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At least 577 records · Page 32

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NASA NTRS1981

Poly/phenylquinoxalines/ containing ethynyl groups

The synthesis of high molecular weight linear poly(phenylquinoxalines) containing pendant ethynyl groups is reported, where thermally-induced reactions of the ethynyl groups provided insoluble, cross-linked polymers with high glass transition temperatures. The ethynyl-containing polymer exhibited fair to poor processability by compression molding due to the thermal reaction of the ethynyl groups, which inhibited polymer flow, depending on ethynyl density. This class of polymers is not expected to be useful as laminating resins or adhesives, due to the processing difficulties. Use for them may be found, however, as solvents and corrosion-resistant high-temperature coatings.

Hergenrother, P. M.↗

NASA NTRS1981

Alignment of fluid molecules in an EHD contact

Dichroic infrared emission spectra have been obtained from an operating elastohydrodynamic contact under conditions showing unequivocally that the molecules of the fluid are aligned under shear flow in the bulk of the fluid and that the extent of the alignment is increased by the presence of an additive in a small concentration. This work applied particularly to polyphenyl ether and to 1,1,2-trichloroethane as the additive, but similar results have been obtained with polycyclohexyls and the same additive. The observation of two separate glass transitions for the polycyclohexyl solution is an indication of the occurrence of a phase separation in the Hertzian inlet zone. A model has been developed to explain the effect of these phenomena and their relation to traction.

Lauer, J. L.↗

NASA NTRS1981

Radiation effects on four polysulfone films

The response of polysulfones to proton and electron radiation is evaluated by assessing the radiation durability of four selected sulfones, establishing radiation interaction mechanisms with the polymer chain, and determining the dependence of radiation durability on chemical structure. Chain scission appears to predominate at lower doses up to about 10 to the 9th rad, and past this threshold the second mechanism, crosslinking, seems to predominate. This is evidenced by the increase in modulus, glass transition temperature, and increased quantity of thermally stable residue at high temperatures. The variations of chemical structure of the polysulfones appear to have little effect on the response to radiation.

Santos, B.↗

NASA NTRS1982

Addition polyimide adhesives containing various end groups

Addition polyimode oligomers have been synthesized from 3,3 prime, 4,4 prime-benzophenone tetracarboxylic acid dianhydride and 3,3 prime-methylenedianiline using a variety of latent crosslinking groups as end-caps. The nominal 1300 molecular weight imide prepolymers were isolated and characterized for solubility in amide, chlorinated and ether solvents, melt-flow and cure properties, glass transition temperature, and thermal stability on heating in an air atmosphere. Adhesive strengths of the polyimides were obtained both at ambient and elevated temperatures before and after aging at 232 C. Properties of the novel addition polyimides were compared to a known nadic end-capped adhesive, LARC-13.

Saint Clair, A. K.↗

NASA NTRS1982

Forced torsional properties of PMR composites with varying nadic ester concentrations and processing histories

PMR polyimide resin was prepared from 4,4'-methylenedianiline, the dimethyl ester of 3,3',4,4'-benzophenonetetracarboxylic acid and the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid (NE). The NE group serves as a chain terminator and crosslinking site. PMR/Celion 6000 composites were fabricated from resins having varying NE concentrations using two molding processes, and the laminates characterized in forced torsion. Glass transition temperatures (T(g)) of 360-390 C were observed in the crosslinked resins, as compared with the literature value of 284 C reported for the uncrosslinked system. T(g) did not decrease with decreasing NE concentrations over the range from 2.0 to 1.25 moles. Stoichiometry, within the range studied, showed little influence on shear properties; however, a 25% variation in matrix shear modulus with processing was observed. The G(12) values determined in forced torsion were in excellent agreement with those reported from tensile tests of + or - 45 deg laminates. A branching and possible secondary crosslink mechanism is proposed based on dynamic mechanical behavior and infrared spectra of the composites.

Hurwitz, F. I.↗

NASA NTRS1983

Aromatic Polyimides With Group VI Linkages

New polymer system combines thermal and solvent resistant properties of aromatic polyimides with processability of PPX polymers. PPX polymers include polyphenylene oxide, polyphenylene sulfide, and polyphenylene sulfone classes. Generally more processable by hot melt or thermoplastic techniques than aromatic polyimides. PPX systems more susceptible to attack by solvents and have lower glass transition temperatures than PI group.

