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At least 235 records · Page 13

High Speed Thermal Imaging on Ballistic Impact of Triaxially Braided Composites

Ballistic impact experiments were performed on triaxially braided polymer matrix composites to study the heat generated in the material due to projectile velocity and penetration damage. Quantifying the heat generation phenomenon is crucial for attaining a better understanding of composite behavior and failure under impact loading. The knowledge gained can also be used to improve physics-based models which can numerically simulate impact of composites. Triaxially braided (0/+60/-60) composite panels were manufactured with T700S standard modulus carbon fiber and two epoxy resins. The PR520 (toughened) and 3502 (untoughened) resin systems were used to make different panels to study the effects of resin properties on temperature rise. Ballistic impact tests were conducted on these composite panels using a gas gun, and different projectile velocities were applied to study the effect on the temperature results. Temperature contours were obtained from the rear surface of the panel during the test through a high speed, infrared (IR) thermal imaging system. The contours show that high temperatures were locally generated and more pronounced along the axial tows for the T700S/PR520 composite specimens; whereas, tests performed on T700S/3502 composite panels using similar impact velocities demonstrated a widespread area of lower temperature rises. Nondestructive, ultrasonic C-scan analyses were performed to observe and verify the failure patterns in the impacted panels. Overall, the impact experimentation showed temperatures exceeding 525 K (485degF) in both composites which is well above the respective glass transition temperatures for the polymer constituents. This expresses the need for further high strain rate testing and measurement of the temperature and deformation fields to fully understand the complex behavior and failure of the material in order to improve the confidence in designing aerospace components with these materials.

thermal imaging↗

Coupling and Decoupling between Stickers and Backbones in Associating Polymers with Terminally Functionalized Side Chains

Associating polymers have recently attracted tremendous attention as self-healing polymers due to the dynamic reversibility of sticker association–dissociation processes. These sticker dynamics inevitably slow significantly as segmental dynamics decelerate below the glass transition temperature that limits the operational temperatures of associating polymers. Using broadband dielectric spectroscopy on a new set of associating polymers composed side chains of various lengths and terminal carboxylic-acid sticker functionality, we discovered an unexpected decoupling near the glass transition (T g ) between the slower backbone and fast sticker motions. These two motions have distinct activation energies for the motion of the sulfur linkage adjacent to the backbone (~22 to 26 kJ/mol) and the carboxylic acid groups (~5 to 8 kJ/mol). A second decoupling appears in the polymer with the longest side chain length at T g – 20 K, reflecting the dynamics of various carboxylic acid binding configurations. Furthermore, our findings open the door to design associating polymers with the capability of sticker association/dissociation at low temperatures.

36 MATERIALS SCIENCE↗

Thermodynamic and Kinetic Transitions of Liquids in Nanoconfinement

Core principles of chemistry are ubiquitously invoked to shed light on the nature of molecular level interactions in nanoconfined fluids, which play a pivotal role in a wide range of processes in geochemistry, biology, and engineering. A detailed understanding of the physicochemical processes involved in the flow, structural transitions, and freezing or melting behavior of fluids confined within nanometer-sized pores of solid materials is thus of enormous importance for both basic research and technological applications. This Account provides a perspective on new insights into the thermodynamic and kinetic transitions of nanoconfined fluids in their stable and metastable forms. After briefly introducing the unique properties of mesoporous silicas from the SBA, MCM, and FDU families that serve as the confinement matrices, combining highly ordered single and bimodal mesopore architectures with tunable pore sizes in the ~2-15 nm range and narrow size distributions, recent studies on melting/freezing behavior of water confined in these host matrices are reviewed. While differential scanning calorimetry (DSC) reveals a linear relationship between melting point depression and pore size (independent of the pore shape), as predicted by the Gibbs-Thomson relation, variable temperature 2 H wide-line nuclear magnetic resonance (NMR) spectroscopy studies confirm the core-shell model of water and give evidence for a layer-by-layer freezing mechanism, which gives rise to an apparent fragile-to-strong transition in the solidification dynamics. In contrast to the freezing/melting behavior of water, the effect of nanoconfinement on the glass transition of supercooled liquids is nonuniversal and the glass transition temperature T g can either increase or decrease with the dimensionality and extent of confinement. This nonuniversal behavior is exemplified by the two glass-forming molecular liquids, glycerol and ortho-terphenyl (OTP). While glycerol shows an increase in T g and a pronounced slowdown of the rotational dynamics of the constituent molecules due to a change in the molecular packing between the bulk and the confined liquid, OTP displays a linear and confining-media-dependent depression of T g with increased confinement that is strongly influenced by the pore-liquid interface characteristics. This Account concludes with a focus on recent experimental evidence of extreme spatial and dynamical heterogeneity in both freezing and glass transition processes. This discovery was enabled by the unique mesoporous structures of SBA-16 and FDU-5, possessing bimodal architectures with two interconnected pore types of different size and shape (spherical and cylindrical). For the very first time, two melting points for water and two glass transitions for supercooled OTP, corresponding to a specific pore type, were observed. Collectively, these observations strongly suggest a close mechanistic connection between the local fluctuations in the structure and dynamics of nanoconfined liquids. Finally, while the findings reviewed in this Account provide new insights into thermodynamic and kinetic transitions of fluids, there remain many unanswered questions regarding the effects of nanoconfinement on the fundamental properties of fluids, which offer exciting future opportunities in chemical research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chromium and Vanadium Incorporation in Sulfate-Containing Sodium Aluminoborosilicate Glass

