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At least 253 records · Page 14

Ultrasonic-Assisted Extrusion Processing for Enhancing Physical Properties of High-Density Polyethylene by Flow-Induced Crystallization

The evolution of crystallinity resulting from stress imposed on a melt, known as flow-induced crystallinity, can strongly influence the mechanical and physical properties of semicrystalline polymers. This study investigates shear-induced crystallization by applying an ultrasonic field to the melt flow as it passes through dies with various geometries. A custom-built sonication die is employed for controlling the dynamic temperature and shear environment, resulting in molecular alignment and potential for flow-induced crystallization. Application of both conventional and ultrasonic shear rates at the equilibrium melt temperature of high-density polyethylene (HDPE) was investigated to accelerate crystallinity and manipulate the crystal morphology across the film in pursuit of improved mechanical and gas barrier properties without the need for additives or other polymer layers. The relationships among ultrasonic-assisted extrusion processing, polymer structure, and performance were analyzed using wide- and small-angle X-ray scattering (WAXS and SAXS), tensile testing, and oxygen transmission rate (OTR) analysis. Multiple linear regression models were implemented to predict the correlation among HDPE structure, process, and properties. Structural analysis revealed that both conventional and ultrasonic shear rates had the most significant influence on lamellar spacing and redistribution of rigid and soft amorphous fractions within the crystalline domains, ultimately dictating the mechanical and physical properties of the films. The goal is to explore the potential of the ultrasonic-assisted high crystallinity monolayer that can replace some of the functionality of complex, heterogeneous multilayer packaging with a single-material film having enhanced oxygen barrier properties.

crystallinity↗

Toolpath considerations for DED: Arc and laser welding

Directed energy deposition (DED) is a form of additive manufacturing that uses localized melted metal, similar to traditional arc welding, to construct an object. In comparison to polymer systems, metal systems can exert additional control over the build process through manipulation of the pool of melted metal, called the “melt pool.” This is especially important to maintain appropriate layer heights and create high quality builds. Additionally, metal systems allow site-specific control of the printed part, which enables advanced construction techniques that would otherwise not be possible. However, both of these types of control require support from the slicing software and, potentially, sensor feedback. This chapter will discuss these control processes and their basic implementation in a slicing program. The processes described here lay the foundation for more advanced solutions, particularly sensor feedback, that will be discussed later.

Borish, Michael↗

Product-specific kinetics reveal effect of epoxy crystallization on thermoset thermal degradation

Crystallization is a common problem for epoxy resins, which are ubiquitous in industrial and commercial use. Integration of crystallized epoxy monomers into cured thermosets has been shown to alter the thermosets’ final mechanical properties. However, no studies have investigated the impact of these crystals on the thermal stability of the thermoset. Here we investigate the degradation kinetics of a bisphenol F–based epoxy thermoset with and without crystallized monomers using Product-Specific Kinetic (PSK) analysis coupled with Evolved Gas Analysis-Mass Spectrometry (EGA-MS). PSK analysis revealed significant differences in evolved product ion kinetics, suggesting changes in the degradation kinetics between thermoset configurations. Further, it was concluded that early stages of degradation are influenced most by crystal presence due to the high concentration of unreacted epoxy monomers and lower cross-linking density of the cured network. After post-cure annealing, significant changes are observed in the degradation kinetics of thermosets without crystal inclusions. Conversely, post-cure annealing procedures of crystal integrated thermosets showed little change in the thermoset degradation kinetics across all conversion extents. These findings suggest that post-cure annealing of thermosets with crystals present at the onset does not alter the cross-linking density of the polymer network enough to significantly change the degradation kinetics. We hypothesize this is because the excess monomers from the melted crystals are unable to find suitable reaction sites for complete binding into the polymer network, which has direct implications for the material properties and final thermal stability of the thermoset.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-healing carbon fiber/epoxy laminates with particulate interlayers of a low-melting-point alloy

