State-of-the-art, high temperature polyimide matrix composites, reinforced with continuous graphite fibers are known to be susceptible to intraply cracking when thermally cycled over their useful service temperature range. It is believed that the transply cracking, in part, results from residual stresses caused by differences in coefficients of thermal expansion (CTE) between the polymer matrix and the reinforcement. Thermal cycling tests to investigate this phenomenon involve expensive time and energy consuming programs which are not economically feasible for use as a part of a materials screening process. As an alternative to thermal cycling studies, a study of unbalanced crossply graphite fiber reinforcement composites was conducted to assess the effect of the composite ply layup and surface condition on the residual stresses that remain after the processing of these materials. The residual stresses were assessed by measuring the radii of curvature of the types of laminates that were studied. The temperature at which stress-free conditions existed were determined and a dye penetrant method was used to observe surface damage resulting from excessive residual stress buildup. These results are compared with some published results of thermal cycling tests that were previously conducted on balanced polyimide composites.
A lightweight sandwich support structure, for the combustor chamber of a new generation liquid propellant rocket engine, was designed and fabricated using a polymer matrix composite (PMC) facesheet on a Ti honeycomb core. The PMC facesheet consisted of high stiffness carbon fiber, M40JB, and high temperature Polyimides, such as PMR-II-50 and HFPE-II-52. Six different fiber architectures; four harness satin (4HS) woven fabric, uni-tape, woven-uni hybrid, stitched woven fabric, stitched uni-tape and triaxial braided structures have been investigated for optimum stiffness-thickness-weight-hygrothermal performance design criteria for the hygrothermal-mechanical propulsion service exposure conditions including rapid heating up to 200 F/sec, maximum operating temperature of 600 F, internal pressure up to 100 psi. One of the specific objectives in this study is to improve composite blistering resistance in z-direction at minimum expense of in-plane mechanical properties. An extensive property-performance database including dry-wet mechanical properties at various temperatures, thermal-physical properties, such as blistering onset condition was generated for fiber architecture down-selection and design guidelines. Various optimized process methods such as vacuum bag compression molding, solvent assistant resin transfer molding (SaRTM), resin film infusion (RFI) and autoclaving were utilized for PMC panel fabrication depending on the architecture type. In the case of stitched woven fabric architecture, the stitch pattern in terms of stitch density and yarn size was optimized based on both in-plane mechanical properties and blistering performance. Potential reduction of the in-plane properties transverse to the line of stitching was also evaluated. Efforts have been made to correlate the experimental results with theoretical micro-mechanics predictions. Changes in deformation mechanism and failure sequences in terms of fiber architecture will be discussed.
A Second generation PMR (in situ Polymerization of Monomer Reactants) polyimide resin, PMR-II-50, has been considered for high temperature and high stiffness space propulsion composites applications for its improved high temperature performance. As part of composite processing optimization, two commercial prepregging methods: solution vs. hot-melt processes were investigated with M40J fabrics from Toray. In a previous study a systematic chemical, physical, thermal and mechanical characterization of these composites indicated that poor resin-fiber interfacial wetting, especially for the hot-melt process, resulted in poor composite quality. In order to improve the interfacial wetting, optimization of the resin viscosity and process variables were attempted in a commercial hot-melt prepregging line. In addition to presenting the results from the prepreg quality optimization trials, the combined effects of the prepregging method and two different composite cure methods, i.e., hot press vs. autoclave on composite quality and properties are discussed.
To increase performance and durability of high-temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high-temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. In this study, the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) and typical fluorinated polyimide resins, such as PMR-11-50 were characterized. A continuous desizing system that uses an environmentally friendly chemical- mechanical process was developed for tow level fiber. Composites were fabricated with fibers containing the manufacturer's sizing, desized, and further treated with a reactive finish. Results of room temperature tests show that desizing reduces interface sensitive properties compared to the manufacturer's sizing and that subsequent surface re-treatment with reactive finish increases interface sensitive properties. Properties of thermally aged composites and composites with varying finish concentrations will also be discussed.
To increase performance and durability of high-temperature composite for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high-temperature polyimide resins. Sizing commercially supplied on most carbon fiber are not compatible with polyimides. In this study, the chemistry of sizing on two high modulus carbon fiber (M40J and M60J, Tiray) was characterized. A continuous desizling system that uses an environmentally friendly chemical-mechanical process was developed for tow level fiber. Composites were fabricated with fibers containing the manufacturer's sizing, desized, and further treated with a reactive finish. Results of room-temperature tests after thermal aging show that the reactive finish produces a higher strength and more durable interface compared to the manufacturer's sizing. When exposed to moisture blistering tests, however, the butter bonded composite displayed a tendency to delaminate, presumably due to trapping of volatiles.
The results of in-plane four-point bend experiments on unidirectionally reinforced composite beams are presented for graphite/epoxy (T300/934) and graphite/polyimide (G30-500/PMR-15) composites. The maximum load and the location of cracks formed during failure were measured for testpieces with fibers oriented at various angles to the beam axis. Since most of the beams failed near one or more of the load points, the strength of the beams was evaluated in terms of a proposed model, for the local stress distribution. In this model, an exact solution to the problem of a localized contact force acting on a unidirectionally reinforced half plane is used to describe the local stress field. The stress singularity at the load points is treated in a manner similar to the stress singularity at a crack tip in fracture mechanisms problems. Using this approach, the effect of fiber angle and elastic material properties on the strength of the beam is described in terms of a load intensity factor. For fiber angles less than 45 deg from the beam axis, a single crack is initiated near one of the load points at a critical value of the load intensity factor. The critical load intensity factor decreases with the increasing fiber angle. For larger fiber angles, multiple cracks occur at locations both near and away from the load points, and the load intensity factor at failure increases sharply with increasing fiber angle.
Plasma-enhanced chemical vapor deposition was used to deposit silicon nitride on graphite-fiber-reinforced polyimide composites to protect against oxidation at elevated temperatures. The adhesion and integrity of the coating were evaluated by isothermal aging (371 C for 500 hr) and thermal cycling. The amorphous silicon nitride (a-SiN:H) coating could withstand stresses ranging from approximately 0.18 GPa (tensile) to -1.6 GPa (compressive) and provided a 30 to 80 percent reduction in oxidation-induced weight loss. The major factor influencing the effectiveness of a-SiN:H as a barrier coating against oxidation is the surface finish of the polymer composite.
Studies were conducted to improve the thermo-oxidative stability (TOS) of PMR type polyimides by the substitution of para-aminostyrene (PAS) for the nadic ester endcap in second generation PMR polyimides (PMR-2). The nadic endcap which provides the PMR polyimides with their relative ease of fabrication, both by limiting the molecular weight of the prepolymer and by undergoing the final addition cure without volatiles, is also the weak link with regard to TOS. A polyimide formulated with PAS endcaps, called V-CAP, utilizes a two step reaction sequence similar to that of the PMR polyimides and can be easily autoclave molded into low void composite materials. Resin studies included two formulations of both PMR-2 and V-CAP, corresponding to n = 9 and n = 14 prepolymer stoichiometry. Unidirectional reinforced T40R graphite fiber laminates were fabricated from each of the resins was post-cured in either air at 385 C or nitrogen at 400 C. Composite specimens were aged in air at 371 C and mechanical properties were measured at 371 C before and after exposure.