In the composition space for Hanford low-activity nuclear waste glass, the waste loading of some formulations is limited by poor incorporation of sulfate. In particular, certain elements identified in previous studies tend to raise or lower sulfate solubility in borosilicate glass. The aim of the current study is to understand how vanadium and chromium each affect a sulfate-containing sodium aluminoborosilicate glass structure. Glass transition temperature, mass density, visible absorption, and Raman scattering were measured to investigate changes in the glass structure. Both Cr6+ (CrO42-) and Cr3+ were found in the chromium-containing glasses while vanadium primarily existed in the 5+ oxidation state in the vanadium-containing glasses. Electron probe microanalysis determined elemental compositions to assess retention of components. Increasing Cr2O3 caused saturation of Cr concentration within the glass and formation of crystalline eskolaite (Cr2O3). On the other hand, all the targeted V was incorporated into the glass. A fraction of batched S was not incorporated in any glass, presumably due to volatilization during melting. Apparently, the details of incorporation of Cr, and to an extent V, are different depending on whether sulfur is added as in this study or in oversaturated conditions as described in the literature, where Cr partitions to a sulfate-containing salt phase.

Borosilicate glass, Waste Glass, vanadium chemistr↗

Characterization of Properties for a Gamma–Irradiated ‘Revised’ International Simple Glass

Simplified surrogate high-level waste glasses from recent national and international testing were irradiated to gamma doses of 100 Mrad and 200 Mrad. Properties of the irradiated glass were measured for comparison to the pristine unirradiated glass. Glass transition temperatures as well as infrared and Raman spectroscopy measurements show no change in the irradiated glass. Short-term aqueous corrosion tests on the glass powders also indicate no measurable differences comparing the irradiated to pristine samples. Some corrosion differences were observed in the pristine glasses due to slight compositional changes. As expected from the observed radiation darkening of the glass, absorbance spectra of the irradiated glass with the pristine glass used as LDRD–2021–00341 LDRD External Report Summary reference indicates a broad absorbance over the range of 400 to 700 nm that is centered around 550-600 nm.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Preparation of highly fluorinated polyurethanes

New polyurethanes, formed from a reaction of a prepolymer diol and a perfluorinated diisocyanate, are nonflammable and possess high corrosion resistance and good low temperature flexibility. Polymer hardness increases rapidly with increasing ratio of diisocaynate to diol, but its glass transition temperature is not adversely affected.

Rochow, S. E.↗

Rubber-toughened polyfunctional epoxies - Brominated vs nonbrominated formulated for graphite composites

A new, commercially available, trifunctional epoxy resin (tris-(hydroxyphenyl)-methane triglycidyl ether) was modified with synthetic rubber to increase the impact resistance of epoxy/graphite composites. These composites were reinforced with commercially available satin-weave carbon cloth using two formulations of epoxies (brominated and nonbrominated) containing various amounts of carboxy-terminated butadience acrylonitrile (CTBN) rubber that had been prereacted with epoxy resin. The impact resistance was determined by measuring the interlaminar shear strength of the composites after impact. The mechanical properties, such as flexural strength and modulus at room temperature and at 93 C, were also determined. Measurements were taken of the flammability and glass transition temperature (Tg); and a thermal-gravimetric analysis was made.

