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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10

Tuning Epoxy Thermomechanics via Thermal Isomerization: A Route to Negative Coefficient of Thermal Expansion Materials

Fine control over the thermal expansion and contraction behavior of polymer materials is challenging. Most polymers have large coefficients of thermal expansion (CTEs), which preclude long performance lifetimes of composite materials. Herein, we report the design and synthesis of epoxy thermosets with low CTE values below their T g and large contraction behavior above T g by incorporating thermally contractile dibenzocyclooctane (DBCO) motifs within the thermoset network. This atypical thermomechanical behavior was rationalized in terms of a twist-boat to chair conformational equilibrium of the DBCO linkages. We anticipate these findings to be generally useful in the preparation of materials with designed CTE values.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Strength Polylactic Acid (PLA) Biocomposites Reinforced by Epoxy-Modified Pine Fibers

The stiffness and tensile strength of biopolymers (e.g., polylactic acid (PLA)) are less than desirable for load-bearing applications in their neat form. The use of natural fibers as reinforcements for composites (for large-scale three-dimensional (3D) printing) has expanded rapidly, attributable to their low weight, low cost, high stiffness, and renewable nature. Silane and acid/alkali are typically used to modify the surface of natural fibers to improve the fiber/polymer interfacial adhesion. In this study, a simple method of impregnation was developed to modify pine fibers (loblolly, mesh size of 90–180 μm, 30 wt %) with a solvent-borne epoxy to reinforce PLA. As a benefit of the epoxy modification (0.5–10 wt %), the tensile strengths and Young’s moduli of the epoxy-modified pine/PLA composites increased by up to 20 and 82%, respectively, as compared to that of neat PLA. Furthermore, the epoxy-modified pine/PLA composites, with an optimum epoxy modification (1.0 wt %), had fewer voids on the fracture surface as compared with pine/PLA composites without the modification of pine fibers via epoxy. Finally, results confirmed that epoxy partially penetrated the pore/hollow inner structures of pine fibers and improved the fiber/matrix interfacial adhesion. Epoxy modification is found to be a simple and effective technique to improve the properties of biocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid epoxy–acrylate resins for wavelength-selective multimaterial 3D printing

Structures in nature have evolved to combine hard and soft materials in precise 3D arrangements, which imbues bulk properties and functionality that remain elusive to mimic synthetically. However, the potential for biomimetic analogs to seamlessly interface hard materials with soft surfaces for applications ranging from robotics and sealants to medical devices (e.g., prosthetics and wearable health monitors) has driven the demand for innovative chemistries and manufacturing approaches. Herein, we unveil a liquid resin for rapid, high resolution digital light processing (DLP) 3D printing of multimaterial objects with an unprecedented combination of strength, elasticity, and resistance to aging. Two enabling discoveries are the use of a covalently bound (hybrid) epoxy-acrylate monomer that precludes plasticization of soft domains and a wavelength-selective photosensitizer that accelerates cationic curing for hard domains. Using dual projection for multicolor DLP 3D printing (UV and violet light), several bioinspired metamaterial structures are fabricated, including one with hard springs embedded in a soft cylinder to adjust compressive behavior and a detailed knee joint featuring “bones” and “ligaments” for smooth motion. Lastly, the application of this system to facilitate selective stretching for electronic devices is demonstrated with a proof-of-concept device.

36 MATERIALS SCIENCE↗

Intumescent coatings containing 4,4'-dinitrosulfanilide

A coating which is stable to the environment and to exposure to water, and which intumesces at a favorable temperature was developed. The composition comprises a mixture of 4, 4 prime dinitrousulfanilide as the intumescent agent in a polymer binder mixture of a chlorinated polyolefin, a bisphenol A epoxy resin, and a rubber-like amine hardener.

Sawko, P. M.↗

Effect of metal ions on positron annihilation characteristics in metal ion containing epoxies

In the course of developing improved moisture-resistant epoxy resins, two different types of epoxy resins containing variable mole ratios of chromium ions per polymer repeat unit were developed. Positron annihilation characteristics have been investigated in these resins as a function of their metal ion content. In both cases, the presence of metal ions reduces the lifetime as well as the intensity of the long life component. The long life component intensity reduction is considerably more pronounced than the lifetime reduction. These results have been discussed in terms of increased unpaired electron density at Ps formation sites due to the presence of chromium ions in the matrix.

