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At least 955 records · Page 53

Ion beam sputter-deposited thin film coatings for protection of spacecraft polymers in low earth orbit

Ion beam sputter-deposited thin films at Al2O3, SiO2, and a codeposited mixture of predominantly SiO2 with small amounts of fluoropolymer were evaluated both in laboratory plasma ashing tests and in space on board Shuttle flight STS-8 for effectiveness in preventing oxidation of polyimide Kapton. Measurements of mass loss and optical performance of coated and uncoated polyimide samples exposed to the low earth orbital environment are presented. Optical techniques were used to measure loss rates of protective films exposed to atomic oxygen. Results of the analysis of the space flight exposed samples indicate that thin film metal oxide coatings are very effective in protecting the polyimide. Metal oxide coatings with a small amount of fluoropolymer codeposited have the additional benefit of great flexibility.

Banks, B. A.↗

Preparation of bis(4-(3,4 dimethylene pyrrolidyl) phenyl) methane as a high temperature reactive oligomer

A major goal in the field of high temperature polymers was to prepare aromatic polyimides that can be easily fabricated with the required thermal and physical properties for aerospace applications. Recent research was directed to achieve polyimides that are: soluable in a common organic solvent; melt-processable; and thermally curable without the evolution of volatile by-products. A monomer, N-phenyl 3,4-dimethylene pyrrolidine, that can be modified to form a bis (exocyclodiene) I for the preparation of polyimides by the Diels-Alder process was developed. Preparation of high temperature polymeric materials by Diels-Alder polymerization that will maintain their integrity and toughness during long exposure time at elevated temperature is sought.

Ottenbrite, Raphael M.↗

Development of an impact- and solvent-resistant thermoplastic composite matrix, phase 4

Polyimides from BTDA with m-phenylenediamine and three aliphatic diamines were prepared in cresol and characterized. Characterization tests included compression strength and modulus, stressed solvent resistance, and melt-flow tests. Efforts to reduce the molecular weights of these polymers by either stoichiometric imbalance or phthalic anhydride end capping produced opacity in the polymer moldings when the stoichiometry was less than 99 percent. Use of 2,4-diaminotoluene in place of the m-phenylenediamine allowed clear polymer moldings to be obtained at all stoichiometries by end capping or stoichiometric imbalance. After melt-flow/molecular-weight studies, carbon fabric composites were prepared from three polyimide compositions containing BTDA, 2,4-diaminotoluene and two aliphatic diamines. Flexural strengths of two of the resins were in excess of 689 MPa (100 ksi) at both room temperature and 93 C. The polyimide from BTDA was selected for scale-up and neat resin characterization tests. The Tg of this polymer was 233 C.

Delano, C. B.↗

Polymer Lubricants For Use In Vacuum

Report describes tests of lubricating properties of 10 polymer-based materials - in particular, polyimides - in vacuum. Commercially available materials, in forms of solid bodies and films on metals, were tested on pin-on-disk apparatus in vacuum. Best low-wear, low-friction material was 80 PMDA/20 BTDA solid-body polyimide. Friction and wear properties of most polyimides so good in vacuum that solid-lubricant additives not necessary.

Fusaro, Robert L.↗

Evaluation of two bisimide additives in LARC-TPI adhesive

The processability of aromatic polyimides can be improved by the addition of bis (amide) acids or bisimides to LARC-TPI. These low molecular weight additives apparently lower the melt viscosity of aromatic polyimides without affecting the glass transition temperature. Well-consolidated, fiber reinforced composites were fabricated using this technology. LARC-TPI can be processed as a thermoplastic polyimide to form high strength bonds, however, this is generally accomplished by processing at relatively high bonding pressures. An adhesive investigation is presented on the effects of two bisimide additives to LARC-TPI in an attempt to improve the bonding process by lowering the viscosity of the material to achieve improved bond strength properties. Apparently, the high flow which is exhibited by the additives when they melt, tended to be masked by the more viscous LARC-TPI.

