Direct‐Write Formation and Dissolution of Silver Nanofilaments in Ionic Liquid‐Polymer Electrolyte Composites
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Fiber-reinforced composites and design analysis methods for these materials are being developed because of the vast potential of composites for decreasing weight and/or increasing use temperature capability in aerospace systems. These composites have potential for use in airbreathing engine components as well as aeronautical and space vehicle structures. Refractory wire-superalloy composites for use up to 2200 F or more and metal-matrix composites for lower temperature applications such as aerospace structures and turbojet fan and compressor blades are under investigation and are discussed. The development of a number of resin systems, including the polyimides and polyphenylquinoxalines, is described and their potential for use at temperatures approaching 315 C (600 F) is indicated. Various molecular modifications that improve processability and/or increase thermal and oxidative resistance of the resins are also described. Structural analysis methods are discussed for determining the stresses and deformations in complex composite systems. Consideration is also given to residual stresses resulting from the curing process and to the foreign object damage problem in fan blade applications.
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Residual stresses in composites are induced during fabrication and by environmental exposure. The theory formulated can describe the shrinkage commonly observed after a thermal expansion test. Comparison between the analysis and experimental data for laminates of various material systems indicates that the residual stress-free temperature can be lower than the curing temperature, depending on the curing process. Effects of residual stresses on ply failure including the acoustic emission characteristics are discussed.
A suitable method for the direct measurement of moisture concentrations after humidity/thermal exposure on state of the art epoxy and polyimide resins and their graphite and glass fiber reinforcements was investigated. Methods for the determination of moisture concentration profiles, moisture diffusion modeling and moisture induced chemical changes were examined. Carefully fabricated, precharacterized epoxy and polyimide neat resins and their AS graphite and S glass reinforced composites were exposed to humid conditions using heavy water (D20), at ambient and elevated temperatures. These specimens were fixtured to theoretically limit the D20 permeation to a unidirectional penetration axis. The analytical techniques evaluated were: (1) laser pyrolysis gas chromatography mass spectrometry; (2) solids probe mass spectrometry; (3) laser pyrolysis conventional infrared spectroscopy; and (4) infrared imaging thermovision. The most reproducible and sensitive technique was solids probe mass spectrometry. The fabricated exposed specimens were analyzed for D20 profiling after humidity/thermal conditioning at three exposure time durations.
The extent to which graphite fibers are released from resin matrix composites that are exposed to fire and impact conditions was determined. Laboratory simulations of those conditions that could exist in the event of an aircraft crash and burn situation were evaluated. The effectiveness of various hybridizing concepts in preventing this release of graphite fibers were also evaluated. The baseline (i.e., unhybridized) laminates examined were prepared from commercially available graphite/epoxy, graphite/polyimide, and graphite/phenolic materials. Hybridizing concepts investigated included resin fillers, laminate coatings, resin blending, and mechanical interlocking of the graphite reinforcement. The baseline and hybridized laminates' mechanical properties, before and after isothermal and humidity aging, were also compared. It was found that a small amount of graphite fiber was released from the graphite/epoxy laminates during the burn and impact conditions used in this program. However, the extent to which the fibers were released is not considered a severe enough problem to preclude the use of graphite reinforced composites in civil aircraft structure. It also was found that several hybrid concepts eliminated this fiber release. Isothermal and humidity aging did not appear to alter the fiber release tendencies.
The results of a program designed to determine the extent to which elemental boron and boron containing fillers added to the matrix resin of graphite/epoxy composites prevent the release of graphite fibers when the composites are exposed to fire and impact conditions are described. The fillers evaluated were boron, boron carbide and aluminum boride. The conditions evaluated were laboratory simulations of those that could exist in the event of an aircraft crash and burn situation. The baseline (i.e., unfilled) laminates evaluated were prepared from commercially available graphite/epoxy. The baseline and filled laminates' mechanical properties, before and after isothermal and humidity aging, also were compared. It was found that a small amount of graphite fiber was released from the baseline graphite/epoxy laminates during the burn and impact conditions used in this program. However, the extent to which the fibers were released is not considered a severe enough problem to preclude the use of graphite reinforced composites in civil aircraft structure. It also was found that the addition of boron and boron containing fillers to the resin matrix eliminated this fiber release. Mechanical properties of laminates containing the boron and boron containing fillers were lower than those of the baseline laminates. These property degradations for two systems: boron (5 micron) at 2.5 percent filler loading, and boron (5 micron) at 5.0 percent filler loading do not appear severe enough to preclude their use in structural composite applications.
