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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Controlled Epoxy Network Structure-Property Relationships: The Effect of Chain Termination
While epoxy thermosets are commonly used and are best known for their high glass transition temperature (Tg), creep resistance, environmental resistance and high stiffness, they are extremely complicated and intractable to thorough investigation. This is in part due to the fact that these are curing systems and gelation marks a turning point in the system’s performance as well as ability to be probed for effective structure-property relationships. In addition, practical formulations often contain multiple components that have subtle but important interactions to the final performance.In this presentation we will cover work that was performed recently to quantitatively probe the effect of one such practical yet important effect, namely chain termination. The effect of the size as well as flexibility of the chain termination group will be examined via a controlled host matrix chemistry that comprises of DER™ 332 as the epoxy, bisphenol A (BA) as extender and tris(4- hydroxyphenyl)ethane (THPE) as a crosslinker. Data and trends pertaining to Tg, stiffness, yield strength, fracture toughness and thermal expansion coefficient will be discussed.
Evaluation of Thermoset UV Curing Kinetics by Calorimetry, Rheology and FTIR Spectroscopy
UV curable polymer systems are commonly characterized for degree and time of cure by thermal methods such as scanning photocalorimetry. In this work, we modified existing thermal and rheological instruments in order to apply a controllable dosage of UV radiation and compare the curing kinetics of two commercial polyester and epoxy powder coating systems differing in rate of cure. In general, there is an optimal temperature range whereby the material is completely cured. The optimal conditions are generally set for material heated above its flow temperature to cure within 5 seconds of UV radiation. Our thermal and rheological results are in good agreement with each other and with manufacturer's published data employing photocalorimetry. The data were analyzed for temperature dependence and efforts were made to correlate thermal and rheological results with time dependent structural changes monitored by FTIR spectroscopy.
Properties of Siloxane-Modified Epoxy Resins
A diglycidyl ether of bisphenol A (DGEBA) epoxy resin was chemically modified using a silanolterminated polymethylphenylsiloxane (PMPS) and two methoxy-terminated PMPS intermediates with high (3.3/1) and low (0.5/1) phenyl/methyl ratios. At room temperature, the methoxy-terminated PMPS with the high phenyl/methyl ratio was miscible with the epoxy resin and formed a one-phase system; however, both the silanolterminated PMPS and the methoxy-terminated PMPS with low phenyl/methyl ratio were incompatible with the epoxy resin and phase separation occurred. While, at 120?, resins modified with all three PMPS intermediates formed homogeneous solutions. A range of the tensile and the fracture properties of unmodified and modified epoxy systems was obtained by changing the modification method, the concentration and the type of PMPS modifiers, the type of curing agent, and the cure cycle. The modified epoxy systems have slightly decreased tensile moduli. The chemical modification method is more efficient in the improvement of the fracture toughness than the physical blending method. The fracture toughness increases with an increase in PMPS concentration. The silanol-terminated PMPS has a better toughening effect than the two methoxyl-terminated PMPS modifiers. The polyoxypropylene diamine (POPDA) cured epoxy systems have much higher fracture toughness values than the 1,3- phenylenediamine (MPDA) cured epoxy systems.
The Effect of Absorbed Moisture on the Elevated Temperature Properties of Polyetherimide
The effects of moisture absorption on products molded from polyamides are well documented. However, other high-performance materials such as polyetherimide and polyethersulfone also absorb significant amounts of moisture from the atmosphere. Early tests suggest that this moisture absorption influences the glass transition temperature of these polymers. This has implications for short-term elevated temperature service as well as creep resistance and fatigue resistance at lower temperatures. This paper quantifies the effects of absorbed moisture on the elevated temperature properties of polyetherimide and characterizes rates of moisture gain and loss at different environmental conditions.
Measurement and Prediction of Fibre Orientation within a Three-Dimensional Flow
In this paper we describe a comparison of the fibre orientation structures developed in a transverse ribbed plate during injection moulding, with those predicted using the Moldflow commercial software, for a model transverse ribbed component. Fibre orientation measurements were carried out using a large area image analysis system developed at the University of Leeds. Moldflow analyses of the ribbed plate were conducted and compared to measured fibre orientation distributions. Adjustments of the fibre interaction coefficient within Moldflow analyses have yielded significant improvements in model accuracy.
