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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Plasticization of Epoxy Network in Epoxy-Nanoclay Systems Due to Stoichiometric Imbalance
It was recently found that the ratio G'/?* plays an important role in determining whether exfoliated or intercalated nanoclay structures can be obtained in epoxynanoclay systems; G' and ?* are the storage modulus and complex shear viscosity of crosslinking epoxy respectively inside and outside the clay galleries. In this study, the possible effects of quaternary ammonium ions on the values of G'/?* ratio were investigated. The first effect was that of plasticization of crosslinked epoxy networks inside the clay galleries by hydrocarbon chains of quaternary ammonium ions, which slowed down the growth of G'. Second, the quaternary ammonium ions derived from primary amines dissociated at elevated temperatures generating amines, which reacted with the epoxide groups, causing an imbalance in stoichiometry. This led to reduction of crosslink density and further plasticization by excess amines.
Specialty Additives Based on Controlled Architecture Material (CAM) Technology: Interfacial Modifiers in Blends, Foams and Composites
Controlled architecture materials (CAMs) (block copolymers, telechelic polymers, starbranched polymers) are being explored as specialty additives for a myriad of melt-processing related applications. These block copolymer-based additives provide interesting solutions to interfacial problems in areas such as blend compatibilization and polymer wood composites. In addition to providing enhanced physical properties and performance, these additives can also aid in the processibility of polymers under extrusion conditions.
New Chemistry for Manufacture of Improved Styrenic Plastics
Of the multitude of polymerization processes available for plastics manufacture, continuous free radical polymerization is preferred because it offers the lowest monomer to polymer conversion cost. However, free radical polymerization offers very poor control of polymer chain architecture because of the multitude of simultaneous termination processes. This leads to the formation of a broad polydisperse resin. In recent years there has been a large global research effort aimed at developing controlled radical polymerization (CRP) technology. CRP provides control of termination by the addition of a stable free radical to the polymerization process. The stable free radical reversibly couples with propagating polymer radicals thus virtually eliminating uncontrolled termination. CRP allows researchers to synthesize new polymers previously inaccessible by conventional polymerization chemistry. This discovery has led to a renaissance in polymer science and has resulted in the development of several new living polymerization processes. CRP technology has given polymer researchers the ability to synthesize advanced macromolecules with control over shape, size and functional group placement not possible using traditional free radical processes. However, to date there has been slow commercial implementation of CRP technology, especially in commodity polymer businesses requiring the lowest conversion cost possible, at the sacrifice of improved plastic performance. This paper describes our research probing the utility and limitations of CRP for the manufacture of improved styrenic resins.
Nanocomposites of Polytrimethylene Terephthalate and Montmorillonite Clay
Polytrimethylene terephthalate (PTT), known as SORONA™, polymer is an example of a condensation polymer that can be made from 1, 3-propanediol and terephthalic acid. Nanocomposites of polytrimethylene terephthalate and organoclay were fabricated in microcompounding equipment. Injection molded samples of these materials were evaluated by mechanical and thermal analysis. To understand the role of clay platelets in the nanocomposites, the microstructure was observed using transmission electron microscopy (TEM) and wide angle X-ray scattering (WAXS). These nanocomposites showed improvement in properties and strong promise for further improvements through process optimization and material combinations.
On-Line Measurement of Dispersion in Nanocomposites
Properties of polymer-clay nanocomposites depend on the degree of dispersion of clay in the polymer matrix. Currently off-line techniques such as transmission electron microscope and x-ray diffraction are used to determine dispersion. This research aimed to determine a property that is affected by dispersion and has the ability to be measured on-line. Polypropylene and Cloiste 15A (nanoclay) were melt blended with the aid of maleic anhydride grafted polypropylene compatibilizer. The mechanical, electrical, optical, and rheological properties were measured for all the trials. Transmission electron microscopy was performed to evaluate the results. The capacitance of the nanocomposites varied with change in the degree of dispersion. The mechanical properties (tensile characteristics) did not show a significant change with dispersion. The rheological properties gave a good indication of exfoliation of clay layers at low shear rates. The visible color test could not give a definite indication of dispersion as compared to the other properties.
