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Potentially useful process for fabrication of fiber-reinforced resinmatrix composites is powder slurry technique. Applicability of technique demonstrated using powdered resin made from thermoplastic polyimide LaRC/ TPI (thermoplastic polyimide). Use of process circumvents need for such high-cost organic solvents as N-methylpyrrolidinone and diglyme (diglycol methyl ether). Two basic slurries for LaRC/TPI powder investigated.
A study was conducted to assess the merits of using graphite/polyimide, NR-150B2 resin, for structural applications on advanced space launch vehicles. The program was divided into two phases: (1) Fabrication Process Development; and (2) Demonstration Components. The first phase of the program involved the selection of a graphite fiber, quality assurance of the NR-150B2 polyimide resin, and the quality assurance of the graphite/polyimide prepreg. In the second phase of the program, a limited number of components were fabricated before the NR-150B2 resin system was removed from the market by the supplier, Du Pont. The advancement of the NR-150B2 polyimide resin binder was found to vary significantly based on previous time and temperature history during the prepregging operation. Strength retention at 316C (600F) was found to be 50% that of room temperature strength. However, the composite would retain its initial strength after 200 hours exposure at 316C (600F). Basic chemistry studies are required for determining NR-150B2 resin binder quality assurance parameters. Graphite fibers are available that can withstand high temperature cure and postcure cycles.
A polymer system has been prepared which has the excellent thermoplastic properties generally associated with polysulfones, and the solvent resistance and thermal stability of aromatic polyimides. This material, with improved processability over the base polyimide, can be processed in the 260-325 C range in such a manner as to yield high quality, tough unfilled moldings; strong, high-temperature-resistant adhesive bonds; and well consolidated, graphite-fiber-reinforced moldings (composites). The unfilled moldings have physical properties that are similar to aromatic polysulfones which demonstrates the potential as an engineering thermoplastic. The adhesive bonds exhibit excellent retention of initial strength levels even after thermal aging for 5000 hours at 232 C. The graphite-fiber-reinforced moldings have mechanical properties which makes this polymer attractive for the fabrication of structural composites.
High temperature stable adhesive systems were evaluated for potential Supersonic Cruise Research (SCR) vehicle applications. The program was divided into two major phases: Phase I 'Adhesive Screening' evaluated eleven selected polyimide (PI) and polyphenylquinoxaline (PPQ) adhesive resins using eight different titanium (6Al-4V) adherend surface preparations; Phase II 'Adhesive Optimization and Characterization' extensively evaluated two adhesive systems, selected from Phase I studies, for chemical characterization and environmental durability. The adhesive systems which exhibited superior thermal and environmental bond properties were LARC-TPI polyimide and polyphenylquinoxaline both developed at NASA Langley. The latter adhesive system did develop bond failures at extended thermal aging due primarily to incompatibility between the surface preparation and the polymer. However, this study did demonstrate that suitable adhesive systems are available for extended supersonic cruise vehicle design applications.
Addition polyimides cure with no evolution of gaseous by-products at relatively low temperatures and may be cured at low pressures to yield composites with excellent hot-wet strength retention. These properaties have made them excellent candidates as matrix resins for advanced composites. However, commercially available bismaleimides are solids and difficult to handle in preimpregnated form. V-378A is an addition polyimide composed of a mixture of bismaleimides and other reactive ingredients formulated to provide good prepreg properties and handling, facile cure and excellent composite mechanical properties. Several curing mechanisms are utilized to provide the characteristics exhibited by V-378A. Part of the mechanism is free radial and takes place at ambient temperature and above. Other mechanisms are principally Diels-Alder in nature. V-378A prepregs are tacky at ambient temperature, but do not have long tacky outlife similar to some epoxies. V-378A yields composites which exhibit hot-wet strength retention which is superior to that provided by epoxy resin systems.
Hexamethylbenzene (HMB) was difficult to be oxidized with an alkaline potassium permanganate solution, since HMB was insoluble in an aqueous alkaline solution. But, when HMB was warmed with 50% nitric acid for a short time, and then treated with aqueous potassium permanganate, the reaction occurred readily and dimethylpyromellitic acid was obtained. When HMB was warmed with 50% nitric acid for 1 to 2 minutes, a yellow material was produced, which was soluble in hot aqueous potassium hydroxide, though free from carboxylic acids. It contained a little amount of bis-(nitromethyl)prehnitene and several unknown compounds. Further, the heat stability of polyimide prepared by the reaction of tetramethyldimethylpyromellitate with 4,4 prime-diaminodiphenylmethane turned out to be nearly equal to that of polyimide prepared from tetramethylpyromellitate.
Desirable qualities achieved by "networking" aromatic and addition polyimides. Novel semi-interpenetrating network (semi-ipn) prepared from two types of polyimides. Semi-ipn results when linear polymer synthesized in presence of cross-linked polymer or vice-versa. Semi-ipn attains certain properties better than those of either polymer alone.
Polyimide-foam airducts low in cost and light in weight. Relatively safe in fires because they resist spread of flames and generate little smoke. Polyimide-foam ducts less expensive to manufacture. Suitable for heating and air-conditioning in airplanes, ships, trains, and buildings.