Design approaches and materials are described from which are fabricated pyrostatic graphite/epoxy (Gr/Ep) laminates that show improved retention of graphite particulates when subjected to burning. Sixteen hybridized plus two standard Gr/Ep laminates were designed, fabricated, and tested in an effort to eliminate the release of carbon (graphite) fiber particles from burned/burning, mechanically disturbed samples. The term pyrostatic is defined as meaning mechanically intact in the presence of fire. Graphite particulate retentive laminates were constructed whose constituent materials, cost of fabrication, and physical and mechanical properties were not significantly different from existing Gr/Ep composites. All but one laminate (a Celion graphite/bis-maleimide polyimide) were based on an off-the-shelf Gr/Ep, the AS-1/3501-5A system. Of the 16 candidates studied, four thin (10-ply) and four thick (50-ply) hybridized composites are recommended.
This program was designed to develop technology for fabrication of graphite/epoxy composites containing selected boron and boron-containing fillers, determine the effects of the fillers on physical and mechanical properties of composites, and evaluate the effectiveness of the boron fillers for fiber retention when the composites are exposed to fire conditions followed by impact. Fillers evaluated were crystalline and amorphous boron, boron carbide, and aluminum boride. The fillers were evaluated by mixing with Narmco 5208 resin matrix at quantities up to 5%. Graphite composites were fabricated and evaluated with respect to their mechanical properties, resistance to humidity, and burning characteristics. Also, the mechanism by which the fillers prevented fiber release was studied.
The time-dependent creep-rupture process in graphite-epoxy laminates is examined as a function of temperature and stress level. Moisture effects are not considered. An accelerated characterization method of composite-laminate viscoelastic modulus and strength properties is reviewed. It is shown that lamina-modulus master curves can be obtained using a minimum of normally performed quality-control-type testing. Lamina-strength master curves, obtained by assuming a constant-strain-failure criterion, are presented along with experimental data, and reasonably good agreement is shown to exist between the two. Various phenomenological delayed failure models are reviewed and two (the modified rate equation and the Larson-Miller parameter method) are compared to creep-rupture data with poor results.
Under certain conditions of combined fire and impact, graphite fibers are released to the atmosphere by graphite fiber composites. The retention of graphite fibers in these situations is investigated. Hybrid combinations of graphite tape and cloth, glass cloth, and resin additives are studied with resin systems. Polyimide resins form the most resistant composites and resins based on simple novolac epoxies the least resistant of those tested. Great improvement in the containment of the fibers is obtained in using graphite/glass hybrids, and nearly complete prevention of individual fiber release is made possible by the use of resin additives.
Methods of improving the fire resistance of graphite epoxy composite laminates were investigated with the objective of reducing the volume of loose graphite fibers disseminated into the airstream as the result of a high intensity aircraft fuel fire. Improvements were sought by modifying the standard graphite epoxy systems without significantly negating their structural effectiveness. The modifications consisted primarily of an addition of a third constituent material such as glass fibers, glass flakes, carbon black in a glassy resin. These additions were designed to encourage coalescense of the graphite fibers and thereby reduce their aerodynamic float characteristics. A total of 38 fire tests were conducted on thin (1.0 mm) and thick (6.0 mm) hybrid panels.
The purpose of the paper is to demonstrate that constitutive equations for moisture sorption and swelling can be obtained with an internal variable method which is rooted in the theory of irreversible thermodynamics. Realism is injected into the model through the concept of free volume. The power of the method is illustrated by the solution of the formidable nonlinear boundary value problem for diffusion with swelling-stress dependent diffusivity.
