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PMR polyimides are safe, easy to handle, can be processed with relatively wide process controls, and offer excellent mechanical properties, with thermo-oxidative stability. Procedures, staging and cure schedules fully dense, crackfree, dimensionally controlled, complex structure: high tip speed fan blades 1.27 cm (0.5 in) thick.
Studies have demonstrated versatility of PMR approach for tailor making polyimide matrix resins with side range of flow characteristics. By simply adjusting molar ratio of reactants in monomer mixture, resins having flow values of as much as 20% can be achieved.
Self-aligning plain spherical and plain cylindical oscillating bearings with self-lubricating elements are composed of 50 weight-percent chopped graphite fibers and 50 weight-percent polyimide.
Processing reproducibility and versatility were demonstrated for producing addition-cured polyimide/graphite fiber composites using an in situ polymerization of monomeric reactants directly on the fiber surface. The polymers so derived, designated PMR polyimides, can be fabricated into composite structures by laminating, random fiber molding or autoclave curing. Composites were determined to be thermally stable and retain useful properties after extended exposures at 550 F to 650 F. The material and fabrication capability were demonstrated by the fabrication and evaluation of prototype complex fan blades.
A study has been made of the thermal behavior of polyimide precursors: an isomeric pair of crystals of the complex formed by p-phenylenediamine with the separated isomers of the di-isopropyl ester of pyromellitic acid. Specimens of this material were isothermally annealed in the temperature range 120 C to 170 C for periods of time up to 1 week. Although this temperature range is well below that customarily used for imidizations, the working hypothesis was that it would be more likely that a polymer embodying at least part of the precursor structure could be formed if the molecular motion was minimized to that actually required for the formation of the imide linkage. The progress of the annealing was followed by: infrared spectroscopy, differential thermal analysis, powder X-ray diffraction, and thermal gravimetric analysis. Single crystal X-ray analysis of the meta monomer yields a structure of chains of alternating acid and base and suggests that this monomer is amenable to polymerization with a minimum of geometrical disruption.
A 50/50 (weight percent) composite of graphite fibers and polyimide was studied in self-aligning plain bearings oscillating + or - 15 degrees at 1 hz. The friction coefficient was 0.15 + or - 0.05 at 250 C, and 0.05 + or - 0.02 at 315 C. Best results were obtained with a molded composite liner with chopped graphite fibers randomly oriented in the composite. The specific wear rate is given. It was found that the dynamic unit load capacity was higher for a composite bushing (thin liner), than for a composite ball.
The friction characteristics of polyimide films bonded to metallic substrates were studied from 25 to 500 C. These results were correlated to molecular structure and the results of torsional braid analysis (TBA). A large friction transition (0.23 to 0.03) was found to occur at 45 C + or - 5 C. It was postulated that this transition was initiated by some molecular relaxation, which gave the molecules a degree of freedom by which an external mechanical stress could rearrange the molecules into a structure, such as an extended chain, which is conducive to easy shear. Above 300 C the friction characteristics were found to be dependent on the thermal prehistory of the film.
Three polyfunctional amines were synthesized. Polyimide films containing varying amounts of the amine crosslinking agents were prepared. Their thermomechanical properties were compared with those of control film samples prepared from difunctional amines. The effect of crosslink density on isothermal weight loss, polymer softening, and glass transition temperature is discussed.
A process of preparing aromatic polyamide-acids for use as adhesives is described. An equimolar quantity of an aromatic dianhydride is added to a stirred solution of an aromatic diamine in a water or alcohol-miscible ether solvent to obtain a viscous polymer solution. The polymeric-acid intermediate polymer does not become insoluble but directly forms a smooth viscous polymer solution. These polyamic-acid polymers are converted, by heating in the range of 200-300 C and with pressure, to form polyimides with excellent adhesive properties.
