow characteristics and balanced properties meeting existing automotive material specifications. In this paper, we will discuss some of the features associated with this new line of products.
Effect of Crystalline Structure on Tear Resistance of LDPE and LLDPE Blown Films
X.M. Zhang, S. Elkoun, A. Ajji, M.A. Huneault, May 2004
Low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) blown films differ significantly in the ratio between machine and transverse direction tear resistance. In this paper, the relation between crystalline morphology and these differences in film tear anisotropy was investigated. The crystalline morphology and its orientation were probed using microscopy and infrared spectroscopy. Significant differences in crystalline morphology were found: LDPE develops a row-nucleated structure, while a spherulitic-like superstructure was observed for LLDPE. These structural differences were shown to translate into different ratios of machine and transverse directions tear strengths.
Effect of Processing Parameters on Properties of LLDPE-Based Mono- and Multilayered Blown Films
S. Elkoun, M.A. Huneault, K. McCormick, F. Puterbaugh, L. Kale, May 2004
In this paper we investigated the effect of processing parameters on end-use mechanical properties of monolayer and 5-layer coextruded polyethylene blown films using three different linear low density (LLDPE) polyethylene resins. The three investigated LLDPEs were: a conventional Ziegler-Natta gas phase ethylene-butene copolymer, and two solution ethylene-octene resins produced with Ziegler-Natta and single site catalysts. The octene copolymers were produced using NOVA Chemicals advanced SCLAIRTECH™ process and catalyst technologies.It was found that tear strength increases in the direction perpendicular to the highest orientation, that impact and puncture strength increase with the overall orientation and finally that the effect of orientation due to shear stresses in the die on final film properties is not significant due to rapid macromolecular relaxation before crystallization.
A Predictive Model for Dart Impact Strengths of Solution Octene LLDPE Film Resins
XiaoChuan (Alan) Wang, Sarah Marshall, Larry Kale, May 2004
A predictive dart model has been developed for solution ethylene/octene linear low density polyethylene (LLDPE) resins produced using a high activity Ziegler- Natta catalyst and NOVA Chemicals’ Advanced SCLAIRTECH technology. By incorporating both polymer properties and blown film processing variables, a robust model was developed through multivariate statistical analysis. The model suggests that dart impact is a nonlinear function of polymer structure, machine direction strain rate and a corrected Deborah number. This model has also demonstrated its utility in product development at both pilot and commercial scales.
Control of Blown Film Tear Strength Anisotropy through Blending of LDPE and LLDPE
X.M. Zhang, A. Ajji, M.A. Huneault, May 2004
Low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) blown films differ greatly in tear strength anisotropy as LDPE generally exhibits MD>>TD tear resistance while LLDPE shows greater TD tear resistance values. In this paper, we examine the role of LLDPE/LDPE blend compositions on tear strength anisotropy and on the crystalline morphology developed during the blown film process. The crystalline morphology and orientation were measured using microscopy and infrared spectroscopy. Blending of LDPE into LLDPE suppressed the development of superstructure of LLDPE. Infrared studies suggested that both the a- and c-axes are oriented towards MD for high LDPE concentration blends. c-axis orientation gradually shifts from MD to the perpendicular plane as LDPE content decreases, accompanied with an increase of a-axis orientation in MD. Correlation between the tear resistance and the crystalline lamellae orientation is discussed.