The progress to date on the development of techniques to toughen continuous thermoplastic composites is summarized. The work, using the approach of toughening the polycarbonate composite matrix with rubber particles, has focused on determining the differences between Double Cantilever Beam (DCB) samples molded inhouse and those molded by NASA. Specifically, an effort was made to account for the differences in fracture toughness observed between the various specimens. In addition, preliminary results of tensile dilatometry tests are described; these tests suggest that processes leading to increased volume and enhanced shear banding are occurring within the rubber toughened system. The results of the effort using another approach, the preparation of random block copolycarbonates, are presented. The synthetic route to these species was modified so that higher molecular weights of these materials can be obtained. In addition, an attempt is being made to determine the exact block length or the number of functional groups in the oligomers since this procedure also should lead to high molecular weight materials. Dynamic mechanical analysis of the copolymer prepared so far indicates that the scale of cooperative molecular motion of the PBA polycarbonate at sub-Tg temperatures is larger than five monomer units. Efforts to find a suitable rubber-toughener for a thermoset system (bismaleimides) is also discussed. Included is a description of the various tougheners intended for use or currently being used.
A theory for the prediction of the creep and the microyield strength of composite laminates with viscoelastic matrices has been developed and tested. Precise creep curves from three laminates with arbitrary orientations provide the necessary input data. The time-dependent lamina properties are derived for subsequent use with standard laminate codes. Both the level and the shape of creep and strain recovery curves can be predicted. Extensions of the theory to include the effects of microcracking are outlined.
An experimental study was conducted to measure the thermooxidative stability of PMR-15 composites reinforced with various fibers and to observe differences in the way they degrade in air. The fibers studied include graphite and the thermally stable Nicalon and Nextel ceramic fibers. Weight-loss rates for the different composites were assessed as a function of mechanical properties, specimen geometry, fiber sizing, and interfacial bond strength. Differences were observed in rates of weight loss, matrix cracking, geometry dependency, and fiber sizing effects. It was shown that Celion 6000 fiber-reinforced composites do not exhibit a straight-line Arrhenius relationship at temperatures above 316 C.
The effect of voids on the interlaminar shear strength of a polyimide matrix composite system is described. The AS4 graphite/PMR-15 composite was chosen for study because this system can be readily processed by using the standard specified cure cycle to produce void-free composites and because preliminary work in this study had shown that the processing parameters of this resin matrix system can be altered to produce cured composites of varying void contents. Thirty-eight 12-ply unidirectional composite panels were fabricated for this study. A significant range of void contents (0 to 10 percent) was produced. The panels were mapped, ultrasonically inspected, and sectioned into interlaminar shear, flexure, and fiber content specimens. The density of each specimen was measured and interlaminar shear and flexure strength measurements were then made. The fiber content was measured last. The results of these tests were evaluated by using ultrasonic results, photomicrographs, statistical methods, theoretical relationships derived by other investigators, and comparison of the test data with the Integrated Composite Analyzer (ICAN) computer program developed at the Lewis Research Center for predicting composite ply properties. The testing is described in as much detail as possible in order to help others make realistic comparisons.
A probabilistic evaluation of an eight ply graphite-epoxy quasi-isotropic laminate was completed using the Integrated Composite Analyzer (ICAN) in conjunction with Monte Carlo simulation and Fast Probability Integration (FPI) techniques. Probabilistic input included fiber and matrix properties, fiber misalignment, fiber volume ratio, void volume ratio, ply thickness and ply layup angle. Cumulative distribution functions (CDFs) for select laminate properties are given. To reduce the number of simulations, a Fast Probability Integration (FPI) technique was used to generate CDFs for the select properties in the absence of fiber misalignment. These CDFs were compared to a second Monte Carlo simulation done without fiber misalignment effects. It was found that FPI requires fewer simulations to obtain the cumulative distribution functions as opposed to Monte Carlo simulation techniques. Furthermore, FPI provides valuable information regarding the sensitivities of composite properties to the constituent properties, fiber volume ratio and void volume ratio.