Progar, Donald J.↗

Surface characterization and adhesion of oxygen plasma-modified LARC-TPI

LARC-TPI, an aromatic thermoplastic polyimide, was exposed to an oxygen plasma as a surface pretreatment for adhesive bonding. Chemical and physical changes which occurred in the polyimide surface as a result of the plasma treatment were investigated using X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IR-RAS), contact-angle analysis, ellipsometry, and high resolution SEM. A 180-deg peel test with an acrylate-based pressure sensitive adhesive as a flexible adherent was utilized to study the interactions of the plasma-treated polyimide surface with other polymeric materials. The surface characterization and adhesion testing results showed that the oxygen plasma treatment, while creating a more hydrophilic, polar surface, also caused chain scission, resulting in the formation of a weak boundary layer which inhibited adhesion.

Chin, J. W.↗

Addition Curing Thermosets Endcapped with 4-Amino (2.2) Paracyclophane

A new family of addition curing polyimides were prepared that contained 4-amino (2.2)-paracyclophane as the endcap. An improved synthesis of the endcap 4-amino-(2.2) cyclophane was accomplished increasing the yield to 60 percent and simplifying the procedure. DSC and rheological analysis of endcapped polyimide oligomers confirmed that the onset for polymerization of the ethylene bridge was 250 C. C-13 CP/MAS NMR was used to determine the structural changes of the oligomers after thermal treatment. The cyclophane capped polyimides were successfully compression molded to form void free neat resin specimens. Tg's as high as 353 C were obtained by thermomechanical analysis for postcured samples. Preliminary thermal stability studies suggest that these resins have a high onset of decomposition ranging from 549 to 567 C.

Waters, John F.↗

Improving processing and toughness of a high performance composite matrix through an interpenetrating polymer network. VI

A simultaneous semi-interpenetrating polymer network (semi-IPN) concept is presented which combines easy-to-process, but brittle, thermosetting polyimides with tough, but difficult to process, linear thermoplastic polyimides. The combination results in a semi-IPN with the easy processability of a thermoset and good toughness of a thermoplastic. Four simultaneous semi-IPN systems were developed from commercially available NR-150B2 combined with each of the four Thermid materials (LR-600, AL-600, MC-600, and FA-700). It is concluded that there is a significant improvement in resin fracture toughness of Thermid-polyimide-based semi-IPN systems and some improvement in composite microcracking resistance compared to Thermid LR-600. Excellent composite mechanical properties have been achieved. These new semi-IPN materials have the potential to be used as composite matrices, adhesives, and molding materials.

Pater, Ruth H.↗

Evaluation of optically transparent polyetherimide films for applications in space

Several series of aromatic polyetherimide films have been synthesized and characterized with the objective of obtaining maximum optical transparency for applications in space. Incorporation of phenoxy groups into aromatic polyimides has resulted in a reduction in the color intensity of these films compared to commercial polyimide film by reducing electronic interactions between polymer chains. The resulting lightly colored to colorless polyetherimide films have been characterized by UV-visible and infrared spectroscopy before and after exposure to varying doses of UV and electron irradiation designed to simulate use as second-surface mirror thermal control coatings. After exposure to 300 equivalent solar hours UV irradiation and 1 MeV electron irradiation, the polyetherimides were 2.2 to 2.6 times more transparent than commercial polyimide film of the same thickness.

St. Clair, Anne K.↗

Investigation of Polymer Liquid Crystals

The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.