In order to prolong the service life of fiber-reinforced polymer composites, the implementation of self-healing ability with the micro-encapsulated healing agent has been extensively studied. However, such microcapsule-based self-healing composites typically suffer from degraded mechanical properties due to the liquid-phase inclusions, thereby limiting their proliferation. Here, in this study, a low-melting-point alloy is utilized as the particulate inclusions of carbon fiber/epoxy laminated composites. Field's Metal particles (melting point: 62 °C) are distributed between woven carbon fiber preforms followed by the resin impregnation to realize laminated composites with a Field's Metal-enhanced interlayer(s). The resulting laminated composites demonstrate the autonomic repair of interlaminar failure with a 40 % of healing efficiency. Most of all, the mechanical properties of these self-healing laminated composites are comparable to the conventional laminated composites attributed to the rigid inclusions that can be compressed to increase the fiber volume. Since the Field's Metal particle inclusions can bestow polymer composites with self-healing ability and the potential increase in mechanical properties, Field's Metal-enhanced fiber-reinforced polymer composites are expected to unlock the practical utility of self-healing composites.

A. polymer-matrix composites (PMCs)↗

LaRC dry powder towpreg process

The dry powder towpreg process overcomes many of the difficulties associated with melt, solution and slurry prepregging of advanced composite materials. In the process, fluidized powder is deposited on spread tow bundles and melted on the fibers by radiant heating to adhere the polymer to the fiber. Bench scale design and operating data have been correlated for use in process scale up to commercial operation. Powdered towpreg has been woven and molded into preform material of good quality. Cost estimates suggest that processing costs are comparable to those of conventional hot melt prepreg. In the future, from a part fabrication point of view, powder coated prepreg tape, woven broad goods and woven and braided preforms may be considered as options to similar materials made by other methods.

Marchello, Joseph M.↗

Effects of Polymer Morphology on Solvent and Catalyst Accessibility during Polyethylene and Polystyrene Autoxidation

Efficient catalytic deconstruction of plastics requires facile solvent and catalyst access to polymer substrates to minimize mass transfer effects. Autoxidation using Co(II) acetate, Mn(II) acetate, and a radical carrier in acetic acid is a promising strategy to deconstruct mixed plastic waste, yet the role of polymer morphology in governing solvent and catalyst accessibility remains poorly understood. Here, in situ simultaneous small- and wide-angle X-ray scattering (SAXS/WAXS), complemented by X-ray fluorescence (XRF) imaging and high-pressure differential scanning calorimetry (DSC), were used to elucidate interactions between acetic acid, a Co/Mn catalyst solution, and semicrystalline polyethylene (PE) and amorphous polystyrene (PS) from room temperature to 160 °C. In PE, acetic acid and catalyst access were confined to amorphous regions and cryomilled particle interfaces at room temperature, while crystalline lamellae remained intact after soaking for up to 34 h. Increasing temperature enabled solvent uptake into PE, followed by solvent-assisted softening above 100 °C, and a modest melting-point depression that removed lamellar transport barriers upon melting. Conversely for PS, acetic acid penetrated the glassy polymer without inducing chain mobility until the glass transition was reached, above which the observed structural changes were consistent with enhanced segmental mobility which enabled bulk penetration. These results suggest that polymer morphology and thermally activated physical transitions arising from diffusion and polymer–solvent interactions can influence whether autoxidation of plastics is transport-limited or kinetically controlled, providing a framework for aligning reaction conditions with reaction outcomes.

09 BIOMASS FUELS↗

Polyimides containing oxyethylene units. II - Polymerization of 3.3', 4.4'-benzophenonetetra carboxylic dianhydride and pyromellitic dianhydride

The study is concerned with the polymerization of diamines 2a-d with readily available dianhydrides, i.e., 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA). The synthesis and polymerization of asymmetric diamines containing substituted alkylene ether linkages are also investigated. It is assumed that the flexibility introduced into the polymer chain through the use of such diamines would result in moderate glass transition temperatures that would allow the systems to be melt processed. Mixtures of diamines are also copolymerized so as to further disrupt the polymer's symmetry and recurrence regularity. The properties of the resulting polymers are briefly discussed.