Structure and Property of Polyester Composite Fibers Reinforced with Thermotropic Liquid Crystal Polymer
The composite fibers based on melt blends of poly(ethylene 2,6-naphthalate) (PEN), poly(ethylene terephthalate) (PET), and a thermotropic liquid crystal polymer (TLCP) were prepared by a process of melt blending, and spinning to achieve high performance fibers with the improved processability. The tensile strength and modulus of the composite fibers can be significantly improved by both the reinforcement of the polymer matrix by the TLCP component and the TLCP fibrillar structure with their high aspect ratio. The increase in the apparent crystallite size with the spinning speed resulted from the development of larger crystallites and more ordered crystalline structure in the composite fibers. As the spinning speed was increased, the birefringence and density of the composite fibers were increased, indicating the improvement of the molecular orientation and the effective crystal packing.
Mechanical Morphology and Thermal Properties of Water-Crosslinked Wood Flour Reinforced Linear Low-Density Polyethylene Composites
Wood flour (WF) reinforced linear low-density polyethylene (LLDPE) composites were prepared. Water-crosslinking technique was used to improve the physical properties of composite. Composites compounded in a twin screw extruder and treated with a coupling agent (vinyltrimethoxysilane, VTMOS) and then be moisture-crosslinked. Composite after water-crosslinking treatment exhibited better mechanical properties than the non-crosslinked one because of the improved chemical bonding between the wood fiber and the polyolefin matrix. Scanning Electron Microscopy (SEM) of the fracture surfaces of water-crosslinked composites showed superior interfacial strength between the wood fiber and the polyolefin matrix. Thermal analyses of water-crosslinked composites indicate that thermal degradation temperature of composite increase with the increasing water-crosslinking time.
Study of High Abrasion Resistant UPR/SiO2 Nanocomposites Prepared by an In-Situ Polymerization Process
Abrasion-resistant nanocomposites, unsaturated polyester resin (UPR)/ silicon dioxide (SiO2), were prepared by an in-situ polymerization process. The effects of nano-SiO2 on the chemical-physical properties of UPR/ SiO2 nanocomposites were studied by performing thermal, morphological, and mechanical analysis, and the abrasion resistance has also been evaluated. The results show that UPR/ SiO2 nanocomposites have an average weight loss about half in comparison with that of neat UPR by adding only 2% of nano-particles. The glass temperature (Tg) of composite materials were measured by DSC. It is found that the Tg of composite materials is higher than that of UP resin, which is in agreement to the results of abrasion resistant properties. The in-situ UPR/SiO2 that reacts a good distribution of nano-SiO2 in the UPR has a better toughness and strength.
Flexural Properties and Morphology of Impact Modified Epoxy-Organoclay Nanocomposites
The flexural and impact properties as well as the morphology of epoxy-organoclay nanocomposites were investigated in this study. The epoxy matrix was impact modified with a polyol which formed an immiscible phase in the epoxy. X-ray Diffraction patterns showed that the interlayer spacing of the modified montmorillonite expanded from 1.83 nm to 3.82 nm when it was incorporated into the impact modified epoxy matrix. Synergistic effects in mechanical properties were observed in samples containing 1 wt % polyol plus 1 wt % organoclay. In these samples, the impact strength of the neat resin increased by 120 % with respect to the impact strength of the neat epoxy resin.
Study on Morphology Development for In-Situ Fiber Reinforced Composites by Blending Polypropylene and Polycaprolactone
In-situ fiber reinforced composites were prepared by blending of polyolefin and polycaprolactone. The dispersions in this blend materials were deformation into fibers using a polymer extrusion. Polymer processing conditions, such as drawing ratio, were measured to study its effect on elongation of dispersed phases. The dispersions have dramatically changed from spherical to spheroidal and filament shapes depending on drawing ratio. Reduced capillary number was used to characterize droplet deformation, thus giving us many informations on fiber formation of the dispersions.
