Modified Epoxy Matrix Resins for Reduced Dependence on Redundant Fasteners in Secondary-Bonded Composite Structures
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The properties of high performnce composites which are strongly dependent on the physical properties of the matrix resin were studied. Moisture adversely affect the properties of both neat epoxy resin and epoxy matrix composites. Inhomogeneous swelling as to the moisture degradation of mechanical properties, both in the neat resin and the composite. It is postulated that the postcuring process can change structure/moisture interactions and partially alleviate its adverse effects. The study is directed toward are understanding of the physical/mechanical/thermodynamic aspects of this problem.
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.
To ensure successful application of composite structure for aerospace vehicles, it is necessary to develop material systems that meet a variety of requirements. The industry has recently developed a number of low-viscosity epoxy resins to meet the processing requirements associated with vacuum assisted resin transfer molding (VARTM) of aerospace components. The curing kinetics and viscosity of two of these resins, an amine-cured epoxy system, Applied Poleramic, Inc. VR-56-4 1, and an anhydride-cured epoxy system, A.T.A.R.D. Laboratories SI-ZG-5A, have been characterized for application in the VARTM process. Simulations were carried out using the process model, COMPRO, to examine heat transfer, curing kinetics and viscosity for different panel thicknesses and cure cycles. Results of these simulations indicate that the two resins have significantly different curing behaviors and flow characteristics.
The epoxy resins currently in use can slowly absorb moisture from the atmosphere over a long period. This reduces those mechanical properties of composites which depend strongly on the matrix, such as compressive strength and buckling instabilities. The effect becomes greater at elevated temperatures. The paper will discuss new phenomena which occur under simultaneous temperature and moisture variations. An analytical model will also be discussed and documented.
Understanding the response of fillers in the epoxy resin crosslinking process and characterizing polymer–filler dynamics are the key features that guide the engineering of new thermosetting resin composites. Here, in this work, X-ray photon correlation spectroscopy (XPCS) is used as a thermal analysis tool to track the microscopic changes occurring during the cure of a functionalized cellulose nanocrystal (mCNC)–epoxy composite. In contrast, traditional methods such as differential scanning calorimetry (DSC) and curing rheology are used to understand the kinetics and properties on macroscopic length scales. Of interest is the influence of the mCNC on the curing kinetics and properties of the thermosetting resin. Two levels of modification (increasing hydrophobicity) were chosen to observe the effect of functionalization. Before cure, the highly functionalized CNC (mCNC3) shows a 44% increase in complex viscosity (η*), while the less functionalized CNC (mCNC2) shows a η* value similar to that of the neat resin. As the cure cycle progresses, results from DSC, rheology, and XPCS further show the enhancement in dispersion for mCNC3. The results show a clear difference in the maximum drift velocity, maximum heat flow, and complex viscosity during the ramp to the isothermal cure temperature (T cure ). Such results suggest that mCNC3 contains a well-dispersed network of particles due to the higher level of functionalization. During T cure , a transition in elastic modulus (G') occurs only for the highly functionalized CNC particle system. We believe that heat-induced aggregation occurs, and the crosslinked resin ultimately dominates the macroscopic properties of the final cured system for all samples. The results from the three techniques are in good agreement and showcase XPCS as a beneficial experimental tool for characterizing the microscopic dynamics of particulate-filled thermosetting resins. Hence, we envision this to be a fundamental curing study for the design of thermosetting resin composites.
Under NAS 8-27435, the Convair Aerospace Division of General Dynamics and their subcontractor, Hercules Incorporated, have conducted studies on the effects of moisture on the properties of fiber-reinforced resin composites and on the epoxy resins presently used in advanced composites. Data are presented on the resins and composites subjected to varying time/temperature/humidity or time/temperature/water-boil exposures. The effects of moisture on matrix, reinforcement, and fiber/resin interface are discussed and supported by experimental test data.
High moduli of elasticity potentially achievable. Suited for application in large diameter antennas on orbiting spacecraft. Fabrication process can accurately place dry graphite fibers and overwrap them with aluminum foil, resulting in straight, slender graphite tubes. Graphite fibers pulled out of creeled spools and fed through ceramic eyelets. Spools of aluminum foil mounted on rotating ring and capture graphite fiber as vertical winding machine carriage moves upward. Epoxy resin applied by mechanically spreading epoxy on tetrafluoroethylene mandrel by means of doctor blade attached to carriage.
