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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.
Studies conducted with addition-type polyimides are reviewed with emphasis on the development of the Polymerization of Monomer Reactants (PMR) approach, in which PMR occurs on the surface of the reinforcing fibers.
A polyimide is a polymer composed of alternating units of diamine and dianhydride, linked to each other via an imide bond. PMR polyimides, commonly used in the aerospace industry, are generally capped at each end by an endcap (such as the nadic endcap used in PMR 15) which serves a double function: (1) it limits the number of repeating units and, hence, the average molecular weight of the various polymer chains (oligomers), thereby improving processibility; (2) Upon further treatment (curing), the endcap crosslinks the various oligomer strands into a tough heat-resistant piece. It is this very endcap, so important to processing, that accounts for much of the weight loss in the polymer on aging in air at elevated temperatures. Understanding this degradation provides clues for designing new endcaps to slow down degradation, and prolong the lifetime of the material.
The use of self-lubricating polymers and polymer composites in space is somewhat limited today. In general, they are only used when other methods are inadequate. There is potential, however, for these materials to make a significant impact on future space missions if properly utilized. Some of the different polymers and fillers used to make self-lubricating composites are surveyed. The mechanisms of composite lubrication and wear, the theory behind transfer film lubricating mechanisms, and some factors which affect polymer composite wear and transfer are examined. In addition, some of the current space tribology application areas for self-lubricating polymer composites and polymer transfer are mentioned.
Workers at NASA Ames Research center are endeavoring to develop durable, oxidation-resistant, foam thermal protection systems (TPSs) that would be suitable for covering large exterior spacecraft surfaces, would have low to moderate densities, and would have temperature capabilities comparable to those of carbon-based TPSs [reusable at 3,000 F (.1,650 C)] with application of suitable coatings. These foams may also be useful for repairing TPSs while in orbit. Moreover, on Earth as well as in outer space, these foams might be useful as catalyst supports and filters. Preceramic polymers are obvious candidates for use in making the foams in question. The use of these polymers offers advantages over processing routes followed in making conventional ceramics. Among the advantages are the ability to plastically form parts, the ability to form pyrolized ceramic materials at lower temperatures, and the ability to form high-purity microstructures having properties that can be tailored to satisfy requirements. Heretofore, preceramic polymers have been used mostly in the production of such low-dimensional products as fibers because the loss of volatiles during pyrolysis of the polymers leads to porosity and large shrinkage (in excess of 30 percent). In addition, efforts to form bulk structures from preceramic polymers have resulted in severe cracking during pyrolysis. However, because the foams in question would consist of networks of thin struts (in contradistinction to nonporous dense solids), these foams are ideal candidates for processing along a preceramic-polymer route.
Lightweight, fire resistant foams have been developed through the modification of conventional neoprene-isocyanate foams by the addition of an alkyl halide polymer. Extensive tests have shown that the modified/neoprene-isocyanate foams are much superior in heat protection properties than the foams heretofore employed both for ballistic and ablative purposes.
Polyimide polymers which are thermally stable and processable are developed. The addition of alkyl substituents to an aromatic ring in the polymer backbone is examined along with polyimide precursor amines containing functional groups that allow for post-cure crosslinking. The synthesis of key monomers is reported, including 2,4,6-tris (m-aminobenzyl) 1,3,5-trimethyl benzene and 2,4,6-tris (p-aminobenzyl) 1,3,5-trimethyl benzene. The preparation of a key monomer, 2,5,3-triamino benzophenone, is reported.
Flexible separators consisting of a substrate coated with a mixture of a polymer and organic and inorganic additives were cycle tested in nickel-zinc cells. By substituting a rubber-based resin for polyphenylene oxide in the standard inorganic-organic separator, major improvements in both cell life and flexibility were made. Substituting newsprint for asbestos as the substrate shows promise for use on the zinc electrode and reduces separator cost. The importance of ample electrolyte in the cells was noted. Cycle lives and the characteristics of these flexible, low-cost separators were compared with those of a standard microporous polypropylene separator.
