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A method of preparing insoluble thermoplastic aromatic polyimides is described, having uniquely low softening temperatures by reacting, in a suitable solvent, an aromatic dianhydride, and a meta-substituted aromatic diamine.
The buffer rod technique for measuring attenuation in thin specimens is modified here to apply to specimens having intermediate thicknesses and high attenuation. The described procedure, which requires only one accessible surface of the material, was used to determine the initial attenuation values of ultrasonic waves in short beam shear specimens of graphite-polyimide composite material. It is shown that there is good correlation between the initial attenuation values and the shear strengths of the specimens determined by the standard short beam shear test method. The modified ultrasonic buffer block technique offers much potential for service as a quantitative, nondestructive, quality assurance test for composite materials.
A high degree of crystallinity has been found in unoriented polymer films formed from 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride (BDSDA) and p-phenylenediamine (PDA). Partial crystallinity for a polymer containing BDSDA and benzidine is also reported. A study of the thermal properties of the crystalline polyimides shows crystalline melting points of 426 C and 483 C respectively for the BDSDA-PDA and the BDSDA-benzidine polymers.
Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.
The stability of alcohol solutions of norborneyl capped PMR-polyimide resins was monitored during storage at ambient and subambient temperatures. Chemical changes during storage were determined spectroscopically using nuclear magnetic resonance. Resin processability and cured resin quality were determined by fabrication of unidirectional, graphite fiber composites using aged solutions and testing of selected composite properties. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-2 solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction produces from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-2 solutions do exhibit precipitates after extended subambient storage, however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.
Adhesive systems which could be used to bond composite-to-composite, composite-to-titanium, and honeycomb sandwich structures with operational capability at 589K for a minimum of 125 hours were evaluated. Evaluations were based on mechanical property tests such as lap shear and flatwise tensile and on processability. Quasi-isotropic Celion 6000/PMR-15 composite adherend was used to construct lap shear and flatwise tensile specimens. Hexcel's HRH-327-3/16-6.0 glass polyimide honeycomb core was also utilized in the flatwise tensile specimens. Numerous processing variations were also studied that led to selected cure cycles for each adhesive. Shear specimens having either 12 mm or 75 mm overlaps were used to determine the effect of bond size on processability and lap shear properties. The data indicate that processing of FM-34, FM-34B-18, LARC-13 and NRO56X can be achieved using a cure compatible with the composite adherend. No significant differences in mechanical properties were observed among the three adhesive systems and all three are suitable candidates for 589K/125 hour service.
The following areas of PMR polyimide research were reviewed: (1) prepreg tack and drape; (2) cure temperature; (3) solution characterization; and (4) elevated temperature composite properties. Recent hardware applications of PMR-15 by various fabricators were also reviewed.
Friction, wear life, rider wear, and film wear for a 440 C high-temperature-stainless-steel, hemispherically tipped rider sliding against polyimide-bonded graphite fluoride films were evaluated in a moist-air atmosphere at 25 C. Optical microscope and surface profilometry observations were made at various sliding intervals to determine how film thickness affected the lubricating and failure mechanisms of the films. Two lubrication regimes operated for the same load. In the first, the film supported the load and the lubricating mechanism consisted of the shear (plastic flow) of a thin layer of the lubricant between the metallic rider and the film surface. In the second, the film did not support the load (it was worn away) and the lubricating mechanism consisted of the shear of very thin lubricant films between flat areas generated on the rider and on sandblasted metallic asperities in the film wear track. Lubricant was supplied from the valleys between the asperities or from the sides of the wear track. With thicker films, wear life increased since a greater lubricant supply was available from the sides of the wear track.
A novel addition polyimide based on the use of liquid monomers is described. The essentially solventless prepreg produced retails good drape, tack, and other mechanical properties.
The stability of alcohol solutions of norbornenyl capped PMR-polyimide resins (both PMR-15 and PMR-II) has been monitored during storage at ambient and subambient (5 C and -18 C) temperatures. PMR-15 solutions exhibit nominally two weeks of useful life and PMR-II solutions exhibit nominally two days of useful life at ambient conditions. The limiting factor is precipitation of imide reaction products from the monomer solutions. Both solutions exhibit substantially longer useful lifetimes in subambient storage. PMR-15 shows no precipitation after several months storage at subambient temperatures. PMR-II solutions do exhibit precipitates after extended subambient storage (nominally three months at -18 C), however, the precipitates formed under these conditions can be redissolved. The chemical implications of these observations are discussed.