St. Clair, T. L.↗

NASA NTRS1982

Effect of matrix resin on the impact fracture characteristics of graphite-epoxy laminates

The effect of resin chemistry on basic impact energy absorbent mechanisms exibited by graphite-epoxy composites was investigated. Impact fracture modes and microscopic resin deformation characteristics were examined for 26 NASA-impacted graphite epoxy laminates with different resin chemistries. Discrete specimen fracture modes were identified through cross sectional examination after impact, and subsequently compared with measured glass transition temperatures, cure cycles, and residual impact capabilities. Microscopic resin deformation mechanisms and their overall relationship to impact loading conditions, voids, and resin content were also characterized through scanning electron microscopic examination of separated fracture surfaces.

Hertzberg, P. E.↗

NASA NTRS1982

Metal ion-containing epoxies

A variety of metallic and organometallic complexes to be used as potential additives for an epoxy used by the aerospace industry as a composite matrix resin were investigated. A total of 9 complexes were screened for compatibility and for their ability to accelerate or inhibit the cure of a highly crosslinkable epoxy resin. Methods for combining the metallic complexes with the resin were investigated, gel times recorded, and cure exotherms studied by differential scanning calorimetry. Glass transition temperatures of cured metal ion containing epoxy castings were determined by thermomechanical analysis. Thermal stabilities of the castings were determined by thermogravimetric analysis. Mechanical strength and stiffness of these doped epoxies were also measured.

Stoakley, D. M.↗

NASA NTRS1982

Polyimides with pendant alkyl groups

The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

Jensen, B. J.↗

NASA NTRS1983

Dynamic Mechanical Properties of N-Phenylnadimide Modified PMR Polyimide Composites

The rheological behavior of newly developd Celion 6000/N-phenylnadimide modified PMR polyimide and PMR-15 composites was investigated. The dynamic mechanical properties were correlated with the structure of N-phenylnadimide modified PMR polyimides. The storage modulus (G'), loss modulus (G''), and loss tangent (tan delta) of four composite systems were measured over a temperature range from -150 to 400 C. Three well defined peaks were seen in the regions of 360, 100, and -120 C, corresponding to the alpha, beta, and gamma relaxations, respectively, of the matrix resins. The activation energies of the alpha, beta, and gamma relaxations were estimated to be 232, 60, and 14 kcal/mole, respectively, for PMR-15. Addition of N-phenylnadimide to the PMR-15 composition lowered the glass transition temperature and the activation energies of PMR-15 polyimide. The dynamic mechanical data appear to be consistent with the formation of a copolymer from N-phenylnadimide and a PMR-15 prepolymer.

Pater, R. H.↗

NASA NTRS1983

Simplified composite micromechanics equations for hygral, thermal and mechanical properties

A unified set of composite micromechanics equations of simple form is summarized and described. This unified set can be used to predict unidirectional composite (ply) geometric, mechanical, thermal and hygral properties using constituent material (fiber/matrix) properties. This unified set also includes approximate equations for predicting (1) moisture absorption; (2) glass transition temperature of wet resins; and (3) hygrothermal degradation effects. Several numerical examples are worked-out to illustrate ease of use and versatility of these equations. These numerical examples also demonstrate the interrelationship of the various factors (geometric to environmental) and help provide insight into composite behavior at the micromechanistic level.

Chamis, C. C.↗

NASA NTRS1983

Epoxy hydantoins as matrix resins

Tensile strength and fracture toughness of castings of the hydantoin resins cured with methylenedianiline are significantly higher than MY 720 control castings. Water absorption of an ethyl, amyl hydantoin formulation is 2.1 percent at equilibrium and Tg's are about 160 C, approximately 15 deg below the final cure temperature. Two series of urethane and ester-extended hydantoin epoxy resins were synthesized to determine the effect of crosslink density and functional groups on properties. Castings cured with methylenedianiline or with hexahydrophthalic anhydride were made from these compounds and evaluated. The glass transition temperatures, tensile strengths and moduli, and fracture toughness values were all much lower than that of the simple hydantoin epoxy resins. Using a methylene bishydantoin epoxy with a more rigid structure gave brittle, low-energy fractures, while a more flexible, ethoxy-extended hydantoin epoxy resin gave a very low Tg.