LLDPE Blown Films Property Enhancement through Coextrusion
S. Elkoun, M.A. Huneault, X.M. Zhang, K. McCormick, F. Puterbaugh, L. Kale, May 2004
In this paper we investigated the performance of multilayer co-extruded LLDPE blown films. We compared five-layer films with monolayer dry-blended films and highlighted the effect of layer composition and layout on the end-use properties of the co-extruded films. Three different LLDPEs were used: a conventional Ziegler-Natta LLDPE gas phase butene copolymer, an advanced Ziegler-Natta LLDPE solution octene copolymer and a single site LLDPE solution octene copolymer. Numerous five-layer co-extruded structures comprising the single site resin and the other two Ziegler- Natta resins were produced. The coextruded structures composed of the LLDPE butene and the single site resin offer improved tear performance, relative to monolayer blended films; this was assumed due to the presence of interfacial transcrystalline layers. Also, blends of the single site LLDPE and the advanced Ziegler-Natta LLDPE octene resins within selected layers of coextruded films showed slightly enhanced tear resistance. Finally, it was found that haze is significantly reduced when the outside layers are composed of the single site resin. IntroductionA large proportion of the Linear Low Density Polyethylene (LLDPE) production is processed into thin films through the film blowing process and used as flexible packaging. An increasing number of PE film producers are equipped with multilayer blown film lines which offers more flexibility in product design and cost reduction. Consequently, it is not surprising to find in the literature several papers exploring the advantages of coextruded structures [1-4].In this work, we first compare the end-use properties of LLDPE-based coextruded blown films with monolayer blended films and then investigate the effect of layer composition and layout on film performance.
Extrusion Foaming of TPVs Using Water-Filled Polymers
Lorin H. Beaber III, May 2004
A novel, physical foaming agent, ‘water filled polymer,’ has been proven successful in producing low density foamed TPV profiles on standard single screw extruders. Extrusion processing parameters and physical properties (cell size, cell shape, tensile properties, specific gravity, compression load deflection, compression set, surface smoothness and water absorption) of TPV foamed profiles are reviewed. These results are compared to results from other types and forms of foaming agents used to produce foamed TPV profiles.
Orientation and Property Correlation on LLDPE Blown Films
H.Y. Chen, C.C. Chau, T. Butler, B. Landes, M. Bishop, D. Bellmore, S.P. Chum, C. Dryzga, May 2004
The orientation and property correlation of polyethylene (PE) blown films has been studied. A LLDPE polymer (DOWLEX* 2045A) was used to fabricate films at different conditions with blow up ratio, die gap, and frost line height as the variables. The White-Spruiell orientation factors of crystal unit cells, amorphous chains, and lamellae were determined from wide-angle X-ray diffraction pole figure, birefringence, and SAXS. It was found that Keller-Machin type 1 row structure exists in these LLDPE blown films. A correlation between the orientation of each element of the morphology hierarchy has been revealed. Key mechanical properties including Elmendorf tear, dart impact, and tensile strength in both MD and TD have been determined. These properties have been correlated to the orientation. These correlations have been linked to underlying morphology and microdeformation mechanisms.
Enhancement of Poly (L-Lactide) Properties through Nanocomposite Formation
Bret H. Calhoun, Jeremy Swanson, Graham Behringer, Robert B. Moore, May 2004
Nanocomposites are materials that exhibit a change in composition and structure over a nanometer length scale. In many cases, these systems have shown remarkable property enhancements compared to traditional polymers. Recently, poly (L-lactide) (PLLA) has received considerable attention because of its “green” nature. However, the end-use properties of this biodegradable polymer typically fall short of typical petroleum based polymers. Therefore, PLLA/montmorrilonite nanocomposites have been prepared via solution blending in an attempt to enhance the properties of PLLA.
Mechanisms of Clay Exfoliation in a Polymer Matrix during an Extrusion Process: A Structure-Property Relationship
C.Y. Lew, W.R. Murphy, G.M. McNally, K. Abe, S. Yanai, G.P. Brennan, May 2004
Polymer-organoclay nanocomposites were prepared by melt extrusion techniques, employing different processing conditions and material formulations. The structure-morphology relationship of the nanocomposites was analysed using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD). Results from the rheological study showed significant correlation between the dynamic rheology of the polymer melt during the extrusion process, and the exfoliation mechanism of the organoclay layered-silicate observed in the WAXD diffractogram and TEM analysis. Results also indicate that the exfoliation process in the extrusion environment could be achieved through different mechanisms and these mechanisms can be optimised by adoption of different extrusion processing conditions and material formulations.