Nir, Z.↗

Design Analysis and Thermo-Mechanical Fatigue of a Polyimide Composite for Combustion Chamber Support

Polyimide composites are being evaluated for use in lightweight support structures designed to preserve the ideal flow geometry within thin shell combustion chambers of future space launch propulsion systems. Principles of lightweight design and innovative manufacturing techniques have yielded a sandwich structure with an outer face sheet of carbon fiber polyimide matrix composite. While the continuous carbon fiber enables laminated skin of high specific stiffness; the polyimide matrix materials ensure that the rigidity and durability is maintained at operation temperatures of 316 C. Significant weight savings over all metal support structures are expected. The protypical structure is the result of ongoing collaboration, between Boeing and NASA-GRC seeking to introduce polyimide composites to the harsh environmental and loads familiar to space launch propulsion systems. Design trade analyses were carried out using relevant closed form solutions, approximations for sandwich beams/panels and finite element analysis. Analyses confirm the significant thermal stresses exist when combining materials whose coefficients of thermal expansion (CTEs) differ by a factor of about 10 for materials such as a polymer composite and metallic structures. The ramifications on design and manufacturing alternatives are reviewed and discussed. Due to stringent durability and safety requirements, serious consideration is being given to the synergistic effects of temperature and mechanical loads. The candidate structure operates at 316 C, about 80% of the glass transition temperature T(sub g). Earlier thermomechanical fatigue (TMF) investigations of chopped fiber polyimide composites made this near to T(sub g), showed that cyclic temperature and stress promoted excessive creep damage and strain accumulation. Here it is important to verify that such response is limited in continuous fiber laminates.

Thesken, J. C.↗

High-Temperature Adhesive Strain Gage Developed

Researchers at the NASA Lewis Research Center have developed a unique strain gage and adhesive system for measuring the mechanical properties of polymers and polymer composites at elevated temperatures. This system overcomes some of the problems encountered in using commercial strain gages and adhesives. For example, typical commercial strain gage adhesives require a postcure at temperatures substantially higher than the maximum test temperature. The exposure of the specimen to this temperature may affect subsequent results, and in some cases may be higher than the glass-transition temperature of the polymer. In addition, although typical commercial strain gages can be used for short times at temperatures up to 370 C, their long-term use is limited to 230 C. This precludes their use for testing some high-temperature polyimides near their maximum temperature capability. Lewis' strain gage and adhesive system consists of a nonencapsulated, unbacked gage grid that is bonded directly to the polymer after the specimen has been cured but prior to the normal postcure cycle. The gage is applied with an adhesive specially formulated to cure under the specimen postcure conditions. Special handling, mounting, and electrical connection procedures were developed, and a fixture was designed to calibrate each strain gage after it was applied to a specimen. A variety of tests was conducted to determine the performance characteristics of the gages at elevated temperatures on PMR-15 neat resin and titanium specimens. For these tests, which included static tension, thermal exposure, and creep tests, the gage and adhesive system performed within normal strain gage specifications at 315 C. An example of the performance characteristics of the gage can be seen in the figure, which compares the strain gage measurement on a polyimide specimen at 315 C with an extensometer measurement.

Pereira, J. Michael↗

Magnetic feed material and its use in producing bonded permanent magnets by additive manufacturing

A method for producing magnet-polymer pellets useful as a feedstock in an additive manufacturing process, comprising: (i) blending thermoplastic polymer and hard magnetic particles; (ii) feeding the blended magnet-polymer mixture into a pre-feed hopper that feeds directly into an inlet of a temperature-controlled barrel extruder; (iii) feeding the blended magnet-polymer mixture into the barrel extruder at a fixed feed rate of 5-20 kg/hour, wherein the temperature at the outlet is at least to no more than 10° C. above a glass transition temperature of the blended magnet-polymer mixture; (iv) feeding the blended magnet-polymer mixture directly into an extruding die; (v) passing the blended magnet-polymer mixture through the extruding die at a fixed speed; and (vi) cutting the magnet-polymer mixture at regular intervals as the mixture exits the extruding die at the fixed speed. The use of the pellets as feed material in an additive manufacturing process is also described.

