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Stoakley, D. M.

Publications and source records attributed to Stoakley, D. M..

Microstructural Characterization of Thin Polyimide Films by Positron Lifetime Spectroscopy

Positron lifetimes have been measured in a series of thin aromatic polyimide films. No evidence of positronium formation was observed in any of the films investigated. All test films exhibited only two positron lifetime components, the longer component corresponding to the positrons annihilating at shallow traps. Based on these trapped positron lifetimes, free volume fractions have been calculated for all the films tested. A free volume model has been developed to calculate the dielectric constants of thin polyimide films. The experimental and the calculated values for the dielectric constants of the films tested are in reasonably good agreement. It has been further noted that the presence of bulky CF(sub 3) groups and meta linkages in the polyimide structure results in higher free volume fraction and, consequently, lower dielectric constant values for the films studied.

Eftekhari, A.

Low coefficient of thermal expansion polyimides containing metal ion additives

Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

Stoakley, D. M.

Low dielectric thermoplastic polyimide resin

NASA-Langley studies of polymer structure-property relationships have led to the development of a method for the reduction of dielectric constants in polyimides through chemical alterations of polymer backbone composition to reduce chain-chain electronic interactions, as well as through the incorporation of fluorine atoms into the polymer molecular structure. Still-greater dielectric constant reductions are obtainable by means of a physical incorporation of diamic acid additives into these low-dielectric polyimide systems; the resulting thermoplastic resins are applicable to polymer matrices for composite structural materials.

Stoakley, D. M.

Polyimide processing additives

A method has been found for enhancing the melt flow of thermoplastic polyimides during processing. A high molecular weight 422 copoly(amic acid) or copolyimide was fused with approximately 0.05 to 5 pct by weight of a low molecular weight amic acid or imide additive, and this melt was studied by capillary rheometry. Excellent flow and improved composite properties on graphite resulted from the addition of a PMDA-aniline additive to LARC-TPI. Solution viscosity studies imply that amic acid additives temporarily lower molecular weight and, hence, enlarge the processing window. Thus, compositions containing the additive have a lower melt viscosity for a longer time than those unmodified.

Pratt, J. R.

Lanthanide-containing polyimides

The preparation of a variety of lanthanide-containing polyimide films is described, and results of their characterization are presented. The properties investigated include the glass transition temperature, thermooxidative stability, magnetic susceptibility, and electrical conductivity of the polymer. Films containing lanthanide chlorides, fluorides, and sulfides are flexible, but those containing lanthanide nitrates are extremely brittle. The addition of lanthanide acetates and acetylacetonates caused immediate gelation of two of the synthesis-mixture ingredients. It was found that, in general, the addition of lanthanide to the polyimide increases the density and glass transition temperature of the polymer but slightly decreases the thermooxidative stability.

Stoakley, D. M.

Selected spectroscopic and magnetic properties of lanthanide complexes in polyimide XU-218

Polyimide XU-218 films containing approximately 5 wt pct of Eu(III), Gd(III), Tb(III), and Er(III) were prepared, and the effects of complexing each of the metals with the following four ligands were investigated: N-phenylphthalamate (NPPA), 2,4-pentanedionate (AcAc), 1,3-diphenyl 1,3-propanedionate (DBM), and a new hexa-aza-macrocyclic (MAC) ligand. The tris-chelated complexes of the mononegative ligands NPPA, AcAc, and DBM produced transparent, flexible films, which had magnetic and spectral properties very similar to those of the parent lanthanide complexes, while complexes of MAC showed problems due to the presence of lattice water and yielded dark brittle films. AcAc caused little or no effect on the glass transition temperature (Tg), while NPPA and DBM complexes lowered Tg to 269-290 C, and MAC indicated moisture by inflexion at 95-100 C with a true Tg at 320 C. All lanthanide-containing films were paramagnetic.

Stoakley, D. M.