A Study on Intercalation and Exfoliation of Layered Silicate Nanoparticles in Thermoplastic Polyurethanes
Asim Pattanayak, Sadhan C. Jana, May 2004
Thermoplastic polyurethanes serve as an attractive system for the study of intercalation and exfoliation of layered silicate nanoparticles. The clay galleries are easily intercalated by low molecular weight diisocyanates, polyols, and butanediol before carrying out condensation polymerization. A majority of existing studies reported intercalation and subsequent polymerization in solutions and obtained fully exfoliated clay structures, although industrial implementation of such technology requires development of bulk polymerization schemes.In this study, we utilized the unreacted isocyanate groups in the chains of prepolymer and chain extended polymers to tether nanoclay particles and studied the properties of the resultant materials produced by sequential addition of organically treated silicate particles into prepolymer and to the fully formed polymer chains. As high as 216% increase in tensile strength and 87 % increase in elongation at break were observed with 1-2 wt% organically treated clay particles.
Introducing a New Miniature Mixer for Specialty Polymer Blends and Nanoscale Composites
O. Breuer, U. Sundararaj, R.W. Toogood, May 2004
A new miniature mixer for polymer blends and nanocomposites has been designed. This mixer uses a single, asymmetric rotor spinning within a cylindrical cavity, for elongational and high-shear mixing. The mixer was evaluated by comparing its performance with an internal mixer and a MiniMAX molder. Both immiscible polymer blends and vapor grown carbon fiber (VGCF) composites were prepared using several mixers, and their morphology was studied. The new mixer was generally found to create a well-dispersed and uniform morphology, with results comparable to those of an internal mixer.
Preparation and Mechanical Property of Synthetic Zirconium Phosphate-Epoxy Nanocomposites
K.T. Gam, N. Bestaoui, N. Spurr, A. Clearfield, H.-J. Sue, May 2004
The morphology and mechanical property of synthetic zirconium phosphate (ZrP) - epoxy nanocomposites were studied. The nanocomposites were characterized using wide angle X-ray scattering and transmission electron microscopy to confirm the exfoliation of the ZrP layer structure in epoxy matrix. The mechanical property and fracture toughness (KIC) of ZrPepoxy nanocomposites were studied using dynamic mechanical analysis, tensile tests, and single-edge-notch three-point-bend test methods. The rubbery plateau modulus of the surface modified ZrP-epoxy nanocomposite (M-ZrPNeat) is found to be about 4.5 times higher than that of the reference epoxy. The tensile modulus of the M-ZrP-Neat nanocomposite is increased by 50% with only 1.9 vol% of ZrP addition. However, the elongation at break was decreased drastically.
Mechanism of Exfoliation of Nanoclay Particles in Epoxy-Clay Nanocomposites
Jonghyun Park, Sadhan C. Jana, May 2004
In this study, a rheological interpretation of exfoliation of clay particles was proposed using experimental observations in the curing of organically treated nanoclay- Epon828 mixtures with three curing agents. The elastic force exerted by cross-linked epoxy molecules inside the clay galleries was found responsible for exfoliation of clay layers from the intercalated tactoids. Complete exfoliation of clay galleries was observed under the conditions of slow increase of complex viscosity and fast rise of storage modulus. Gel time presented an upper bound of time available for exfoliation. Faster intra-gallery polymerization, although expedited clay exfoliation, was found to be not a necessary condition.
Epoxy-Aided Dispersion of Nanoclay in PMMA
Jonghyun Park, Sadhan C. Jana, May 2004
The dispersion of organically treated nanoclay particles in thermoplastic polymers using thermosetting epoxies was investigated using polymethylmethacrylate (PMMA) and a mixture of aromatic and aliphatic epoxies. The values of tensile and impact strengths of the resultant composites were compared with PMMA-clay, epoxy-clay, and PMMA-epoxy composite systems. It was found by wide-angle-x-ray diffraction (WAXD) and transmission electron microscopy (TEM) that epoxy helped produce exfoliated clay structures, although the exfoliated clay particles remained inside phase separated domains of epoxy of ~1?m in diameter. Nevertheless, tensile and impact strength improved by respectively 40% and 25% for clay loading of 2wt% over both PMMA and PMMA with 2wt% clay.


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