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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
Hybrid PANI/CNT Nanocomposites Prepared by an Inverse Emulsion Polymerization Technique
Ran Y. Suckeveriene, Guy Mechrez, Moshe Narkis, May 2014
Carbon nanotubes (CNT) have drawn much attention in recent years. CNT have remarkable properties i.e. mechanical properties, electrical and thermal conductivity, thus offering opportunities for development of new nanocomposites. An homogeneous dispersion of nanoparticles in polymers using conventional processing techniques is difficult to produce since nanoparticles tend to agglomerate, thus efficient methods for agglomerate breakdown have been sought in recent years. The combination of CNT with intrinsically conductive polymers may lead to new and improved properties of the resulting materials. This work describes an in-situ inverse emulsion polymerization method of aniline in the presence of multiwalled carbon nanotubes (MWNT) in organic solvents using ultrasonication. PANI dispersion, as a reference, and the PANI/MWNT dispersions were stable for long periods of time without visible precipitation. Highresolution scanning electron microscopy (HRSEM) has shown that MWNT are coated with PANI, leading to a remarkably improved dispersability of the nanotubes, thus PANI coating reduces the tendency of MWNT to reagglomerate. The neat MWNT have a diameter of ~10nm, while the core-shell MWNT/PANI nanofibers exhibit a diameter of ~40nm. The dispersions obtained may have important potential applications in the fields of sensors, acoustic actuators, semi-conductors, solar cells and more. CNT containing materials suitable for the manufacture of thin, transparent, electrically conductive films have poor mechanical properties and are expensive. Our work on hybrid conducting nanocomposites has led to a remarkable combination of high conductivity and transparency along with low haze and good mechanical properties, aiming at competing with the existing ceramic materials, such as Indium Tin Oxide, (ITO).
Highly-Tunable Polymer/CNTs Nanostructures: A Rapid and Facile Approach for Controlled Architecture and Composition
Guy Mechrez, Ran Y. Suckeveriene, Moshe Narkis, Ester Segal, May 2014
This research presents a new fabrication method for tailoring polymer/carbon nanotubes (CNTs) nanostructures with controlled architecture and composition. The CNTs are finely dispersed in a polyacrylate latex, via ultrasonication, followed by a microfiltration process. This step allows preserving the uniform dispersion structure in the resulting solid nanocomposite. This original fabrication method is applied for supercapacitorc, biocatlytic membrane and low reflecting coatings. The combination of microfiltration and proper choice of the polymer latex allows the design of complex nanostructures with tunable properties e.g., porosity, mechanical properties. An important attribute of this methodology is the ability to tailor any desired composition of polymer-CNTs systems, i.e., nanotubes content can practically vary anywhere between 0 to 100 wt%. Thus, for the first time a given polymer/CNTs system is studied over the entire CNTs composition, resembling immiscible binary polymer blends. The polymer in these systems exhibits a structural transition from a continuous matrix (nanocomposite) to segregated domains dispersed within a porous CNTs network. An analogy of this structural transition to phase inversion phenomena in immiscible polymer blends is suggested.
High-Temperature Steam-Treatment of PBI and Its Blends with PEEK and PEKK: A Solid-State NMR Study
Jacqueline C. Pope, Janet Blümel, Tim Bremner, May 2014
Blends of polyaryletherketones (PAEK), such as polyetheretherketones (PEEK) and polyetherketone-ketones (PEKK), with polybenzimidazole (PBI) are of commercial interest due to their improved high-temperature stability and wear properties. Regarding the PBI component, the origins of the properties that are generally thought to be disadvantageous in thermally or chemically aggressive environments are not well understood. The same accounts for the specifics of the interactions between the PBI and PAEK components in melt or dry blend systems. In this presentation, we focus on the molecular changes of PEEK-PBI and PEKK-PBI blends and their pure components after treating them with liquid water and steam at elevated temperatures and pressures. The pure polymer components and the PAEK-PBI (50:50 wt%) blends are steam-treated at 150 °C (302 °F) and 315 °C (599 °F), also with deuterated water (D2O). The overall goal is to understand the chemical changes on the molecular scale that might take place upon high-temperature steam-treatment and to examine the extent and reversibility of moisture uptake. Changes of the materials, as well as interactions and reactions of the water with the functional groups of the polymer components have been studied by 15N and 13C CP/MAS, 2H MAS, and 1H wideline NMR spectroscopy, in combination with using deuterated water.