Mechanical and Morphological Properties of Kevlar-Fiber Reinforced Polyamide 6,6 (PA66) Composites
The effects of fiber loading and surface treatment on the mechanical and morphological properties of nylon 6 (PA66)/Kevlar composites were studied. The effect of fiber surface treatment on modulus is not pronounced for 10% Kevlar fiber-reinforced composite (KFRC) but it succeeded in enhancing modulus in 24% KFRC. The reinforcement of PA66 by Kevlar fibers was indicated by the increase in tensile strength with increasing fiber content. However, there was no evidence to suggest that the surface treatments have any significant effect on the tensile strength of the composites. The failure surfaces of both surface treatments are similar to the untreated fiber as indicated by the massive fiber pulled out. However, less fiber splitting can be seen on the failure surfaces of the treated samples. Fiber breakage is also indicative of good interfacial bonding but the massive fiber pullout in high fiber content samples would complement the toughness and strength of the fibers itself.
Preparation of High Barrier Containers Based on Nanocomposies
The current study deals with application of nanocomposies to high barrier products such as blow bottle, sheet, and film. Olefin based barrier containers have been prepared for storage of hydrocarbon solvents. Solvent permeation tests have shown that incorporation of small amount of nano clay particles (3-5%) with appropriate carrier, led to significant reduction of permeation of hydrocarbon solvent by a factor of 40 to 200, compared to neat HDPE.The patent pending technology of the above application based on nano-clay dispersion with a appropriate carrier, which is named as single wall barrier nanocomposite.
Online Determination of Wear Using X-Ray Fluorescence Spectroscopy
According to new developments in the field of X-ray fluorescence spectroscopy (XFS) the wear of processing devices (e. g. plastics processing machines) can be determined. This method allows the determination of the time-dependent development of wear processes. The main advantages of XFS are the broad detection range and the simultaneous detection of different elements. Up to now the analysis of wear is mainly done by means of gravimetric methods. These methods have the disadvantage of slow evaluation and low precision when low abrasive media are used. The disadvantages can be overcome by XFS methods. Some detailed results from studies of wear processes are shown and discussed.
Application and Limitations on Thermal and Spectroscopic Methods for Polymer Shelf-Life Prediction
In medical products, shelf-life after thermoplastic processing and radiation sterilization is important. Previously, we have successfully applied thermal analytical methods to predict shelf-life for many polyolefins. However, as the material of construction becoming more sophisticated: multiphase alloys and blends, multilayer constructions etc., issues existed that require clarification as to what extent these methodologies are applicable.In sharp contrast with previous studies, it was found that complexities through alloying has rendered ineffective the predictive method based solely on thermal techniques. In an expanded study, we employed thermal methods in conjunction with other spectroscopic and morphological methods to study the applicability and limitation of the combined techniques. Results comparing with real life simulated aging experiments are presented in this article.
Gas Chromatography/Mass Spectroscopy for Plastics Failure Analysis
Gas Chromatography/mass spectroscopy is particularly useful as an analytical method for plastics failure analysis in cases where detection of an unknown contaminant or other compositional factor may be the cause or a contributor to failure. It takes advantage of the fact that GC is a method of separating compounds in a mixture, permitting their identification and possibly quantification. MS is not only a very sensitive detector but also gives mass spectra of GC peaks, permitting their identification in many cases.In thermal desorption GC/MS compounds are transferred from the sample to the GC with heat. Completely nonvolatile materials are not detected. Using desorption temperatures up to 300-350°C, many components of plastics can be analyzed. In pyrolysis GC/MS the sample is decomposed at temperatures up to 900°C; GC/MS analyzes the pyrolyzate. Examples are given of causes of plastics failures that have been determined by GC/MS.