Effect of Freeze-Drying on the Glass Temperature of Cyclic Polystrenes
The calorimetric glass temperature was measured for three cyclic polystyrenes with apparent molecular weights ranging from 4.0 x 103 to 195.5 x 103 g/mol for both bulk material and for samples freeze-dried from dilute solution. Freeze-drying from dilute solution was found to reduce the glass temperature by 7 to 14 K depending on the sample. These Tg depressions are 5 to 12 K greater than those found previously for freeze-dried linear polystyrene. Annealing at 403.2 K and 443.2 K (130 °C and 170 °C) resulted in recovery of the Tg back to the bulk value with the time scales depending on both temperature and the magnitude of the Tg reduction; the low apparent activation energy dependence of the recovery of Tg precludes its being due to viscous flow.
Modeling the Yield Behavior of Glassy Networks using Molecular-Based Parameters
Recent findings suggest that the yield behavior of glassy networks is governed primarily by two molecular based parameters. The first of these parameters is the glass transition temperature, Tg, and reflects the network stiffness including backbone stiffness, crosslink density, crosslink functionality, and other inter and intra-molecular interactions. The second of these parameters is the cohesive energy density, Ecoh, reflects the cohesive strength of the network. In this paper, we present a framework to incorporate these parameters in a molecular-based yield model. We extend the framework to include alterations in temperature, strain rate, stress state, and molecular composition (through these parameters). We also outline current experiments to evaluate the limits and capabilities of the hypothetical model presented and summarize recent findings.
The Temperature Dependent Viscoelastic and Viscoplastic Properties of Nylon 12
We report the viscoelastic and viscoplastic properties of Nylon 12 by treating the polymer as an equivalent network of chains bridged by temporary junctions (entanglements, physical cross-links and lamellar blocks). The network is thought of as an ensemble of meso-regions linked with each other. Tensile tests were carried out with constant crosshead speeds (ranging from 5 to 200 mm/min) from 35 to 140°C using a tensile test machine with an oven attachment. Stress strain relations for uniaxial deformation were developed by using thermodynamic principles. These governing equations involve two material constants that were derived by fitting the experimental observations. Good agreement was obtained between the numerical simulation and experimental data. These results will be used as a basis for characterizing the bending prior to thermoforming of Nylon 12 automotive tubing.
Finite Element Analysis of Hyperelastic Materials: Elastomeric Seal
Seals are critical components in virtually all mechanical devices, which are used for closing the gap and/or to separate two liquids or gasses in static or dynamic applications. But the complexity of seals and the difficulties associated with resolving essential parameters, both material and geometric, have hindered the effectiveness of experimental and theoretical understanding of seal design. The present paper describes the axisymmetric analysis of elastomeric seals at medium strain (strain less than 100%) under static and dynamic conditions using Abaqus software. The stress strain behavior of a black filled ethylene propylene (EPDM) rubber are studied in extension over a range of temperature to examine the validity of Arruda-Boyce, Mooney-Rivlin, Neo-Hooke, Ogden, Polynomial, Reduced polynomial, Van der Waals and Yeoh models. The analytical form for strain energy density function of Arruda-Boyce model gives a very good fit to the experimental data for strains less than 100%, which cover the range of interest for most engineering applications.
Review of the Ultrasensitive Oxygen Consumption Method for Making More Reliable Extrapolated Predictions of Polymer Lifetimes
Predicting polymer lifetimes in air is often based on unconfirmed extrapolations of elevated-temperature Arrhenius behavior. To improve confidence in such extrapolations, we describe an ultrasensitive oxygen consumption approach. Measurements are made at elevated temperatures to confirm correlation between activation energies (Ea) for consumption and conventionally measured properties (e.g., mechanical). In addition, the sensitivity of the consumption approach allows measurements to be made in the lower-temperature extrapolation region, thereby testing whether the hightemperature Ea remains constant.