Influence of Cellulose Fiber on the Foaming Behavior of a Polypropylene Copolymer
Bernd Geissler, Anna Uray, Stephan Laske, Clemens Holzer, Günter R. Langecker, May 2014
This paper investigates the effect of different cellulose fiber grades on the rheological properties and the foaming behavior of a linear polypropylene copolymer. Three cellulose fiber grades with different fiber lengths were used in this study. The average length of the fiber grades were 300 ?m, 500 ?m and 700 ?m. The preparation of the compounds were carried out on a co-rotating twin screw extruder and the foaming experiments were executed with a grooved feeded 45 mm single screw extruder. For the foaming experiments supercritical CO2 was used as blowing agent. All compounds were characterized with a cone plate rheometer to compare the influence of the fiber length and the amount on the rheological properties. The different formulations were compared, due to their effect on the maximum cell density, in terms of cell size and the foam density. It was shown that the effect on the materials viscosity increases with increasing fiber length. The foam morphology was not affected by the fiber length. However the volume expansion ratio depends on the fiber length.
Styrene-Butadiene Rubber- Surface Modified Carbon Nanotube Nanocomposites: Morphology, Rheology and Dynamic Mechanical Properties
Sateesh K. Peddini, Clive P. Bosnyak, Nancy M. Henderson, Christopher J. Ellison, Donald R. Paul, May 2014
Because of the exceptionally high modulus of multiwall carbon nanotubes (MWCNT), they can be used as reinforcing fillers in polymer and rubber nanocomposites. However, the commercial implementation of such nanocomposites has generally been met with very limited success owing to poor dispersion of the MWCNT in the polymer matrix. A strategy that overcomes many of these difficulties is described here with a view towards replacing a portion of the carbon black or silica with MWCNT for improved elastomer performance. Tire treads are very prone to experience micro-cracking at the edges, which eventually leads to overall failure. MWCNT can serve as good bridging elements to avoid the growth of micro-cracks if they are well dispersed and discreet in the rubber matrix. A concentrated, easy to process MWCNT-rubber masterbatch, with the freedom of diluting to various lower loadings, and feasibility of blending with different rubbers, would be of commercial benefit to the tire industry. Discreet oxidized MWCNTs were dispersed in an SBR matrix and the rheology, tube dispersion, dynamical mechanical, and electrical properties of these composites were examined. Morphology and mechanical properties of the cured nanocomposites were investigated and related to the effective aspect ratio of MWCNTs.
Quinacridones – A High Rolling Performance Overview and Winning Styling Options
Michael Willis, May 2014
Quinacridone chemistry provides impressive high performance organic pigments for diverse applications and industries. These heterocyclic compounds achieve color range abilities through auxochromic substitutions such as methyl and chlorine groups, as well as polymorphism. Solid solutions of mixed quinacridone molecules further the already expansive coloring options. Chemical fortitude of lightfastness, bleed and heat resistance can generally be attributed to molecular lattice interactions and surface chemistry. With bright tones and good tinting values, quinacridone pigments permit coloration with high performance characteristics. This paper provides an overview of quinacridone pigments from molecular identification to color point position as well as typical polymer suitability and performance.
Graphene-Based Multilayered Poly(Methyl Methacrylate) Nanocomposites via Forced Assembly Coextrusion
Xiguang Li, Gregory B. McKenna, Guillaume Miquelard-Garnier, Alain Guinault, Gilles Regnier, Artur Rozanski, May 2014
The ability to achieve enhanced mechanical properties through in-plane orientation of platelet-like nanofillers is a challenge for nanocomposite fabrication and performance. Here we use forced assembly to orient graphene nanoplatelets in PMMA/PMMA-graphene films produced through multilayer coextrusion. Electron microscopy confirms the alternating layer structure of PMMA and PMMA containing oriented graphene. Relative reinforcement of 11 % at a concentration of 0.2 wt % graphene in the total film was achieved without loss of toughness. The reinforcement is attributed to the planar orientation and improved dispersion of the graphene as the layer thickness decreases.