36 MATERIALS SCIENCE↗

Crystallization behavior and properties of BaO-Al2O3-2SiO2 glass matrices

Glass of stoichiometric celsian composition, BaO-Al2O3-2SiO2, is a potential glass-ceramic matrix for high-temperature composites. The glass has a density of 3.39 g/cu cm, thermal expansion coefficient of 6.6 x 10(exp -6)/deg C glass transition temperature of 910 C, and dilatometric softening point of 925 C. On heat treatment, only hexacelsian crystallized out on the surface, but both celsian and hexacelsian were present in the bulk. Effects of cold isostatic pressing (CIP), sintering, and hot pressing, in the presence and absence of an additive, on the formation of the celsian phase in the glass were studied. CIP'ed samples, after appropriate heat treatments, always crystallized out as celsian whereas the presence of 5 to 10 weight percent of an additive was necessary for formation of celsian in sintered as well as hot pressed specimens. Green density increased with CIP'ing pressure but had no effect on sintered density. Hot pressing resulted in fully dense samples.

Drummond, Charles H., III↗

Variation of Resin Properties Through the Thickness of Cured Samples

It is the purpose of this work to gain knowledge of the glassy materials used as matrices in composites and to study the homogeneity resulting from the curing process. An attempt is made to link the glass transition quantitatively with the presence of a given material. Expoxy resins containing various amounts of hardener (TGDDM/DDS system) were cured in a muffle furnace at 473 K for seven hours. The glass transition temperature, T sub g versus weight minus percent of hardener in the epoxy resin were measured. A limit was rapidly reached in T sub g at only two percent hardener. Thus, the glass transition of the fully cured epoxy-amine matrix seems not much different from the epoxide-epoxide cure. The T sub g versus cure-time for the epoxide-epoxide reaction was also studied. My 720 was cured by itself in an oil bath at 473 K for different lengths of time. The T sub g was found to increase exponentially with the cure time, and a maximum T sub g of about 450 K was reached after eleven hours. The reaction was found to be inhibited by running the sample under argon.

Source record↗

High Temperature Thermoplastic Additive Manufacturing Using Low-Cost, Open-Source Hardware

Additive manufacturing (or 3D printing) via Fused Filament Fabrication (FFF), also known as Fused Deposition Modeling (FDM), is a process where material is placed in specific locations layer-by-layer to create a complete part. Printers designed for FFF build parts by extruding a thermoplastic filament from a nozzle in a predetermined path. Originally developed for commercial printers, 3D printing via FFF has become accessible to a much larger community of users since the introduction of Reprap printers. These low-cost, desktop machines are typically used to print prototype parts or novelty items. As the adoption of desktop sized 3D printers broadens, there is increased demand for these machines to produce functional parts that can withstand harsher conditions such as high temperature and mechanical loads. Materials meeting these requirements tend to possess better mechanical properties and higher glass transition temperatures (Tg), thus requiring printers with high temperature printing capability. This report outlines the problems and solutions, and includes a detailed description of the machine design, printing parameters, and processes specific to high temperature thermoplastic 3D printing.

Gardner, John M.↗

Applying state diagrams to food processing and development

The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.

Non-NASA Center↗

Effect of substituted phenylnadimides on processing and properties of PMR polyimide composites

Three nitrophenylnadimide cure initiators and two phenylnadimides (without nitros) were evaluated as additives to PMR-15 resins and Celion 6000 graphite fiber composites. The results of a resin screening study eliminated all of the additives except 3-nitrophenylnadimide (NO2PN) for use as a low temperature curing additive for PMR-15. Thus, NO2PN and the two control additives were investigated in PMR-15 formulations from which Celion 6000 graphite fiber/PMR-15 composites were processed both with low temperature (274 C) and normal (316 C) cure cycles. Comparisons of the two processing cycles, the resultant glass transition temperatures (Tg), the ambient, 274 and 316 C composite mechanical properties determined before and after 316 C postcure, the 316 C thermo-oxidative weight losses and the retention of 316 C composite mechanical properties are presented. Empirical correlations of the type and amount of nadimide additives with processing parameters, Tg, composite mechanical properties, composite thermo-oxidative stability and long term retention of 316 C composite mechanical properties are also presented.