Studies performed to demonstrate the feasibility of using the polymerization of monomer reactants (PMR) approach in order to 'tailor-make' processable polyimide matrix resins are described. Monomeric reactant solutions containing the dimethyl ester of 3, 3', 4, 4'-benzophenonetetracarboxylic acid, 4, 4'-methylenedianiline and the monomethyl ester of 5-norborene-2, 3-dicarboxylic acid were used to impregnate Hercules HTS graphite fiber. Six different monomeric reactant stoichiometries were studied. The processing characteristics and elevated temperature mechanical properties of the PMR polyimide/HTS graphite fiber composites are described.
Processing reproducibility and versatility were demonstrated for producing addition-cured polyimide/graphite fiber composites using a unique in situ polymerization of monomeric reactants directly on the fiber surface. The polymers so derived, designated PMR polyimides, can be fabricated into composite structures by laminating, random fiber molding or autoclave curing. Composites were determined to be thermally stable and retain useful properties after extended exposures at 550 to 650 F. The material and fabrication capability were demonstrated by the fabrication and evaluation of prototype complex fan blades.-
Chemistry and processing modifications of the poly(Diels Alder) polyimide (PDA) resin were performed to obtain structural composites suitable for 589 K (600 F) service. This work demonstrated that the PDA resin formulation is suitable for service at 589 K (600 F) for up to 125 hours when used in combination with Hercules HTS graphite fiber. Sandwich panels were autoclave molded using PDA/HTS skins and polyimide/glass honeycomb core. Excellent adhesion between honeycomb core and the facing skins was demonstrated. Fabrication ease was demonstrated by autoclave molding three-quarter scale YF-12 wing panels.
Friction and wear experiments conducted on polyimide films bonded to 440C stainless steel disks indicated that a wear transition (from high wear to low wear) accompanied a friction transition (from high friction to low friction). In dry argon or dry air (less than 20 ppm H2O), the transition was found to occur at 40 plus or minus 10 C; when H20 was present in air (10,000 ppm H2O), the transition was found to be elevated to a temperature between 100 and 200 C. Wear rate calculations made at 25, 100, and 200 C indicated that film wear was relatively constant for particular experimental conditions; however, the rate was strongly dependent on temperature and atmosphere.
Spectral and chomatographic studies were conducted which established the presence of tri- and tetraester impurities in aged monomer solutions employed in fabrication of PMR-polyimide resin composites. The equilibrium constant and apparent rate of the esterification were determined. It was demonstrated, using differential scanning calorimetry, that the ortho-ester moiety of these impurities does not completely react at typical cure conditions. It is concluded that voids formed in composites fabricated with aged monomer solution are due to gaseous decomposition products evolved by ester impurities and/or unreacted amine during elevated temperature post-cure treatment.
Friction and wear experiments conducted on polyimide films bonded to 440C stainless steel disks indicated that a wear transition (from high wear to low wear) accompanied the friction transition (from high friction to low friction). The transition was found to be atmosphere dependent as well as temperature dependent. Wear rate calculations indicated that at temperatures above the transition, wear could be up to 600 times less than at temperatures below the transition. Transfer to metallic riders was also investigated and found to be considerably different at temperatures above and below the transition.
A preliminary study was conducted to determine the dielectric properties of glass fabric reinforced composites as influenced by the reactions occurring during the preparation of crosslinked polyimides by the PMR process. The variables studied included: formulated molecular weight, staging temperature and time; rate of temperature increase to cure temperature; and cure temperature and time. The changes of capacitance and, particularly, of dissipation factor were found to be strongly dependent on each of the variables studied.
The effects were investigated of partial substitution of tetraamine crosslinking agents for diamine reactants on the thermomechanical properties of PMR polyimide resins and graphite fiber-reinforced composites. The effect of tetraamine content on isothermal weight loss, glass transition, and softening temperatures of neat resin samples is discussed. Composites were fabricated using PMR methodology. Monomeric solution of various stoichiometric ratios was used to impregnate Hercules HTS graphite fiber. The mechanical property retention characteristics of the composites at 316 C (600 F) are described.
Melting point depression of addition-type polyimides through use of proper amine mixtures improves processability.