Controlled Migration of Antifog from Flexible Polyethylene Films
Jasmine Rosen Kligvasser, Ran Y. Suckeveriene, Roza Tchoudakov, Moshe Narkis, May 2014
Antifog (AF) agents are chemicals that prevent the condensation of water as small droplets on hydrophobic surfaces which resemble fog. Antifogs function by minimizing the water surface energy, thus resulting in a continuous film of water rather than single droplets. Inside a greenhouse, the temperature and humidity are usually higher than the outside temperature and fog will thus appear on the inner surface of the PE film. In the present work, a new method of controlled migration of AF is described, by grafting AF molecules to the surface of sub-micron inorganic particles. Glycerides and fatty acids are used as AF. During the grafting reaction two fractions are formed: attached AF fraction to the inorganic particles’ surface, a fraction which cannot be detached by extraction, and an unreacted, thus unattached AF fraction. Aging tests, developed in the present work, have shown a significant decrease of the AF migration rate.
Investigation of Chemically Aged Elastomers Based on Analytical Methods
Nabila Rabanizada, Michael Johlitz, Alexander Lion, May 2014
For over one hundred years, components made of elastomers have been commonly used in practice. However, the knowledge concerning the aging behavior of the material lags behind the existing demands of modern day industries. The property spectrum of elastomeric components extends across a broad range. Areas of application for such materials include aerospace, automotive, and mechanical engineering, plant construction, shipbuilding and civil engineering sectors. When considering the moldability, workability, flexibility and adhesion of elastomers, it is unsurprising that these materials are employed in so many industries. Yet, despite their application in numerous fields, only limited amounts of research has been carried out concerning these materials, and hardly exceeds basic examinations. Hence, intensive studies are necessary in this area. Previous research has already verified that the mechanical properties of elastomers change over time. These scientific findings make intensified research regarding the long-term behavior of elastomers indispensable. Chemical aging studies are highly significant, because the molecular structure and the networking of the material change during the aging process. Due to these changes, various material properties may also alter. In order to be able to make more accurate predictions concerning the life span and durability of elastomeric components, all environmental influences must be intensively researched experimentally. Basic research in the field of chemical aging is essential. In this paper, the aging behavior of natural rubber was tested using the media air, distilled water, and 3%- and 6% de-icing salt solutions.
Using Twin Screw Extrusion Technology to Determine the Effects of Surfactant Concentrations by Melt Blending Organoclays with PET Nanocomposites
Karnik Tarverdi, Peter Allan, Somchoke Sentikaew, May 2014
The effects of the use of a surfactant for the dispersion of the nanoparticles in a nano-clay/PET composite have been evaluated. An increase in the amount of surfactant improved the dispersion of the particles and consequently led to an enhancement of the mechanical properties of the nanocomposite. The composites were melt-blended using co-rotating intermeshing twin screw extrusion technology and although there was degradation of the surfactant during processing, it did not affect the dispersion of the nano particles in the PET. A range of techniques used to characterise these materials will be discussed, including morphology, differential scanning calorimetry, (DSC), Scanning electron microscopy (SEM), including experimental techniques like mechanical property evaluations.
Biobased Fillers for Polypropylene for Interior Application
Ayse Ademuwagun, Joel Myers, May 2014
Coconut shell and torrefied wood are bio-sourced and renewable materials that can be used as fillers in various polymer matrices. Torrefied wood material can be produced from numerous cellulose based materials, such as wood, sunflower hulls, flax shive, hemp and oat hulls. These bio-fillers would replace talc and glass bubbles which are not a renewable resource. Additionally, the implementation of torrefied wood and coconut would reduce the carbon footprint and improve sustainability of Hyundai and Kia vehicles. In this study, coconut and torrefied wood filled polypropylene properties are tested for a HVAC Case application.