Han, Kwang S.↗

Organometallic Polymeric Conductors

For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for over 150 days in air at ambient temperature. The conductivity of the films dropped only half an order of magnitude in that time. Films aged under vacuum at ambient temperature diminished slightly in conductivity in the first day, but did not change thereafter. An experimental design approach will be applied to maximize the efficiency of the laboratory effort. The material properties (initial and long term) will also be monitored and assessed. The experimental results will add to the existing database for electrically conductive polymer materials. Attachments: 1) Synthesis Crystal Structure, and Polymerization of 1,2:5,6:9,10-Tribenzo-3,7,11,13-tetradehydro(14) annulene. 2) Reinvestigation of the Photocyclization of 1,4-Phenylene Bis(phenylmaleic anhydride): Preparation and Structure of (5)Helicene 5,6:9,10-Dianhydride. 3) Preparation and Structure Charecterization of a Platinum Catecholate Complex Containing Two 3-Ethynyltheophone Groups. and 4) Rigid-Rod Polymers Based on Noncoplanar 4,4'-Biphenyldiamines: A Review of Polymer Properties vs Configuration of Diamines.

Youngs, Wiley J.↗

Comparison of Graphite Fabric Reinforced PMR-15 and Avimid N Composites After Long Term Isothermal Aging at Various Temperatures

Extensive effort is currently being expended to demonstrate the feasibility of using high-performance, polymer-matrix composites as engine structural materials over the expected operating lifetime of the aircraft, which can extend from 18,000 to 30,000 hr. The goal is to develop light-weight, high-strength, and high-modulus materials for use in higher temperature sections of advanced 21 st century aircraft propulsion systems. To accomplish this goal, it is necessary to pursue the development of thermal and mechanical durability models for graphite-fiber-reinforced, polymer-matrix composites. Numerous investigations have been reported regarding the thermo-oxidative stability (TOS) of the polyimide PMR-15 (1-5). A significant amount of this work has been directed at edge and geometry effects, reinforcement fiber influences, and empirical modeling of high-temperature weight loss behavior. It is yet to be determined if the information obtained from the PMR-15 composite tests is applicable to other polyimide-matrix composites. The condensation-curing polymer Avimid N is another advanced composite material often considered for structural applications at high temperatures. Avimid N has better thermo-oxidative stability than PMR-15 (6), but the latter is more easily processed. The most comprehensive study of the thermo-oxidative stability of Avimid N neat resin and composites at 371 (infinity)C is found in Salin and Seferis (7). The purposes of the work described herein were to compare the thermal aging behavior of these two matrix polymers and to determine the reasons for and the consequences of the difference in thermal durability. These results might be of some use in improving future polymer development through the incorporation of the desirable characteristics of both polyimides.

Bowles, Kenneth J.↗

Preparation, Fabrication, and Evaluation of Advanced Polymeric and Composite Materials

The thesis titles are given below: physical and mechanical behavior of amorphous poly(arylene ether-co-imidasole)s and poly(arylene ether-co-imidasole) modification epoxies; the requirements of patentability as applied to the chemical arts; fabrication of thermoplastic polymer composite ribbon; blend of reactive diluents with phenylethynyl-terminated arylene ether oligomers; the synthesis, characterization, and application of ether-containing polyimides; the synthesis of reflective and electrically conductive polyimide films via an in-situ self-metalization procedure using silver (I) complexes; the thermal cure of phenylethynyl terminated polyimides and selected model compounds; and the synthesis, characterization, and molecular modeling of cyclic arylene ether oligomers.

Orwoll, Robert A.↗

Stirling Space Engine Program: Final Report - Volume 1

The objective of this program was to develop the technology necessary for operating Stirling power converters in a space environment and to demonstrate this technology in full-scale engine tests. Hardware development focused on the Component Test Power Converter (CTPC), a single cylinder, 12.5-kWe engine. Design parameters for the CTPC were 150 bar operating pressure, 70 Hz frequency, and hot-and cold-end temperatures of 1050 K and 525 K, respectively. The CTPC was also designed for integration with an annular sodium heat pipe at the hot end, which incorporated a unique "Starfish" heater head that eliminated highly stressed brazed or weld joints exposed to liquid metal and used a shaped-tubed electrochemical milling process to achieve precise positional tolerances. Selection of materials that could withstand high operating temperatures with long life were another focus. Significant progress was made in the heater head (Udimet 700 and Inconel 718 and a sodium-filled heat pipe); the alternator (polyimide-coated wire with polyimide adhesive between turns and a polyimide-impregnated fiberglass overwrap and samarium cobalt magnets); and the hydrostatic gas bearings (carbon graphite and aluminum oxide for wear couple surfaces). Tests on the CTPC were performed in three phases: cold end testing (525 K), engine testing with slot radiant heaters, and integrated heat pipe engine system testing. Each test phase was successful, with the integrated engine system demonstrating a power level of 12.5 kWe and an overall efficiency of 22 percent in its maiden test. A 1500-hour endurance test was then successfully completed. These results indicate the significant achievements made by this program that demonstrate the viability of Stirling engine technology for space applications.