Investigation of the effects of cobalt ions on epoxy properties

The effects of Co(acac)sub x complexes on MY-720 epoxy properties have been investigated. It appears that Co2(+) ions form antibonding or nonbonding orbitals which increase the free volume and also reduce the cohesiveness of the host epoxy. The effects of Co2(+) ions, on the other hand, seem to result in increased Cohesiveness of the epoxy. The experimental values of magnetic moments of both types of ions in MY-720 suggest that the orbital momentum contributions of the (3d) electrons are partially conserved, though the effect is more pronounced for Co2(+) ions. The coordination environment of the cobalt ions in the host epoxy does not appear to be uniquely defined. These results indicate that the effects of metal ions on resin properties cannot be easily predicted on the basis of ligand field theory argument alone. Complex interactions between metal ions and host epoxy molecular structure suggest the desirability of parallel experimental investigations of electronic, magnetic, and mechanical properties of metal ion-containing epoxy samples for comparison with theory.

Singh, J. J.

Polyether/Polyester Graft Copolymers

Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

Bell, Vernon L., Jr.

Chromium Ions Improve Moisure Resistance of Epoxy Resins

Broad spectrum of thermosetting epoxy resins used on commercial and military aircraft, primarily as composite matrices and adhesives. In new technique, chromium-ion containing epoxy with improved resistance to moisture produced where chromium ions believed to prevent absorption of water molecules by coordinating themselves to hydroxyl groups on epoxy chain. Anticipated that improved epoxy formulation useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft. Improvement made without sacrifice in mechanical properties of polymer.

St. Clair, A. K.

Cobalt Ions Improve the Strength of Epoxy Resins

Technique developed for improving mechanical strength of epoxy resins by adding cobalt ions in form of tris(acetylacetonato)cobalt (III) complex. Solid cast disks prepared from cobalt ion-containing epoxy resins tested for flexural strength and stiffness. Incorporation of cobalt ions into epoxies increased flexural strength of resins by 10 to 95 percent. Suitable resins for this technique include any liquid or solid TGMDA resins. Improved epoxy formulation proves useful as composite matrix resin, adhesive, or casting resin for applications on commercial and advanced aircraft.

Stoakley, D. M.

Process for improving mechanical properties of epoxy resins by addition of cobalt ions

A resin product useful as an adhesive, composite or casting resin is described as well as the process used in its preparation to improve its flexural strength mechanical property characteristics. Improved flexural strength is attained with little or no change in density, thermal stability or moisture resistance by chemically incorporating 1.2% to 10.6% by weight Co(3) ions in an epoxidized resin system.

Stoakley, D. M.

An investigation of chemically-induced improvement in saturation moisture characteristics of epoxies

MY-720/DDS epoxy samples were treated with three selected chemical compounds to render the active H-sites inactive for moisture absorption. Treating the epoxy castings with acetyl chloride and dichlorodimethyl silane leads only to surface changes indicating that these molecules are too large to penetrate the epoxy castings. Boron trifluoride, on the other hand, does penetrate the epoxy chain as is indicated by the formation of green domains in the interior of the castings. However, the process of saturating the specimens with moisture appears to leach out the chemical additives--thereby nullifying their possible ameliorative effects.

Singh, J. J.

Effect of metal ions on positron annihilation characteristics in metal ion containing epoxies

In the course of developing improved moisture-resistant epoxy resins, two different types of epoxy resins containing variable mole ratios of chromium ions per polymer repeat unit were developed. Positron annihilation characteristics have been investigated in these resins as a function of their metal ion content. In both cases, the presence of metal ions reduces the lifetime as well as the intensity of the long life component. The long life component intensity reduction is considerably more pronounced than the lifetime reduction. These results have been discussed in terms of increased unpaired electron density at Ps formation sites due to the presence of chromium ions in the matrix.

Singh, J. J.

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.

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.

Impact penetration studies of graphite/epoxy laminates

A study was conducted to provide an initial insight into the role of the matrix in impact energy absorption of graphite/epoxy laminates. A single epoxy system, NARMCO 5208, in both composite and cured neat-resin form was studied with a constant velocity impact test apparatus. The parameters investigated include resin cure temperature, fiber type, ply thickness and orientation, and impact velocity. The results from the study show that matrix chemistry, as obtained by cure temperature changes, has a significant effect upon the failure mode and energy absorption during impact.

Sykes, G. F.