Advanced resin systems and 3D textile preforms are being evaluated at Lockheed Aeronautical Systems Company (LASC) under NASA's Advanced Composites Technology (ACT) Program. This work is aimed towards the development of low-cost, damage-tolerant composite fuselage structures. Resin systems for resin transfer molding and powder epoxy towpreg materials are being evaluated for processability, performance and cost. Three developmental epoxy resin systems for resin transfer molding (RTM) and three resin systems for powder towpregging are being investigated. Various 3D textile preform architectures using advanced weaving and braiding processes are also being evaluated. Trials are being conducted with powdered towpreg, in 2D weaving and 3D braiding processes for their textile processability and their potential for fabrication in 'net shape' fuselage structures. The progress in advanced resin screening and textile preform development is reviewed here.
Pigmented epoxy resin and silicone resin as white paint coatings for inflatable spacecraft
Improved polyurethane and epoxy resins for use as adhesives at cryogenic temperatures
Photoelastoplastic method using creep and stress characteristics of epoxy resins under thermal cycle, discussing stress-strain behavior
Resin systems for coating hybrids prior to hermetic sealing are described. The resin systems are a flexible silicone junction resin system and a flexible cycloaliphatic epoxy resin system. The coatings are intended for application to the hybrid after all the chips have been assembled and wire bonded, but prior to hermetic sealing of the package. The purpose of the coating is to control particulate contamination by immobilizing particles and by passivating the hybrid. Recommended process controls for the purpose of minimizing contamination in hybrid microcircuit packages are given. Emphasis is placed on those critical hybrid processing steps in which contamination is most likely to occur.
Thirty-seven cured phenolic resin compositions were prepared and tested for their ability to provide improved char residues and moisture resistance over state of the art epoxy resin composite matrices. Cyanate, epoxy novolac and vinyl ester resins were investigated. Char promoter additives were found to increase the anaerobic char yield at 800 C of epoxy novolacs and vinyl esters. Moisture resistant cyanate and vinyl ester compositions were investigated as composite matrices with Thornel 300 graphite fiber. A cyanate composite matrix provided state of the art composite mechanical properties before and after humidity exposure and an anaerobic char yield of 46 percent at 800 C. The outstanding moisture resistance of the matrix was not completely realized in the composite. Vinyl ester resins showed promise as candidates for improved composite matrix systems.
Glass flake and epoxy resin matrix for liner of filament-wound fiberglass cryogenic propellant tank structures
Very large composite structures, such as those used in NASA's Space Launch System, push the boundaries imposed by current autoclaves. New technology is needed to maintain composite performance and free manufacturing engineers from the restraints of curing equipment size limitations. Recent efforts on a Phase II project by Cornerstone Research Group, Inc. (CRG), have advanced the technology and manufacturing readiness levels of a unique two-part epoxy resin system. Designed for room-temperature infusion of a dry carbon preform, the system includes a no-heat-added cure that delivers 350 F composite performance in a matter of hours. This no-oven, no-autoclave (NONA) composite processing eliminates part-size constraints imposed by infrastructure and lowers costs by increasing throughput and reducing capital-specific, process-flow bottlenecks. As a result of the Phase II activity, NONA materials and processes were used to make high-temperature composite tooling suitable for further production of carbon-epoxy laminates and honeycomb/ sandwich-structure composites with an aluminum core. The technology platform involves tooling design, resin infusion processing, composite part design, and resin chemistry. The various technology elements are combined to achieve a fully cured part. The individual elements are not unusual, but they are combined in such a way that enables proper management of the heat generated by the epoxy resin during cure. The result is a self-cured carbon/ epoxy composite part that is mechanically and chemically stable at temperatures up to 350 F. As a result of the successful SBIR effort, CRG has launched NONA Composites as a spinoff subsidiary. The company sells resin to end users, fabricates finished goods for customers, and sells composite tooling made with NONA materials and processes to composite manufacturers.
The fatigue resistance of a multiaxial braided (3-D) graphite/expoxy composite in both unnotched and post impacted conditions has been evaluated. The material tested is a (+/- 30/0 deg) multiaxial braid constructed from AS4/12K tow graphite fibers and British Petroleum E905L epoxy resin. These materials were braided as dry preforms and the epoxy was added using a resin transfer molding process (RTM). The unnotched and post-impact specimens were tested in compression-compression fatigue at 10 Hz with a stress ratio of R=10. The unnotched tension-tension fatigue specimens were tested at S Hz with a stress ration of R=0.1. Damage initiation and growth was documented through the application of radiography and ultrasonic through transmission (C-scans). Visible inspection of surface and edge damage was also noted to describe the initiation and progression of damage in these materials. The mechanisms leading to damage initiation were established and failure modes were determined. Stiffness and strength degradation were measured as a function of applied cycles. These 3-D braided composite results were compared to strain levels currently used to design primary structure in commercial aircraft composite components made from prepreg tape and autoclave cured.