Dhar, Manmohan↗

High Frequency Interconnects on Silicon Substrates

The measured propagation constant of coplanar waveguide (CPW) on silicon wafers as a function of the line dimensions and the resistivity of the Si wafer; CPW on GaAs wafers as a function of the line dimensions, and thin film microstrip (TFMS) polyimide fabricated with polyimide on the surface of a silicon wafer is presented. It is shown that the attenuation of CPW on 2500 Omega-cm Si wafers and-of TFMS with a polyimide thickness of 4 micrometer or greater is comparable to the attenuation of similar lines on GaAs.

Ponchak, George E.↗

Properties of M40J Carbon/PMR-II-50 Composites Fabricated with Desized and Surface Treated Fibers. Characterization of M40J Desized and Finished Fibers

To increase performance and durability of high temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. This study was an extension of prior work characterizing the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) with typical fluorinated polyimide resins, such as PMR-II-50. A continuous desizing system which utilizes environmentally friendly chemical- mechanical processes was developed for tow level fiber and the processes were optimized based on weight loss behavior, surface elemental composition (XPS) and morphology (FE-SEM) analyses, and residual tow strength of the fiber, and the similar approaches have been applied on carbon fabrics. Both desized and further treated with a reactive finish were investigated for the composite reinforcement. The effects of desizing and/or subsequent surface retreatment on carbon fiber on composite properties and performance including fiber-matrix interfacial mechanical properties, thermal properties and blistering onset behavior will be discussed in this presentation.

Allred, Ronald E.↗

NMR Guided Design of Endcaps With Improved Oxidation Resistance

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 a norbornene endcap 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. Norbornenyl-end capped PMR polyimide resins' are widely used as polymer matrix composite materials for aircraft engine applications,2 since they combine ease of processing with good oxidative stability up to 300 C. PMR resins are prepared by a twestep approach involving the initial formation of oligomeric pre-polymers capped at both ends by a latent reactive end cap. The end cap undergoes cross-linking during higher temperature processing, producing the desired low density, high specific strength materials, as shown for PMR-15.

Meador, Mary Ann B.↗

Optimal Substrate Preheating Model for Thermal Spray Deposition of Thermosets onto Polymer Matrix Composites

High velocity oxy-fuel (HVOF) sprayed, functionally graded polyimide/WC-Co composite coatings on polymer matrix composites (PMC's) are being investigated for applications in turbine engine technologies. This requires that the polyimide, used as the matrix material, be fully crosslinked during deposition in order to maximize its engineering properties. The rapid heating and cooling nature of the HVOF spray process and the high heat flux through the coating into the substrate typically do not allow sufficient time at temperature for curing of the thermoset. It was hypothesized that external substrate preheating might enhance the deposition behavior and curing reaction during the thermal spraying of polyimide thermosets. A simple analytical process model for the deposition of thermosetting polyimide onto polymer matrix composites by HVOF thermal spray technology has been developed. The model incorporates various heat transfer mechanisms and enables surface temperature profiles of the coating to be simulated, primarily as a function of substrate preheating temperature. Four cases were modeled: (i) no substrate preheating; (ii) substrates electrically preheated from the rear; (iii) substrates preheated by hot air from the front face; and (iv) substrates electrically preheated from the rear and by hot air from the front.

Ivosevic, M.↗