Singh, J. J.↗

Improved Composites Using Crosslinked, Surface-Modified Carbon Nanotube Materials

Individual carbon nanotubes (CNTs) exhibit exceptional tensile strength and stiffness; however, these properties have not translated well to the macroscopic scale. Premature failure of bulk CNT materials under tensile loading occurs due to the relatively weak frictional forces between adjacent CNTs, leading to poor load transfer through the material. When used in polymer matrix composites (PMCs), the weak nanotube-matrix interaction leads to the CNTs providing less than optimal reinforcement.Our group is examining the use of covalent crosslinking and surface modification as a means to improve the tensile properties of PMCs containing carbon nanotubes. Sheet material comprised of unaligned multi-walled carbon nanotubes (MWCNT) was used as a drop-in replacement for carbon fiber in the composites. A variety of post-processing methods have been examined for covalently crosslinking the CNTs to overcome the weak inter-nanotube shear interactions, resulting in improved tensile strength and modulus for the bulk sheet material. Residual functional groups from the crosslinking chemistry may have the added benefit of improving the nanotube-matrix interaction. Composites prepared using these crosslinked, surface-modified nanotube sheet materials exhibit superior tensile properties to composites using the as received CNT sheet material.

polymer matrix composite↗

Analysis of Fiber Clustering in Composite Materials Using High-Fidelity Multiscale Micromechanics

A new multiscale micromechanical approach is developed for the prediction of the behavior of fiber reinforced composites in presence of fiber clustering. The developed method is based on a coupled two-scale implementation of the High-Fidelity Generalized Method of Cells theory, wherein both the local and global scales are represented using this micromechanical method. Concentration tensors and effective constitutive equations are established on both scales and linked to establish the required coupling, thus providing the local fields throughout the composite as well as the global properties and effective nonlinear response. Two nondimensional parameters, in conjunction with actual composite micrographs, are used to characterize the clustering of fibers in the composite. Based on the predicted local fields, initial yield and damage envelopes are generated for various clustering parameters for a polymer matrix composite with both carbon and glass fibers. Nonlinear epoxy matrix behavior is also considered, with results in the form of effective nonlinear response curves, with varying fiber clustering and for two sets of nonlinear matrix parameters.

composite materials↗

Phase-Shifting Liquid Crystal Interferometers for Microgravity Fluid Physics

The initial focus of this project was to eliminate both of these problems in the Liquid Crystal Point-Diffraction Interferometer (LCPDI). Progress toward that goal will be described, along with the demonstration of a phase shifting Liquid Crystal Shearing Interferometer (LCSI) that was developed as part of this work. The latest LCPDI, other than a lens to focus the light from a test section onto a diffracting microsphere within the interferometer and a collimated laser for illumination, the pink region contained within the glass plates on the rod-mounted platform is the complete interferometer. The total width is approximately 1.5 inches with 0.25 inches on each side for bonding the electrical leads. It is 1 inch high and there are only four diffracting microspheres within the interferometer. As a result, it is very easy to align, achieving the first goal. The liquid crystal electro-optical response time is a function of layer thickness, with thinner devices switching faster due to a reduction in long-range viscoelastic forces between the LC molecules. The LCPDI has a liquid crystal layer thickness of 10 microns, which is controlled by plastic or glass microspheres embedded in epoxy 'pads' at the corners of the device. The diffracting spheres are composed of polystyrene/divinyl benzene polymer with an initial diameter of 15 microns. The spheres deform slightly when the interferometer is assembled to conform to the spacing produced by the microsphere-filled epoxy spacer pads. While the speed of this interferometer has not yet been tested, previous LCPDIs fabricated at the Laboratory for Laser Energetics switched at a rate of approximately 3.3 Hz, a factor of 10 slower than desired. We anticipate better performance when the speed of these interferometers is tested since they are approximately three times thinner. Phase shifting in these devices is a function of the AC voltage level applied to the liquid crystal. As the voltage increases, the dye in the liquid crystal tends to become more transparent, thus introducing a rather large amount of error into the phase-shifting measurement. While that error can be greatly reduced by normalization, we prefer eliminating the source of the error. To that end, we have pursued development of a 'blend' of custom dyes that will not exhibit these properties. That goal has not yet been fully achieved. Guardalben, et al, presented a similar set of interferograms in a paper partially funded by this grant. Shearing interferometers are a second class of common path interferometers. Typically they consist of a thick glass plate optimized for equal reflection from the front and back surface. While not part of the original thrust of the project, through the course of laboratory work, we demonstrated a prototype of a shearing interferometer capable of phase shifting using a commercial liquid crystal retardation plate. A schematic of this liquid crystal shearing interferometer (LCSI) and a sample set of interferograms are in the reference. This work was also supported by the U.S. Department of Energy Office of Inertial Confinement Fusion under Cooperative Agreement No. DE-FC03-92SF19460, the University of Rochester, and the New York State Energy Research and Development Authority. The support of DOE does not constitute an endorsement by DOE of the views expressed in this article. Additional information is included in the original extended abstract.