Real-Time Synchrotron X-Ray Techniques for Polymer Processing Research
The Advanced Polymers Beamline (X27C) at the National Synchrotron Light Source (NSLS), Brookhaven National Laboratory (BNL) was commissioned in January 1997 by Ben Hsiao and Ben Chu from the State University of New York at Stony Brook (SUNY-Stony Brook). This facility is the first synchrotron facility in the United States dedicated to chemistry/materials research (with emphasis on polymers) using combined small-angle x-ray scattering (SAXS) and wide-angle x-ray diffraction (WAXD) techniques. Today, X27C has become a major workhorse serving the U.S. polymer community for time-resolved and in-situ x-ray scattering and diffraction studies. The primary focus of the X27C beamline is to investigate polymer structures, morphologies and dynamics from atomic, nanoscopic, and microscopic to mesoscopic scales in real-time and/or in-situ using SAXS and WAXD techniques. Selected examples of studies carried out in X27C include characterizations of nanocomposites, crystallization, melting and phase transition of polymers, polymer melts and solutions during shear, fiber formation and deformation, high pressure study under supercritical conditions, biopolymers, organic/inorganic hybrid nanocomposites and supramolecular structured biological molecules. In this presentation, we will focus on the current research opportunities of using real-time synchrotron techniques to assist varying polymer processing research.
Some Recent Developments in Melt Rheometry
The linear viscoelastic behavior of the melt provides a wealth of information concerning the structure of a highly-entangled polymer and is widely used to characterize polyolefins. Long-time relaxation processes are most sensitive to molecular structure but are difficult to probe in the case of polymers with broad molecular weight distributions or long-chain branching. By combining complex modulus data with creep/creep recovery data using a continuous relaxation spectrum one can often reach the terminal zone even when this zone is inaccessible using standard techniques. Nonlinear viscoelascitity plays an important role in many melt processing operations, but the characterization of nonlinear behavior poses major challenges for the rheologist. The sliding plate rheometer has proven valuable for establishing nonlinear behavior in shear and for the study of wall slip and melt rupture. A new extensional rheometer designed as an accessory for a standared rotational rheometer has also been evaluated.
The Use of Rheology to Characterize the Branching Structure in Sparsely Branched Metallocene Catalyzed Polyethylenes
A series of six commercial polyethylenes are investigated including four metallocene catalyzed (mc) PE resins having varying degrees of long-chain branching and narrow MWD and a LDPE and a LLDPE. The degree of branching (i.e. the number of long chain branches per 10,000 carbon atoms) is estimated via dilute solution light scattering measurements. However, whether the branching in the mc PE's is random or concentrated on a few chains cannot be assessed by means of dilute solution measurements. Shear and extensional viscosity measurements along with the use of molecular theory are employed to determine which is the most likely scenario.
Real-Time Monitoring of Mass-Change during the Structural Evolution of an Epoxy Glass Subsequent to Relative Humidity Jumps through the Glass Transition
The structural recovery response of an epoxy resin subjected to relative humidity (RH) and carbon dioxide (PCO2) jumps has been investigated by the real time monitoring of the mass change. Results show that, the structural recovery phenomenon is qualitatively similar to that observed by volume change measurements and also qualitatively similar to results obtained after temperature jumps (T-jumps). In addition, sorption/desorption measurements during up- and down-jumps in relative humidity are the first demonstration of the real-time monitoring of mass-change during the structural evolution of a glassy epoxy subjected to plasticizer jumps.
Applications of Nanostructured Carbons in Polymer-Based Materials
Nanostructured carbons include carbon nanotube, carbon nanofiber and carbon black. Their incorporation in polymer matrices allows practical applications. Evaluation of the feasibility of the applications required comparison with competing materials in terms of cost and performance. The evaluation provided in this paper shows that nanostructured carbons in polymer-based materials are suitable for electromagnetic, electrochemical and thermal applications, such as shielding, battery electrodes and thermal pastes for microelectronic cooling. A limited structural application in the area of vibration reduction is also feasible.