Edge delamination tension and double cantilever beam tests were used to characterize the interlaminar fracture toughness of continuous graphite-fiber composites made from experimental thermoplastic polyimides and a model thermoplastic. Residual thermal stresses, known to be significant in materials processed at high temperatures, were included in the edge delamination calculations. In the model thermoplastic system (polycarbonate matrix), surface properties of the graphite fiber were shown to be significant. Critical strain energy release rates for two different fibers having similar nominal tensile properties differed by 30 to 60 percent. The reason for the difference is not clear. Interlaminar toughness values for the thermoplastic polyimide composites (LARC-TPI and polyimidesulfone) were 3 to 4 in-lb/sq in. Scanning electron micrographs of the EDT fracture surfaces suggest poor fiber/matrix bonding. Residual thermal stresses account for up to 32 percent of the strain energy release in composites made from these high-temperature resins.
A study was performed with the objective of developing matrix resins that exhibit improved thermo-oxidative stability over state-of-the-art high temperature resins for use at temperatures up to 644 K (700 F) and air pressures up to 0.7 MPa (100 psia). The work was based upon a TRW discovered family of polyimides currently licensed to and marketed by Ethyl Corporation as EYMYD(R) resins. The approach investigated to provide improved thermo-oxidative properties was to use halogenated derivatives of the diamine, 2, 2-bis (4-(4-aminophenoxy)phenyl) hexafluoropropane (4-BDAF). Polyimide neat resins and Celion(R) 12,000 composites prepared from fluorine substituted 4-BDAF demonstrated unexpectedly lower glass transition temperatures (Tg) and thermo-oxidative stabilities than the baseline 4-BDAF/PMDA polymer.
Studies were performed to determine the toughness characteristics of composites prepared from modified addition-type polyimides, using Celion 6000 graphite fiber as the reinforcement. The polyimides were prepared from aromatic diamines containing flexibilizing ether connecting groups. The composite flexural and short beam shear strengths were determined at room temperature and elevated temperatures. Composite toughness was evaluated using 10 deg off axis tensile tests and double cantilever beam fracture tests at room temperature. The effects of the flexibilized resin structure on composite mechanical properties, toughness characteristics, and thermo-oxidative stability are discussed.
The invention is a process for the production of solid aromatic polyamic acid and polyimide fibers from a wet gel or coagulation bath wet gel using N,N-dimethylacetamide (DMAc) solution of the polyamic acid derived from aromatic dianhydrides such as 3,3',4,4'-benzo phenone tetracarboxylic dianhydride (BTDA) and aromatic diamines such as 4,4'oxydianiline (4,4'-ODA). By utilizing the interrelationship between coagulation medium and concentration, resin inherent viscosity, resin percent solids, filament diameter, and fiber void content, it is possible to make improved polyamic acid fibers. Solid polyimide fibers, obtained by the thermal cyclization of the polyamic acid precursor, have increased tensile properties compared to fibers containing macropores from the same resin system.
It is the primary object of the present invention to prepare high temperature polymeric materials, especially linear aromatic polyimides, which maintain their integrity and toughness during long exposure times at elevated temperatures. According to the present invention, this object is achieved, and the attending benefits are obtained, by first providing the bis(exocyclodiene) bis(4-(3,4-dinethylene pyrrolidyl) phenyl) methane, which is formed from the monomer N-phenyl 3,4-dimethylene pyrrolidine. This bis-(exocyclodiene) undergoes Diels-Alder reaction with a bismaleimide without the evolution of gaseous by-products, to form the aromatic polyimide.
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.
Edge delamination tension and double cantilever beam tests were used to characterize the interlaminar fracture toughness of continuous graphite-fiber composites made from experimental thermoplastic polyimides and a model thermoplastic. Residual thermal stresses, known to be significant in materials processed at high temperatures, were included in the edge delamination calculations. In the model thermoplastic system (polycarbonate matrix), surface properties of the graphite fiber were shown to be significant. Cricital strain energy release rates for two different fibers having similar nominal tensile properties differed by 30 to 60 percent. The reason for the difference is not clear. Interlaminar toughness values for the thermoplastic polyimide composites (LARC-TPI and polyimidesulfone) were 3 to 4 in-lb/sq in. Scanning electron micrographs of the EDT fracture surfaces suggest poor fiber/matrix bonding. Residual thermal stresses account for up to 32 percent of the strain energy release in composites made from these high-temperature resins.
Analytical techniques including low angle laser light scattering photometry (LALLS), differential viscometry (DV), gel permeation chromatography (GPC), GPC-LALLS and GPC-DV, were used to characterize the molecular weight and molecular weight distribution of several advanced thermoplastics. A discussion is presented of various molecular-weight-related parameters obtained by these techniques on an experimental polyimide and poly(arylene ether ketone) and a commercially available polysulfone. Where possible, these parameters are correlated with processability and selected mechanical properties. The molecular weight was found to vary during the thermal conversion of poly(amic acid) to polyimide. However, no change in composition of the polysulfone was noted in response to various processing procedures.
The use of a semiinterpenetrating polymer network (SIPN) of the high-performance polyimide NR-150B2 to reduce brittleness and improve processability in the highly crosslinked acetylene-terminated polyimides Thermid LR-600, AL-600, MC-600, and FA-700 is described. The theoretical basis of the SIPN process is reviewed; the preparation and characterization of the neat SIPN resins and unidirectional graphite-fiber composites are explained; and the results are presented in extensive tables, graphs, and micrographs and discussed in detail. Significant increases in fracture energy were observed with SIPN, from 93 J/sq m for unmodified LR-600 to 283-603 J/sq m for the SIPN materials; the room-temperature flexural strength of the unidirectional composites also increased, from 1344 MPa for an unmodified MC-600 composite to 2020-1751 MPa for the SIPN composites. The potential applicability of SIPN-based composites to aerospace structures and electronic components is indicated.
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.