Adding complexed aluminum ions raises useful temperature of polyimide adhesive without embrittling it or reducing long term stability. Adhesives may be applied to prepared substrate surface without supports. Possible substrates are metal, composite, or polymeric film. Adhesive is excellent where bond flexibility is required.
Polyimide foam products having greatly improved burn-through and flame-spread resistance are prepared by the reaction of aromatic polyisocyanates with aromatic dianhydrides in the presence of metallic salts of octoic acid. The salts, for example stannous octoate, ferric octoate and aluminum octoate, favor the formation of imide linkages at the expense of other possible reactions.
The tribological properties of polyimide-bonded graphite fluoride films were studied with a pin-on-disk friction apparatus. A 440 C HT stainless steel rider with a 0.95 millimeter diameter flat area was slid against the film in order to achieve a light, closely controlled contact stress. A 1 kilogram load was applied to this flat to give a projected contact stress of 14 megapascals. Two stages of lubrication were operating. In the first stage, the film supported the load and the lubricating mechanism appeared to be the shear of a thin surface layer of the film between the rider and the bulk of the film. The second stage began after the original film was worn away, and the lubricating mechanism appeared to be the shear of very thin lubricant layers between the flat area on the rider and flat plateaus generated on the sandblasted asperities of the metallic substrate. The major difference between the lubricating mechanisms of the hemispherical and flat riders was that the flat wore through the film much more slowly than did the hemisphere.
A quality assurance program was developed which included specifications for celion/LARC-160 polyimide materials and quality control of materials and processes. The effects of monomers and/or polymer variables and prepeg variables on the processibility of celion/LARC prepeg were included. Processes for fabricating laminates, honeycomb core panels, and chopped fiber moldings were developed. Specimens and conduct tests were fabricated to qualify the processes for fabrication of demonstration components.
The effects of repetitive thermal cycling on the temperature-thermal deformation relation of graphite-polyimide were determined. The bending and axial strains, measured with strain gages, of unsymmetric 0 deg sub 2/90 deg sub 2 and 0 deg sub 4/90 deg sub 4 laminates were used as an indication of thermal deformation. The strains were measured as a function of temperature and two temperature ranges were used, room temperature to 180 C and room temperature to 315 C. Five cycles were run in each temperature range and the cycling was done in quasistatic fashion. The response of a flat 0 deg sub 8 laminate was measured as were the effects of repetitive cycling on the strain gages themselves. A piece-wise linear theory, based on classical lamination theory and using the variation of mechanical and thermal expansion properties with temperature, was compared with the experimental results. The correlation between theoretical predictions and experimental results for the thinner laminate was poor.
High strength, intermediate modulus graphite fibers were obtained from various commercial suppliers, and were used to fabricate PMR-15 and PMR-2 polyimide composites. The effects of the improved high strength graphite fibers on composite properties after exposure in air at 600 F were investigated. Two of the improved fibers were found to have an adverse effect on the long term performance of PMR composites. The influence of various factors such as fiber physical properties, surface morphology and chemical composition were also examined.
The effects of room temperature tensile loading and five thermal loadings, in the range -320 F (-196C) to 625F (330CC), upon the development of transverse microcracks (TVM) in Celion 6000/PMR-15 graphite-polyimide laminates were investigated. Microcracks were observed using a replicating technique, microscopy and X-ray. The mechanical or thermal load at which microcracking initiates and the ply residual stresses were predicted using laminate analysis with stress- and temperature-dependent material properties.
By varying the stoichiometry of the reactants in the preparation of PMR polyimide resin, changes occur in molecular weight distribution which influence the rheological properties and thus the processability of the resin, as well as the mechanical properties of the composite. The influence of 1-10 percent molar excess MDA on the molecular weight distribution and rheological properties of an imidized PMR system were exposed. Molecular weight distribution is characterized by gel permeation chromatography of the imidized molding compound; shear viscosity is related to changes in average molecular weight. The thermo-oxidative stability at 600 F, glass transition temperature, flexural and interlaminar shear properties of PMR polyimide/Celion 6000 graphite fiber composites are compared as a function of the percent excess MDA in the monomer reactant mixture.