Functional and Design Opportunities Using Physical Vapor Deposition and UV Curable Coatings
Eileen Weber, Jason Eich, Phil Abell, Kristy Wagner, Chris Mack, May 2014
Interest in alternatives to electroplated chrome is expanding dramatically. Color and appearance affects are limited with traditional chrome electroplating and successful “paint-on-chrome” applications are expensive and highly proprietary. Collectively the automotive, home appliance and cosmetic market are actively searching for alternatives with the appearance and durability of electroplating, but without the environmental side effects, appearance and functional design limitations, and costs associated with this decades old process. “Chrome look” processes and coatings for decorative and automotive lighting PVD applications have been used in the UV curable coating industry for over twenty years. As development of UV curable coatings for PVD has progressed, so has the understanding of the process and its unique capabilities and applications. This paper will address the advantages of PVD as a chrome alternative to include functional / design capabilities that are either cost prohibitive, or impossible to achieve with electroplated applications, as well as describe some of the tradeoffs associated when using coatings systems as an alternative for chrome electroplating.
Experimental Examination of Gap Bridging in Contour Welding
Dirk Bonefeld, Patrick Lakemeyer, Volker Schöppner, May 2014
Because of the many advantages of laser transmission welding such as high-precision energy input and very fine weld seams, the process is used in a wide variety of applications in, for example, medical technology and the automotive industry. To join together large parts, use is frequently made of contour welding because the process combines good flexibility with a considerable amount of freedom regarding the geometry [1]. Contour welding also offers the possibility of producing complex, robot-controlled free-form weld geometries. At the same time, however, the process does have disadvantages. Because the contour welding process involves guiding a beam with relatively high energy density slowly along the seam, the melt pool is very small. In front of the beam, the material is not yet plasticized, and behind it, the melt has cooled down again, making it virtually impossible to produce any meltdown without the parts becoming tilted. Even with complicated clamping devices, perfect contacting conditions are almost impossible to achieve. Especially in the presence of production-related distortion or surface tolerances, air gaps can form between the parts, which act as thermal insulators. In the areas close to the surface of the absorbing part, the laser beam is then converted into heat. This heat is dissipated only into the absorbing part (largely through thermal conductivity) and is not transmitted into the transparent part. This can lead to an undesirable temperature increase, resulting in thermal decomposition of the absorbing part. Knowledge of the relationships between process parameters and the quality of the manufactured part is therefore essential. In the tests described here, the gap-bridging capacity of semi-crystalline (PA 6.6) and amorphous (PC) materials is examined in more detail in relation to the process parameters. For experimental studies a special specimen geometry was used. A result of this study is the high influence of the geometry of the gap, beside
Effect of Surface Treatment on the Mechanical Properties of Wood-Plastics Composites Produced by Dry-Blending
Ambre Verdaguer, Denis Rodrigue, May 2014
In this work, wood-plastics composites (WPC) were produced by a simple dry-blending technique. In particular, the effect of wood surface treatment with maleated polyethylene (MAPE) is presented. The effect of wood content was also studied by using different concentrations (0, 10, 20 and 30% wt.) and the samples were mechanically characterized in terms of tensile, torsion, and flexural properties. From the tensile stress-strain curves, modulus, strength, and strain at break are reported, while only shear and flexural moduli were studied for torsion and bending tests. The results show that simple dry-blending can be used to produce homogeneous ultra-high molecular weight polyethylene (UHMWPE)/maple flour composites and that surface treatment can improve the moduli by up to 110%.
Polypropylene and Polypropylene-SEBS Blends for Medical Films
Martina Sandholzer, Katja Klimke, Klaus Bernreitner, May 2014
Due to the negative publicity of PVC [1], polypropylene is attracting increasing attention as an alternative material for flexible medical packaging, such as bottles, films and for disposable medical items. Propylene-ethylene random copolymers are usually the materials of choice as they are suitable for the preparation of transparent films and transparent molded items that can withstand steam sterilization. External elastomers such as stryrene-ethylene/butylene-styrene triblock-copolymers (SEBS) usually need to be added to achieve the desired stiffness (softness) of the final item. In the current study, it was demonstrated that modifying random copolymers with SEBS also improves the toughness and the optical properties of films. The second part of the study investigated whether the use of random-heterophasic polypropylene copolymers instead of random copolymers would allow for a reduction of the costly SEBS elastomers. This study showed that random-heterophasic polypropylenes containing a significantly reduced (30%) amount of SEBS or even containing no SEBS at all can in fact achieve the same performance as SEBS modified propylene-ethylene random copolymers. These results illustrate that random-heterophasic copolymers are an attractive alternative to propylene-ethylene random copolymers as they allow for a reduction of costly SEBS in medical packaging systems.