FTIR and TOF-SIMS Analysis and Imaging of Cracked Polybutylene Piping
Polybutylene resin was used in the manufacture of water supply piping for a number of years from the late 70's through to the mid 90's. A number of lawsuits were filed in the 1980's to recoup homeowner losses when their polybutylene water pipes failed in service.The cracks in a number of these pipes which had failed in service were examined by Fourier transform infrared spectroscopy (FTIR) suing a microscope attachment. The microscopic FTIR examination of the cracks enabled us to show the location and extent of the oxidative degradation of the polymer. Deconvolution of the carbonyl peak arising from the oxidation provides information regarding the likely functional groups present in the oxidized layer.These cracks were also examined in cross section and plan view using time-of-flight secondary ion mass spectrometry (TOF-SIMS). This very surface sensitive technique enables one to isolate and image the location of specific mass units. The relative compositions of the cracked areas and reference areas will be discussed in terms of the presence and distribution of various mass fragments.
Photo-Induced Scission and Crosslinking in LDPE, LLDPE and HDPE
Chain scission and crosslinking concentrations have been derived from molecular weight distributions obtained by gel permeation chromatography after three weeks and six weeks laboratory ultraviolet (UV) exposure on samples taken at different depths from the exposed surfaces of 3mm thick injection molded bars made from LDPE, LLDPE and HDPE. Degradation was rapid near the exposed surfaces but very little change occurred in the bar centers, due to oxygen starvation. The most rapid rises in scission and crosslink concentrations were observed with LDPE, for which the concentrations after 6 weeks exposure were approximately double those measured after 3 weeks. With LLDPE and HDPE the scission and crosslink concentrations after 6 weeks exposure were much greater than twice those after 3 weeks. Scission dominated over crosslinking at all depths and for all materials and was always ?3, with a value of ~9 recorded for HDPE near the exposed surface after 6 weeks exposure.
Lifetime Prediction of Glass Fiber/DERAKANE 411-350 Composites
The goal of the present effort is to develop and verify a lifetime prediction approach for glass fiber reinforced DERAKANE 411-350 composites subjected to fatigue loading, as well as moisture aging. The approach taken is to use fatigue lifetime data taken from samples that were not aged and use it in conjunction with long-term immersed aging data (for a different laminate), as inputs to a residual strength based lifetime prediction scheme entitled MRLife. We will compare our predicted results to those measured experimentally, and comment on discrepancies observed.
Oxidation Induction Time Analysis of Degradation of Poly(1-Butene) Pipe
The Oxidation Induction Time Test is a powerful technique for evaluating the oxidative stability and or degradation of polymers. It is especially effective in examining the relative utility of antioxidants on the stability of oxidizable polymers. It is also useful in determining whether or not antioxidants have been leached from the polymer, thus negating their effectiveness. In this study OIT has been used to show the loss in antioxidant from the interior surface of poly(1-butene) pipe used to convey potable water. The loss in antioxidant was confirmed by significantly reduced OIT times. Confirmation of oxidation of the polymer was subsequently made by IR analysis.
Newer Compatible Conducting Polymeric Composites for Elimination of Electromagnetic Radiations
Conducting polyaniline composites prepared by using hybrid dopant systems with different loading levels provided highly compatible structures, with a significant increase in intermolecular adhesion. Composites with even lower loading of 1.5% was much efficient to remove the static charge from the surface, while the composites with higher loadings from 20% to 50% were found to be highly efficient for the elimination of electromagnetic interference. A constant increase in shielding value was observed with the increased loading level, followed by a decrease in the tensile strength. Composites shows higher thermal stability while morphological studies represents complete dominance of one phase over the other at higher loading levels. The intermolecular interaction between two different polymeric matrix results in the formation of a thermodynamically homogenous stable structures, resulting the formation of highly compatible conducting composite systems.
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