A thermally modified polymer matrix composite material with structural integrity to 371 C

The potential for utilizing surface coatings to inhibit the thermal oxidation of polymer matrix composites was studied. Isothermal, inert gas exposures of graphite/PMR-15 composites indicated that after an initial loss of weight, no significant amounts of thermal degradation products are given off during high temperature exposures in the absence of oxygen. As long as a coating remains effective, the composite material should remain stable. It was also found that the glass transition temperature T sub g of the matrix resin could be increased to values in excess of 400 C. This resulted in measured short beam shear strengths of 75.9 MPa (11 Ksi), flexural strengths of 1172 MPa (170 Ksi) and flexural moduli of 141 GPa (20.5 Msi) for the material at a test temperature of 371 C. The treatment that was used caused a decrease in the PMR-15 resin density from 1.31 to 1.29 gm/cc. It was concluded that state-of-the-art composites, protected by oxygen-impervious coatings, can be used as materials of construction with structural integrity to at least 371 C and possibly above

Thermo-oxidative stability studies of PMR-15 polymer matrix composites reinforced with various fibers

An experimental study was conducted to measure the thermo-oxidative stability of PMR-15 polymer matrix composites reinforced with various fibers and to observe differences in the way they degrade in air. The fibers that were studied included 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

Transverse flexural tests as a tool for assessing damage to PMR-15 composites from isothermal aging in air at elevated temperatures

To date, the effect of thermo-oxidative aging on unidirectional composite mechanical properties has been monitored by the measurement of interlaminar shear strength (ILSS) and either three or four point longitudinal flexural strength (LFS) of the composites being tested. Both results are affected by the fiber-to-matrix bonding, the former being dependent on the shear resistance of the interface and the latter on the degree of load sharing by the fibers through the fiber/matrix interface. Recently, fiber/matrix interfacial bond strengths have been monitored using a transverse flexural strength (TFS) test method. This test method was used to evaluate the effect of fiber surface treatment on the fiber/matrix bond. The interface bonding was varied in these tests using Hercules A-fibers with three-types of surfaces that produce bonds of poor, better, and good quality. The TFS was found not only to be sensitive to the bonding, but also to the aging time of unidirectional A-fiber/PMR-15 composites. This relationship reflects the mechanism by which the PMR-15 degrades during thermal aging

Effect of fiber reinforcements on thermo-oxidative stability and mechanical properties of polymer matrix composites

A number of studies have investigated the thermo-oxidative behavior of polymer matrix composites. Two significant observations have been made from these research efforts: (1) fiber reinforcement has a significant effect on composite thermal stability; and (2) geometric effects must be considered when evaluating thermal aging data. A compilation of some results from these studies is presented, and this information shows the influence of the reinforcement fibers on the oxidative degradation of various polymer matrix composites. The polyimide PMR-15 was the matrix material that was used in these studies. The control composite material was reinforced with Celion 6000 graphite fiber. T-40R graphite fibers, along with some very stable ceramic fibers were selected as reinforcing fibers because of their high thermal stability. The ceramic fibers were Nicalon (silicon carbide) and Nextel 312 (alumina-silica-boron oxide). The mechanical properties of the two graphite fiber composites were significantly different, probably owing to variations in interfacial bonding between the fibers and the polyimide matrix. The Celion 6000/PMR-15 bond is very tight but the T-40/PMR-15 bond is less tight. Three oxidation mechanisms were observed: (1) the preferential oxidation of the Celion 6000 fiber ends at cut surfaces, leaving a surface of matrix material with holes where the fiber ends were originally situated; (2) preferential oxidation of the composite matrix; and (3) interfacial degradation by oxidation. The latter two mechanisms were also observed on fiber end cut surfaces. The fiber and interface attacks appeared to initiate interfiber cracking along these surfaces

Relationship between voids and interlaminar shear strength of polymer matrix composites

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

Use of unbalanced laminates as a screening method for microcracking

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

Mechanical properties characterization of composite sandwich materials intended for space antenna applications