Artificial Weathering of Materials Used in Collapsible Fuel Storage Tanks
James M. Sloan, D. Flanagan, P. Touchet, H. Feuer, May 2014
The purpose of this work was to perform a comparative analysis of various candidate nitrile coated fabric materials supplied by potential vendors to be used as fuel storage tanks and compare the results to the currently fielded polyurethane storage tanks. Our strategy is to utilize advanced environmental aging methods to simulate extended weathering conditions. Our results demonstrate that the nitrile coated fabrics performed well in our evaluation. Their breaking strengths are about equal to the currently fielded urethanes and they performed comparably when subjected to environmental aging conditions.
Confounding of Hydrolytic Stability Results by Physical Aging
James De Rudder, Robert R. Gallucci, Amanda M. Flores, May 2014
Determining the correct test method to predict the real-world behavior of a resin can be challenging. For hydrolytic stability, various industries measure a resin’s ability to maintain key properties following exposure to elevated temperature and humidity (hydroaging). One of the properties frequently requested for testing is the notched Izod impact. In this paper, it will be discussed why the results of notched impact testing following hydroaging are actually confounded. Other methods for monitoring a resins hydrostability will be suggested.
Molded-On Mechanical Fastener Ensures Uniform Force Transmission and Sealing of the Joint Surface: Joining Parts Together with the Aid of Self-Tapping Screws
Elmar Moritzer, Jens Krugmann, May 2014
While metal rivet connections have been the subject of widespread research in the past and have since become particularly well-established for use in lightweight structures [1], the field of plastic rivet fasteners still needs to be researched as it holds significant potential. The fastener system presented here is one possible solution and is seen as a viable alternative to existing connections. The direct molding-on of a boss with an optimized geometry produces a mechanical fastening element, which, in the finished component, produces a sealing undercut due to a uniform force transmission. The method of direct screwing plays an important role in the development of the new fastening solution. The insertion of the thread-forming or self-tapping screw produces the tension needed for compression of the boss, and, together with the necessary pre-load force, thus ensures a reliable connection. The mechanical fastener system was studied in various sizes in order to be able to perform a scale-up of the fastener system. This publication is related to the results of the mechanical fastening element for a nominal screw diameter of 4 mm. The results of the plastic fastener for a nominal screw diameter of 6 mm are presented in [2].
Influence of Mineral Fillers on the Flame Retardancy of Expandable Graphite / Polypropylene Materials
Hannelore I. Mattausch, Stephan Laske, Dieter Hohenwarter, Clemens Holzer, May 2014
Halogen-free flame retardant applications attract great interest of industry as well as of research. Most commercial available flame retardants for polypropylene have to be used with high filler loading, which leads to difficulties in processability, poor mechanical properties and unfavorable cost performance. Therefore it is important to gain fundamental knowledge about synergistic combinations of flame retardants and filler to reduce all disadvantages. In this research the combustion and burning behavior of expandable graphite polypropylene compounds with various mineral fillers were investigated. The results of the burning and combustion characterization were different and also partly contradicting. Combined compounds with EG and additional fillers obtain good results for protecting the material against combustion, while compounds filled with expandable graphite, layered silicates or zeolite show good protection against burning.
Morphology and its Influence on Rheological Parameters of Nanocomposites Filled with Layered Silicates Based on Polylactic Acid
Bernd E. Haar, Stephan Laske, Petr Stloukal, Sabine Bodner, Clemens Holzer, May 2014
In this research work the morphology of polylactic acid (PLA) filled with various types of layered silicates, as well as its influence on the rheological properties regarding melt strength and complex viscosity, were investigated. Thereby the morphology of the produced nanocomposites were examined with small angle X-ray scattering (SAXS) measurements. For the determination of melt strength a Rheotens apparatus, fed by a bypass system during extrusion, was used. Complex viscosities were measured with a rotational rheometer with cone-plate setup. Results show that the different modifications of the layered silicates have a significant impact on the final morphology as well as on the rheological properties of the produced nanocomposites. Beside different achieved interlayer distances and grades of intercalation of the layered silicates inside the polymer matrix, also increased melt strength as well as increased complex viscosities were observed. Thereby a homogenous dispersion and high grade of exfoliation is also preferable for the production of thin products like films.

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