Harris, F. W.↗

Synthesis of optically clear polymeric materials for high temperature windows

A polymer has been developed that has excellent potential for use as windows in spacecraft as well as conventional aircraft. This polymer, phenolphthalein polycarbonate, has outstanding thermal properties, e.g., in place of melting or burning, it produces an insulating charred foam that closes off transmission of radiant heat through the window. This fact, coupled with an oxygen index of 0.43 and a 177 C tensile strength of 58 mega Newtons/sq m, makes this polymer a prime candidate for further development. Pilot plant preparation in a 20 gallon Pfaudler kettle was accomplished and large test specimens were prepared for evaluations.

Pannell, C. E.↗

Thermoplastic coating of carbon fibers

A continuous powder coating system was developed for coating carbon fiber with LaRC-TPI (Langley Research Center-Thermoplastic Polyimide), a high-temperature thermoplastic polymide invented by NASA-Langley. The coating line developed used a pneumatic fiber spreader to separate the individual fibers. The polymer was applied within a recirculating powder coating chamber then melted using a combination of direct electrical resistance and convective heating to make it adhere to the fiber tow. The tension and speed of the line were controlled with a dancer arm and an electrically driven fiber wind-up and wind-off. The effects of heating during the coating process on the flexibility of the prepreg produced were investigated. The uniformity with which the fiber tow could be coated with polymer also was examined. Composite specimens were fabricated from the prepreg and tested to determine optimum process conditions. The study showed that a very uniform and flexible prepeg with up to 50 percent by volume polymer could be produced with this powder coating system. The coating line minimized powder loss and produced prepeg in lengths of up to 300 m. The fiber spreading was found to have a major effect on the coating uniformity and flexibility. Though test results showed low composite tensile strengths, analysis of fracture surfaces under scanning electron microscope indicated that fiber/matrix adhesion was adequate.

Edie, D. D.↗

The crystallization of tough thermoplastic resins in the presence of carbon fibers

The presence of carbon fibers increased the crystallization rates of both PEEK and PPS thermoplastic polymers. The effect was most pronounced at higher crystallization temperatures. Isothermal crystallization rates were analyzed by applying classical phenomenological nucleation theory. Unusually high values of the so-called Avrami exponent were found for neat PEEK. Isothermal crystallization of PEEK and PPS polymers produced crystalline samples having a wide variety of melting temperatures. The melting as observed by differential scanning calorimetry occurred as dual endotherms which were called primary (higher temperature) and secondary melting peaks. Each primary peak accounted for most of the crystallinity present. The secondary peaks represented the melting of crystallites formed later than those attributable to the primary endotherms. The presence of carbon fibers increased the thermal stability of both PEEK and PPS crystallites as manifested by higher temperatures for the primary melting peaks. This may be attributable to increased crystallite size, greater crystallite perfection, and/or favorable modification of the crystallite interface. Over the range studied, crystallization temperature strongly influenced the positions of the secondary peaks but not the primary peaks.

Theil, Michael H.↗

Characterization of medium and high flow series 1500 LARC-TPI

An imidized version of LARC-TPI was developed on NASA's request for use by both aerospace and electronic industries. Two batches of LARC-TPI 1500 Series, consisting of medium-flow and high-flow pellets with different inherent viscosities, are characterized for their dynamic and isothermal melt flow properties at 340 C, mechanical properties of extrudates, extrudate porosity, and degree of crystallinity. The Series shows significantly better melt flow properties than previosly examimed forms of this polymer.