Alston, W. B.↗

Effect of substituted phenylnadimides on processing and properties of PMR polyimide composites

Three nitrophenylnadimide cure initiators and two phenylnadimides (without nitros) were evaluated as additives to PMR-15 resins and Celion 6000 graphite fiber composites. The results of a resin screening study eliminated all of the additives except 3-nitrophenylnadimide (NO2PN) for use as a low temperature curing additive for PMR-15. Thus, NO2PN and the two control additives were investigated in PMR-15 formulations from which Celion 6000 graphite fiber/PMR-15 composites were processed both with low temperature (274 C) and normal (316 C) cure cycles. Comparisons of the two processing cycles, the resultant glass transition temperatures (Tg), the ambient, 274 and 316 C composite mechanical properties determined before and after 316 C postcure, the 316 C thermo-oxidative weight losses and the retention of 316 C composite mechanical properties are presented. Empirical correlations of the type and amount of nadimide additives with processing parameters, Tg, composite mechanical properties, composite thermo-oxidative stability and long term retention of 316 C composite mechanical properties are also presented.

Alston, W. B.↗

Liquid-Crystal Thermosets, a New Generation of High-Performance Liquid-Crystal Polymers

One of the major challenges for NASA's next-generation reusable-launch-vehicle (RLV) program is the design of a cryogenic lightweight composite fuel tank. Potential matrix resin systems need to exhibit a low coefficient of thermal expansion (CTE), good mechanical strength, and excellent barrier properties at cryogenic temperatures under load. In addition, the resin system needs to be processable by a variety of non-autoclavable techniques, such as vacuum-bag curing, resin-transfer molding (RTM), vacuum-assisted resin-transfer molding (VaRTM), resin-film infusion (RFI), pultrusion, and advanced tow placement (ATP). To meet these requirements, the Advanced Materials and Processing Branch (AMPB) at NASA Langley Research Center developed a new family of wholly aromatic liquid-crystal oligomers that can be processed and thermally cross-linked while maintaining their liquid-crystal order. All the monomers were polymerized in the presence of a cross-linkable unit by use of an environmentally benign melt-condensation technique. This method does not require hazardous solvents, and the only side product is acetic acid. The final product can be obtained as a powder or granulate and has an infinite shelf life. The obtained oligomers melt into a nematic phase and do not exhibit isotropization temperatures greater than the temperatures of decomposition (Ti > T(sub dec)). Three aromatic formulations were designed and tested and included esters, ester-amides, and ester-imides. One of the major advantages of this invention, named LaRC-LCR or Langley Research Center-Liquid Crystal Resin, is the ability to control a variety of resin characteristics, such as melting temperature, viscosity, and the cross-link density of the final part. Depending on the formulation, oligomers can be prepared with melt viscosities in the range of 10-10,000 poise (100 rad/s), which can easily be melt-processed using a variety of composite-processing techniques. This capability provides NASA with custom-made matrix resins that meet the required processing conditions for the fabrication of textile composites. Once the resin is in place, the temperature is raised to 375 C and the oligomers are cross-linked into a high-glass-transition-temperature (Tg) nematic network without releasing volatiles. The mechanical properties of the fully crosslinked, composite articles are comparable to typical composites based on commercially available epoxy resins.

Dingemans, Theo↗

Unleashing the potential of waste: A supercharged high-performance 3D printing resin from discarded polylactic acid

In additive manufacturing/3D printing, the limitation no longer lies in people’s imagination but in the very materials that one can print with. While the additive manufacturing process can virtually create any geometry, available applications are often limited by factors like parts’ mechanical strength, glass transition temperature, and heat deflection temperature. These factors are especially critical for polymer-based printing. Here we introduce a simple formulation derived from the aminolysis of polylactic acid (PLA) plastic waste, namely the N-lactoyl ethanolamine (N-LEA). The N-LEA is next reacted with excess methacrylic anhydride, forming a photo-crosslinkable resin for MSLA 3D printing. The resulting 3D printed part has a set of impressive properties that is unrivaled amongst engineering grade 3D printing resins on the market and research literature. The 3D printed part has an ultrahigh tensile strength of 131.7 MPa, glass transition at ~190 °C, and heat deflection temperature at 162.6 °C. Furthermore, this work demonstrates a true upcycling approach for turning PLA waste into a value-added product in a simple and efficient manner while also expanding the high-performance material portfolio available for photocuring additive manufacturing.

36 MATERIALS SCIENCE↗