Griffin, DeVon W.↗

Highly Conducting Graphite Epoxy Composite Demonstrated

Weight savings as high as 80 percent could be achieved if graphite polymer composites could replace aluminum in structures such as electromagnetic interference shielding covers and grounding planes. This could result in significant cost savings, especially for the mobile electronics found in spacecraft, aircraft, automobiles, and hand-held consumer electronics. However, such composites had not yet been fabricated with conductivity sufficient to enable these applications. To address this lack, a partnership of the NASA Lewis Research Center, Manchester College, and Applied Sciences, Inc., fabricated nonmetallic composites with unprecedented electrical conductivity. For these composites, heat-treated, vapor-grown graphite fibers were selected which have a resistivity of about 80 mW-cm, more than 20 times more conductive than typical carbon fibers. These fibers were then intercalated with iodine bromide (IBr). Intercalation is the insertion of guest atoms or molecules between the carbon planes of the graphite fibers. Since the carbon planes are not highly distorted in the process, intercalation has little effect on mechanical and thermal properties. Intercalation does, however, lower the carbon fiber resistivity to less than 10 mW-cm, which is comparable to that of metal fibers. Scaleup of the reaction was required since the initial intercalation experiments would be carried out on 20-mg quantities of fibers, and tens of grams of intercalated fibers would be needed to fabricate even small demonstration composites. The reaction was first optimized through a time and temperature study that yielded fibers with a resistivity of 8.7 2 mW-cm when exposed to IBr vapor at 114 C for 24 hours. Stability studies indicated that the intercalated fibers rapidly lost their conductivity when exposed to temperatures as low as 40 C in air. They were not, however, susceptible to degradation by water vapor in the manner of most graphite intercalation compounds. The 1000-fold scaleup experiments concluded that 114 C was near the optimum temperature, but that the intercalation time needed to be lengthened by a factor of 3.

Gaier, James R.↗

High Strain Rate Deformation Modeling of a Polymer Matrix Composite: Matrix Constitutive Equations - Part 1

Recently applications have exposed polymer matrix composite materials to very high strain rate loading conditions, requiring an ability to understand and predict the material behavior under these extreme conditions. In this first paper of a two part report, background information is presented, along with the constitutive equations which will be used to model the rate dependent nonlinear deformation response of the polymer matrix. Strain rate dependent inelastic constitutive models which were originally developed to model the viscoplastic deformation of metals have been adapted to model the nonlinear viscoelastic deformation of polymers. The modified equations were correlated by analyzing the tensile/ compressive response of both 977-2 toughened epoxy matrix and PEEK thermoplastic matrix over a variety of strain rates. For the cases examined, the modified constitutive equations appear to do an adequate job of modeling the polymer deformation response. A second follow-up paper will describe the implementation of the polymer deformation model into a composite micromechanical model, to allow for the modeling of the nonlinear, rate dependent deformation response of polymer matrix composites.

Goldberg, Robert K.↗

A Spectacular Viscoelastic Model Calibration for 828/D230/Alox Generated from Legacy Sandia Data

The nonlinear viscoelastic Spectacular model is calibrated to the thermo-mechanical behavior of 828/D230/Alox with an alox volume fraction of 20 %. Legacy experimental data from Sandia’s polymer properties database (PPD) is used to calibrate the model. Based on known densities of the epoxy 828/D230 and the alox filler, the alox volume fractions listed on the PPD were likely reported incorrectly. The alox volume fractions are recalculated here. Using the recalculated alox volume fractions, the PPD contains experimental data for 828/D230/Alox with alox volume fractions of 16 %, 24 %, and 33 %, so the thermo-mechanical behavior at 20 % alox volume fraction is estimated by interpolating between the bounding cases of of 16 % and 24 %. Because the Spectacularmodel can be fairly challenging to calibrate, the calibration procedure is described in detail. Several of the calibration steps involve inverse parameter identification, where an experiment is simulated and parameters are iteratively updated until the model response matches the experimental data. As the PPD does not fully describe all experimental procedures, the experimental simulations use assumed thermal and mechanical loading rates that are typical for the viscoelastic characterization of epoxies. Spectacular uses four independent relaxation functions related to volumetric (ƒ 1 ), shear (ƒ 2 ), thermal strain (ƒ 3 ), and thermal relaxations (ƒ 4 ). The previous SPEC model form, also known as the universal_polymer model, uses two independent relaxation functions related to volumetric and thermal relaxation (ƒ ν = ƒ 1 = ƒ 3 = ƒ 4 ) and shear relaxation (ƒ s = ƒ 2 ). The two constitutive choices are briefly evaluated here, where it is found that the four relaxation function approach of Spectacular was better suited for fitting the coefficient of thermal expansion during both heating and cooling.