Burks, H. D.↗

Tailorable Dielectric Material with Complex Permittivity Characteristics

A dielectric material includes a network of nanosubstrates, such as but not limited to nanotubes, nanosheets, or other nanomaterials or nanostructures, a polymer base material or matrix, and nanoparticles constructed at least partially of an elemental metal. The network has a predetermined nanosubstrate loading percentage by weight with respect to a total weight of the dielectric material, and a preferential or predetermined longitudinal alignment with respect to an orientation of an incident electrical field. A method of forming the dielectric material includes depositing the metal-based nanoparticles onto the nanosubstrates and subsequently mixing these with a polymer matrix. Once mixed, alignment can be achieved by melt extrusion or a similar mechanical shearing process. Alignment of the nanosubstrate may be in horizontal or vertical direction with respect to the orientation of an incident electrical field.

Dudley, Kenneth L.↗

Fabrication and Testing of Low Cost 2D Carbon-Carbon Nozzle Extensions at NASA/MSFC

Subscale liquid engine tests were conducted at NASA/MSFC using a 1.2 Klbf engine with liquid oxygen (LOX) and gaseous hydrogen. Testing was performed for main-stage durations ranging from 10 to 160 seconds at a chamber pressure of 550 psia and a mixture ratio of 5.7. Operating the engine in this manner demonstrated a new and affordable test capability for evaluating subscale nozzles by exposing them to long duration tests. A series of 2D C-C nozzle extensions were manufactured, oxidation protection applied and then tested on a liquid engine test facility at NASA/MSFC. The C-C nozzle extensions had oxidation protection applied using three very distinct methods with a wide range of costs and process times: SiC via Polymer Impregnation & Pyrolysis (PIP), Air Plasma Spray (APS) and Melt Infiltration. The tested extensions were about 6" long with an exit plane ID of about 6.6". The test results, material properties and performance of the 2D C-C extensions and attachment features will be discussed.

Greene, Sandra Elam↗

Experimental Observations of PMMA Spheres Burning at Reduced Gravity

Polymer combustion is a very complicated process which involves the coupling of gas-phase combustion, melting, pyrolysis, and possible charring of the condensed phase. Although only a few studies on the combustion of a spherically shaped polymer have been conducted, there is renewed interest in the subject. At the Third International Microgravity Combustion Workshop, we presented a preliminary experimental plan and proposed an apparatus to study the combustion of a PolyMethylMethAcrylate (PMMA) sphere at reduced gravity. In this paper, we describe the experimental hardware in detail, summarize our observations since the last workshop, and describe future studies. The main objective is to determine the burning rate of PMMA spheres at reduced gravity under different ambient oxygen concentrations and total pressures. The dependence of the burning rate on the initial sphere diameter will be examined. It is anticipated that the simple spherical geometry in conjunction with reduced gravity will facilitate an assessment of the effect of condensed phase behavior on polymer burning processes and can be used as a means to test polymer combustion models.

Yang, Ji-Ann C.↗

Tunable PA6 Polymer System for Thermoplastic Reinforced Body Panels

Project Goal: Overall, a redesigned polyamide system will combine the ductility and processing of a PA6 matrix, the strength and modulus of CF, and the facile recyclability of esters. Approach: PEA can be synthesized under conventional, industrially relevant pathways. Material properties and processing will be analyzed and compared to commercial PA6 material. Results: Polycondensation, traditional for polyesters, was successful in synthesized a PEA. PEA exhibited fast crystallization and bimodal melting behavior suggesting beneficial crystallization kinetics. PEA exhibit reduced melting temperatures owed to the incorporation of ester units in the polymer structure.