Potassium thiochromite, sodium thiochromite, and Ti 0.5V 0.5S 2 prepared and used in cycling studies. In addition, some electrochemical studies with polymer electrolyte (PEO-NaSCN) cells were also attempted.
Since composite laminates are beginning to be identified for use in reusable launch vehicle propulsion systems, a task was undertaken to assess the feasibility of making cryogenic feedlines with integral flanges from polymer matrix composite materials. An additional level of complexity was added by having the feedlines be elbow shaped. Four materials, each with a unique manufacturing method, were chosen for this program. Feedlines were to be made by hand layup (HLU) with standard autoclave cure, HLU with electron beam cure, solvent-assisted resin transfer molding (SARTM), and thermoplastic tape laying (TTL). A test matrix of fill and drain cycles with both liquid nitrogen and liquid helium, along with a heat up to 250 F, was planned for each of the feedlines. A pressurization to failure was performed on any feedlines that passed the cryogenic cycling testing. A damage tolerance subtask was also undertaken in this study. The effects of foreign object impact to the materials used was assessed by cross-sectional examination and by permeability after impact testing. At the end of the program, the manufacture of the electron beam-cured feedlines never came to fruition. All of the TTL feedlines leaked heavily before any cryogenic testing, all of the SARTM feedlines leaked heavily after one cryogenic cycle. Thus, only the HLU with autoclave cure feedlines underwent the complete test matrix. They passed the cyclic testing and were pressurized to failure.
A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.
Melt-processable polyimides maintain desirable polymer properties prepared by adding small amounts of certain low-molecular-weight, thermally stable additives. Useful in preparing void-free polyimide composites from higher flow resins that wet out fibers at lower processing temperatures. Applied to preparing high-temperature polyimide adhesives allowing enhanced wetting of adherends and ultimately better adhesion. Improvement to processing polyimides and potential application for production of films, coatings, adhesives, and composites.
Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.
Polymer Laser Sintering (LS) is an additive manufacturing technique that builds 3D models layer by layer using a laser to selectively melt cross sections in powdered polymeric materials, following sequential slices of the CAD model. LS generally uses thermoplastic polymeric powders, such as polyamides (i.e. Nylon), and the resultant 3D objects are often weaker in their strength compared to traditionally processed materials, due to the lack of polymer inter-chain connection in the z-direction. The objective of this project is to investigate the possibility of printing a melt-processable RTM370 imide resin powder terminated with reactive phenylethynyl groups by LS, followed by a postcure in order to promote additional crosslinking to achieve higher temperature (250-300 C) capability. A preliminary study to build tensile specimens by LS and the corresponding DSC and rheology study of RTM370 during LS process is presented.
A synthesis scheme was developed for a host of nonclassical addition-type thermoplastics (ATT) that can be cured by an addition reaction, leading to a linear polymer structure. The synthesis involves the reaction of an acetylene-terminated prepolymer with either a bismaleimide (BMI) or a biscitraconimide. A new polymer, designated LaRC-RP80, synthesized using this scheme, was found to exhibit several significantly improved properties over the commercial BMI, Kerimid 601, including an eight-fold increase in toughness while maintaining a high Tg, a higher (by 167 C) heat stability, and a 50-percent increase in moisture resistance. In addition, LaRC-RP80 has good hot/wet lap shear strength and processes easily at 288 C without voids in the finished product.
The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.
A process for preparing an ultra-thin, adhesiveless, multi-layered, patterned polymer substrate is disclosed. The process may be used to prepare both rigid and flexible cables and circuit boards. A substrate is provided and a polymeric solution comprising a self-bonding, soluble polymer and a solvent is applied to the substrate. Next, the polymer solution is dried to form a polymer coated substrate. The polymer coated substrate is metallized and patterned. At least one additional coating of the polymeric solution is applied to the metallized, patterned, polymer coated substrate and the steps of metallizing and patterning are repeated. Lastly, a cover coat is applied. When preparing a flexible cable and flexible circuit board, the polymer coating is removed from the substrate.
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.