Mechanical Properties of Multiwalled Carbon Nanotube-Epoxy Nanocomposites
Epoxy-multi wall carbon nanotube composites have been fabricated. By choosing two different curing agents, both hard, rigid epoxy and soft, flexible rubbery matrices have been investigated. Since multi-walled nanotubes have a high strain to failure originating from telescopic deformation, the influence of matrix strain was examined. The concentration dependence of the nanotubes was examined by comparing two concentrations- 1wt% and 4wt%. Dynamic mechanical tensile tests using a three-point bend geometry was utilized to probe the glass transition, and plateau modulus effects of the material. Separate tensile tests showed that increasing filler concentration increases Young's modulus and decreases percent elongation to break for both rigid and flexible samples. Both rigid and flexible epoxy/nanotube composites have higher ultimate tensile strength and lower percent elongation to break than corresponding epoxy matrices. Flexible epoxy/nanotube composites however showed a larger percent increase in ultimate tensile strength and smaller percent decrease in elongation to break than rigid matrices supporting the concept that the strain match of the matrix is vital to effect multiwalled nanotube composites. SEM of the fracture surfaces showed fiber pullout to be the dominating failure mechanism.
Investigation of Reinforcement Mechanisms of Carbon Nanotube-Polymer Composites with Numerical Simulation
The tensile modulus of carbon nanotube reinforced polymer composites was calculated with 3-D Finite Element Method. The effects of nanotube orientation and nanotube agglomeration on tensile modulus of the composites were investigated. The simulation results show that the tensile modulus of a nanotube reinforced composite drops sharply either when the nanotubes diverge from the applied load direction, or when the nanotube agglomerations are formed. This finding could explain why the predicted tensile modulus of a nanotube composite, based on the assumption that the nanotubes are fully isolated and aligned in polymer matrix, is much higher than the values obtained from experiments.
Effects of Free-Surface and Interfacial Effects and Plasticizer Content on the Distribution of Glass Transition Temperatures in Nanoconfined Polymers
A novel fluorescence/multilayer method has been developed allowing the first determination of the distribution of glass transition temperatures (Tg) in thin and ultrathin polymer films. The perturbation in polymer dynamics associated with Tg near a free surface of a polymer film, leading to a lower Tg at the surface, affects the local Tg several tens of nanometers into the film. The extent to which the Tg dynamics smoothly transition from enhanced to bulk states depends strongly on nanoconfinement. However, the impact of nanoconfinement on Tg is also a strong function of plasticizer content and attractive interactions at a polymer-substrate interface. The potential of these studies for understanding polymer nanocomposite behavior is discussed.
Effect of Montmorillonite Layered Silicate (MLS) on Crystallization Growth Rate in Semi-Crystalline PET Nanocomposites
The influence of montmorillonite-layered silicates (MLS) on the isothermal and non-isothermal crystallization and growth rates of semi-crystalline PET is investigated. The non-isothermal DSC measurements show that the cold crystallization temperature decreases with increasing concentration of MLS. A concomitant decrease in melting temperature and enthalpy shows that this decrease is not a result of the increased crystallinity in the PET. Therefore it is clear that the surface area afforded by the MLS platelet leads to changes in the metastable fraction of polymer that is more responsive to thermal energy. The isothermal Avrami analysis shows that the crystallite shape is not affected by MLS but the growth rate is significantly affected. For low concentrations, the growth rate increases but additional MLS concentration then inhibits the growth.
Epoxy + Montmorillonite Nanocomposite Processing Influences on Dispersion
Alkyl ammonium treated montmorillonite used in conjunction with polymer matrices has shown promising results for improved strength, barrier properties and dimensional stability at temperatures higher than the matrix phase. Here we investigate the effect of montmorillonite concentration and premix temperature on dispersion of the clay platelets into the matrix. It is found that for an epoxy cured by alkyl amines, a critical concentration is obtained at 2.25% montmorillonite by weight when the premix temperature is 80 degrees. If the temperature is dropped to 75 degrees the kinetics reflect an micelle like transition.
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