42 ENGINEERING↗

Bead–Spring Simulation of Ionomer Melts—Studying the Effects of Chain-Length and Associating Group Fraction on Equilibrium Structure and Extensional Flow Behavior

Ionomers are associative polymers with diverse applications ranging from selective membranes and high-performance adhesives to abrasion- and chemical-resistant coatings, insulation layers, vacuum packaging, and foamed sheets. Within equilibrium melt, the ionic or associating groups are known to form thermally reversible, associative clusters whose presence can significantly affect the system’s mechanical, viscoelastic, and transport properties. It is, thus, of great interest to understand how to control such clusters’ size distribution, shape, and stability through the designed choice of polymer architecture and the ionic groups’ fraction, arrangement, and interaction strength. In this work, we represent linear associating polymers using a Kremer–Grest type bead–spring model and perform large-scale MD simulations to explore the effect of polymer chain-length (l) and fraction (f s ) of randomly placed associating groups on the size distribution and stability of formed clusters. We consider different chain-lengths (below and above entanglement), varying fractions of associating groups (represented by ‘sticky’ beads) between 5 and 20%, and a fixed sticky–sticky nonbond interaction strength of four times that between regular non-associating beads. For all melts containing associating groups the equilibrium structure factor S(q) displays a signature ionomer peak at low wave vector q whose intensity increases with increasing f s and l. The average cluster size Nc increases with f s . However, the effect of chain-length on Nc appears to be pronounced only at higher values of f s . Under extensional flows, the computed stress (and viscosity) is higher at higher f s and l regardless of strain rate. Beyond a critical strain rate, we observe fragmentation of the associative clusters, which has interesting effects on the stress/viscous response.

36 MATERIALS SCIENCE↗

Review of Low-Cost Organic and Inorganic Phase Change Materials with Phase Change Temperature between 0°C and 65°C

Phase change materials (PCMs) that undergo a phase transition may be used to provide a nearly isothermal latent heat storage at the phase change temperature. This work reports the energy storage material cost ($/kWh) of various PCMs with phase change between 0-65°C. Four PCM classes are analyzed for their potential use in building systems: 1) inorganic salt hydrates, 2) organic fatty acids, 3) organic fatty alcohols, and 4) organic paraffin waxes. Many salt hydrates have low material costs (0.09 - 2.53 $-kg-1), high latent heat of fusion (100-290 J-g-1), and high densities (1.3-2.6 g-cm-3), leading to favorable volumetric storage density and low energy storage costs, 50-130 kWh-m3 and 0.90-40 $-kWh-1, respectively. Some salts are notably more expensive due to their scarcity or pressures from competing industries such as lithium-based salts. Fatty acids have the lowest energy storage cost in the temperature range 8-17°C at 6.50 – 40 $-kWh-1. Despite favorable latent heat (125 – 250 J-g-1) their low density gives (0.9 g-cm3) gives poor volumetric storage capacity, 32 – 80 kWh-m3. Fatty alcohols generally have high material costs 2.50 – 200 $-kg-1 which leads to high energy storage costs, 40-3000 $/kWh. With latent heat and density similar to fatty acids, fatty alcohols have poor volumetric energy storage, 43 – 55 kWh-m-3.Paraffin waxes containing only a single length carbon chain have a higher energy cost (15 – 500 $-kWh-1) than generic paraffin waxes containing many lengths of carbon chains (7 – 30 $-kWh-1). Pure waxes have a discrete phase change temperature due to their homogeneity. In contrast, a less refined generic wax with several carbon chain lengths is more likely to have a pronounced temperature glide during its phase change. Pure single carbon chain waxes are generally required for applications <45°C as generic paraffin waxes melt between 45-70°C. For many waxes, a solid-solid transition occurs at temperatures below the solid-liquid phase change. For pure paraffins with carbon content ≥22 C atoms, these transitions may appear near the same temperature resembling a temperature glide.The challenges with fatty acids, fatty alcohols, and waxes are low thermal conductivity, low density, some flammability concerns, and compatibility issues with some common engineering materials such as polymers. Challenges with salt hydrates are pronounced supercooling (>5°C), incongruent melting, and corrosiveness. All PCMs may degrade if exposed to ambient conditions and therefore require proper sealing.

Hirschey, Jason↗