36 MATERIALS SCIENCE↗

Fabrication, thermal analysis, and heavy ion irradiation resistance of epoxy matrix nanocomposites loaded with silane-functionalized ceria nanoparticles

This paper describes a detailed understanding of how nanofillers function as radiation barriers within the polymer matrix, and how their effectiveness is impacted by factors such as composition, size, loading, surface chemistry, and dispersion. Here, we designed a comprehensive investigation of heavy ion irradiation resistance in epoxy matrix composites loaded with surface-modified ceria nanofillers, utilizing tandem computational and experimental methods to elucidate radiolytic damage processes and relate them to chemical and structural changes observed through thermal analysis, vibrational spectroscopy, and electron microscopy. A detailed mechanistic examination supported by FTIR spectroscopy data identified the bisphenol A moiety as a primary target for degradation reactions. Results of computational modeling by the Stopping Range of Ions in Matter (SRIM) Monte Carlo simulation were in good agreement with damage analysis from surface and cross-sectional SEM imaging. All metrics indicated that ceria nanofillers reduce the damage area in polymer nanocomposites, and that nanofiller loading and homogeneity of dispersion are key to effective damage prevention. The results of this study represent a significant pathway for engineered irradiation tolerance in a diverse array of polymer nanocomposite materials. Numerous areas of materials science can benefit from utilizing this facile and effective method to extend the reliability of polymer materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrically conductive carbon fiber layers as lightning strike protection for non-conductive epoxy-based CFRP substrate

A large amount of electrically conductive fillers is needed to enhance a Carbon Fiber Reinforced Plastics (CFRP) electrical conductivity enough to withstand lightning strikes of peak currents. However, such large alien constituents hamper the inherent good mechanical properties of CFRP structures. In this work, a solution has been proposed to retain both desired properties in a CFRP laminate. Layer-wise hybrid laminate has been demonstrated as a solution for lightning strike protection of Carbon Fiber Reinforced Plastics (CFRP). Top few layers of a hybrid laminate are prepared using electrically conductive polymer-based resin (CF/C-POLY) to provide effective dissipation of lightning current while epoxy-based CFRP substrate (CF/Epoxy) provides the main structural strength. An insulating adhesive layer is used to bond CF/C-POLY and CF/Epoxy to prepare the laminate. The hybrid laminates were tested for their effectiveness against lightning strikes. Laminates were struck by modified lightning waveform of component A with peak current of -14 kA and -40 kA. The performance of the laminates against lightning strike were evaluated using high speed camera, high-speed and thermal camera. It is found that CF/C-POLY layer successfully defended the main structural component i.e. CF/Epoxy from lightning direct damage.

36 MATERIALS SCIENCE↗

One-pot ternary sequential reactions for photopatterned gradient multimaterials

Seamless multimaterial construction is a common motif in animal physiology. Such continuous mechanical gradients remain challenging to reproduce in engineered systems, as current resin chemistries typically result in a single fixed set of properties. As an alternative to single-property materials, we introduce a thiol-ene-epoxy-based photothermal reaction scheme that produces multimaterials by altering the polymer microstructure within a single resin. In this system, the photodosage during the first stage of processing dictates the extent of conversion for each subsequent reaction. As a result, our photochemistry can exhibit a diverse range of soft (Young’s modulus, E ~ 400 kPa; elongation, dL/L0 ~ 300%) and stiff (E ~ 1.6 GPa; dL/L 0 ~ 3%) mechanical properties. Furthermore, we pattern photostable and mechanically robust modulus gradients (d[E r, stiff /E r , soft] /dx > 1,000 mm -1 ) that exceed those found in squid beaks and human knee entheses. We demonstrate the ability to build intricate multimaterial architectures including a soft, wearable braille display.

36 MATERIALS SCIENCE↗

A composite system approach to aircraft cabin fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of one of the baremaleimide composites are detailed.

Kourtides, D. A.↗

Materials research for aircraft fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of the state-of-the-art and the advanced bismaleimide composites are detailed.

Kourtides, D. A.↗

A composite system approach to aircraft cabin fire safety

The thermochemical and flammability characteristics of two polymeric composites currently in use and seven others being considered for use as aircraft interior panels are described. The properties studied included: (1) limiting oxygen index of the composite constituents; (2) fire containment capability of the composite; (3) smoke evolution from the composite; (4) thermogravimetric analysis; (5) composition of the volatile products of thermal degradation; and (6) relative toxicity of the volatile products of pyrolysis. The performance of high-temperature laminating resins such as bismaleimides is compared with the performance of phenolics and epoxies. The relationship of increased fire safety with the use of polymers with high anaerobic char yield is shown. Processing parameters of one of the bismaleimide composites is detailed.

Kourtides, D. A.↗