Weiss, J.↗

NASA NTRS1983

Development of low viscosity alkane-based urethane for connector potting applications

Two series of saturated hydrocarbon-based urethanes were prepared with isophorone diisocyanate and one series with methyl bis (4-cyclohexyl isocyanate). The urethanes with molecular weights as great as 2500 had viscosities low enough and a working life long enough to be used in potting, molding, and coating applications. Specimens were prepared and mechanical properties such as hardness, tensile strength elongation, and tear strength were determined. Thermomechanical properties (glass transition and expansion coefficient) and thermogravimetric properties were determined.

Morris, D. E.↗

NASA NTRS1982

The effect of physical aging on the time-dependent properties of carbon-fiber-reinforced epoxy composites

Annealing in nitrogen below the glass transition temperature T(g) is found to affect the matrix-dominated physical properties of postcured, (+ and -45)2s specimens of Thornel 300 carbon fiber/Fiberite 934 epoxy composite as well as neat Fiberite 934 epoxy resin. The damping behavior, stress-relaxation rate and enthalpic state of the matrix material are found to decrease as functions of annealing time. The time-dependent change in physical properties is explained on the basis of free-volume collapse related to the physical aging of the nonequilibrium glassy network of epoxy. Such physical aging in network epoxy has been demonstrated to be thermoreversible through the monitoring of its kinetics by differential scanning calorimetry, stress relaxation tests, and dynamic mechanical analysis.

Kong, E. S. W.↗

NASA NTRS1983

Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)

Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.

Hurwitz, F. I.↗

NASA NTRS1983

Cobalt ion-containing epoxies

Varying concentrations of an organometallic cobalt complex were added to an epoxy system currently used by the aerospace industry as a composite matrix resin. Methods for combining cobalt (III) acetylacetonate with a tetraglycidyl 4,4 prime - diaminodiphenylmethane-based epoxy were investigated. The effects of increasing cobalt ion concentration on the epoxy cure were demonstrated by epoxy gel times and differential scanning calorimetry cure exotherms. Analysis on cured cobalt-containing epoxy castings included determination of glass transition temperatures by thermomechanical analysis, thermooxidative stabilities by thermogravimetric analysis, and densities in a density gradient column. Flexural strength and stiffness were also measured on the neat resin castings.

Stoakley, D. M.↗

NASA NTRS1983

Plasma polymerized high energy density dielectric films for capacitors

High energy density polymeric dielectric films were prepared by plasma polymerization of a variety of gaseous monomers. This technique gives thin, reproducible, pinhole free, conformable, adherent, and insoluble coatings and overcomes the processing problems found in the preparation of thin films with bulk polymers. Thus, devices are prepared completely in a vacuum environment. The plasma polymerized films prepared all showed dielectric strengths of greater than 1000 kV/cm and in some cases values of greater than 4000 kV/cm were observed. The dielectric loss of all films was generally less than 1% at frequencies below 10 kHz, but this value increased at higher frequencies. All films were self healing. The dielectric strength was a function of the polymerization technique, whereas the dielectric constant varied with the structure of the starting material. Because of the thin films used (thickness in the submicron range) surface smoothness of the metal electrodes was found to be critical in obtaining high dielectric strengths. High dielectric strength graft copolymers were also prepared. Plasma polymerized ethane was found to be thermally stable up to 150 C in the presence of air and 250 C in the absence of air. No glass transitions were observed for this material.

Yamagishi, F. G.↗

NASA NTRS1984

Phenoxy resins containing pendent ethynyl groups

As part of an effort on tougher/solvent resistant matrix resins for composites, research was directed towards exploring methods to improve the solvent resistance of linear amorphous thermoplastics. Ethyl reactive groups were placed on the ends of oligomers and pendent along the polymer chain and subsequently thermally reacted to provide crosslinking and thus improvement in solvent resistance. This concept is extended to another thermoplastic, a phenoxy resin. A commercially available phenoxy resin (PKHH) was systematically modified by reaction of the pendent hydroxyl groups on the phenoxy resin with various amounts of 4-ethynylbenzoyl chloride. As the pendent ethynyl group content in the phenoxy resin increased, the cured resin exhibited a higher glass transition temperature, better solvent resistance and less flexibility. The solvent resistance was further improved by correcting a low molecular weight diethynyl compound, 2,2-bis(4-ethynylbenzoyloxy-4'-phenyl)propane, with a phenoxy resin containing pendent ethynyl groups.

Hergenrother, P. M.↗