The composite materials proposed for use in the Advanced Communications Technology Satellite (ACTS) Program contains a new, high modulus graphite fiber as the reinforcement. A study was conducted to measure certain mechanical properties of the new fiber-reinforced material as well as of a composite-faced aluminum honeycomb sandwich structure. Properties were measured at -157, 22, and 121 C. Complete characterization of this material was not intended. Longitudinal tensile, picture-frame shear, short-beam shear, and flexural tests were performed on specimens of the composite face-sheet materials. Unidirectional, cross-plied, and quasi-isotropic fiber composite ply layup designs were fabricated and tested. These designs had been studied by using NASA's Integrated Composite Analyzer (ICAN) computer program. Flexural tests were conducted on (+/- 60/0 deg) sub s composite-faced sandwich structure material. Resistance strain gages were used to measure strains in the tensile, picture-frame, and sandwich flexural tests. The sandwich flexural strength was limited by the core strength at -157 and 22 C. The adhesive bond strength was the limiting factor at 121 C. Adhesive mechanical properties are reflected in sandwich structure flexural properties when the span-to-depth ratio is great enough to allow a significant shear effect on the load-deflection behavior of the sandwich beam. Most measured properties agreed satisfactorily with the properties predicted by ICAN

A predictive model for failure properties of thermoset resins

A predictive model for the three-dimensional failure behavior of engineering polymers has been developed in a recent NASA-sponsored research program. This model acknowledges the underlying molecular deformation mechanisms and thus accounts for the effects of different chemical compositions, crosslink density, functionality of the curing agent, etc., on the complete nonlinear stress-strain response including yield. The material parameters required by the model can be determined from test-tube quantities of a new resin in only a few days. Thus, we can obtain a first-order prediction of the applicability of a new resin for an advanced aerospace application without synthesizing the large quantities of material needed for failure testing. This technology will effect order-of-magnitude reductions in the time and expense required to develop new engineering polymers

Light weight polymer matrix composite material

A graphite fiber reinforced polymer matrix is layed up, cured, and thermally aged at about 750 F in the presence of an inert gas. The heat treatment improves the structural integrity and alters the electrical conductivity of the materials. In the preferred embodiment PMR-15 polyimides and Celion-6000 graphite fibers are used

Long-Term Durability of a Matrix for High-Temperature Composites Predicted

Polymer matrix composites (PMC's) are being increasingly used in applications where they are exposed for long durations to harsh environments such as elevated temperatures, moisture, oils and solvents, and thermal cycling. The exposure to these environments leads to the degradation of structures made from these materials. This also affects the useful lifetimes of these structures. Some of the more prominent aerospace applications of polymer matrix composites include engine supports and cowlings, reusable launch vehicle parts, radomes, thrust-vectoring flaps, and the thermal insulation of rocket motors. This demand has led to efforts to develop lightweight, high-strength, high-modulus materials that have upper-use temperatures over 316 C. A cooperative program involving two grants to the Massachusetts Institute of Technology and in-house work at the NASA Glenn Research Center was conducted to identify the mechanisms and the measurement of mechanical and physical properties that are necessary to formulate a mechanism-based model for predicting the lifetime of high-temperature polymer matrix composites. The polymer that was studied was PMR-15 polyimide, a leading matrix resin for use in high-temperature-resistant aerospace composite structures such as propulsion systems. The temperature range that was studied was from 125 to 316 C. The diffusion behavior of PMR-15 neat resin was characterized and modeled. Thermogravimetric analysis (TGA) was also conducted in nitrogen, oxygen, and air to provide quantitative information on thermal and oxidative degradation reactions. A new low-cost technique was developed to collect chemical degradation data for isothermal tests lasting up to 4000 hr in duration. In the temperature range studied, results indicate complex behavior that was not observed by previous TGA tests, including the presence of weight-gain reactions. These were found to be significant in the initial periods of aging from 125 to 225 C. Two types of weight loss reactions dominated at aging temperatures above 225 C. One was concentrated at the surface of the polymer and was very active at temperatures above 225 C. The second was observed to dominate in the latter stages of aging at temperatures below 260 C. This three-reaction model satisfactorily explains past findings that the degradation mechanism of PMR-15 appears to change around 316 C. It also indicates that the second weight gain mechanism is a significant factor at temperatures below 204 C. On the basis of these results, a predictive model was developed for the thermal degradation of PMR-15 at 316 C. A comparison of data generated by this model with actual experimental data is shown in the following figure