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At least 199 records · Page 11

Degradation and crosslinking of perfluoroalkyl polyethers under X-ray irradiation in ultrahigh vacuum

Degradation of three types of commercially available perfluoroalkyl polyethers (PFPE)-Demnum S200, Fomblin Z25, and Krytox 16256-by X-ray irradiation was studied by using X-ray photoemission spectroscopy (XPS) and a mass spectrometer under ultra-high-vacuum conditions. The carbons in the polymers were characterized by chemical shifts of Cls binding energies. Gaseous products containing COF2 and low-molecular-weight fluorocarbons were formed. From Fomblin Z25, which has acetal linkages (-OCF2O-), a large quantity of COF2 gas was evolved. Liquid products became tacky after a long irradiation time, and some did not dissolve in Freon. High-pressure liquid chromatography (HPLC) showed that molecular weight distribution became broader and that higher molecular weight polymers were formed from Demnum and Krytox. We concluded from these results that degradation and cross-linking took place simultaneously. Demnum crosslinked more easily than the other fluids. The time dependence of both XPS spectra of Cls and mass spectra showed that C-O-bonded carbons in PFPE'S were removed faster than other carbons. There was no substrate effect on the degradation reaction because the first-order rate constants calculated from the change of gaseous products were similar when stainless steel (440C) and gold-coated surfaces were used. Metal fluorides were formed on stainless steel during the reaction. A mechanism for the degradation of PFPE'S is discussed on the basis of their molecular structures.

Mori, Shigeyuki↗

Structural materials for space applications

The long-term performance of structural materials in the space environment is a key research activity within NASA. The primary concerns for materials in low Earth orbit (LEO) are atomic oxygen erosion and space debris impact. Atomic oxygen studies have included both laboratory exposures in atomic oxygen facilities and flight exposures using the Shuttle. Characterization of atomic oxygen interaction with materials has included surface recession rates, residual mechanical properties, optical property measurements, and surface analyses to establish chemical changes. The Long Duration Exposure Facility (LDEF) is scheduled to be retrieved in 1989 and is expected to provide a wealth of data on atomic oxygen erosion in space. Hypervelocity impact studies have been conducted to establish damage mechanisms and changes in mechanical properties. Samples from LDEF will be analyzed to determine the severity of space debris impact on coatings, films, and composites. Spacecraft placed in geosynchronous Earth orbit (GEO) will be subjected to high doses of ionizing radiation which for long term exposures will exceed the damage threshold of many polymeric materials. Radiation interaction with polymers can result in chain scission and/or cross-linking. The formation of low molecular weight products in the epoxy plasticize the matrix at elevated temperatures and embrittle the matrix at low temperatures. This affects both the matrix-dominated mechanical properties and the dimensional stability of the composite. Embrittlement of the matrix at low temperatures results in enhanced matrix microcracking during thermal cycling. Matrix microcracking changes the coefficient of thermal expansion (CTE) of composite laminates and produces permanent length changes. Residual stress calculations were performed to estimate the conditions necessary for microcrack development in unirradiated and irradiated composites. The effects of UV and electron exposure on the optical properties of transparent polymer films were also examined to establish the optimum chemical structure for good radiation resistance. Thoughts on approaches to establishing accelerated testing procedures are discussed.

Tenney, Darrel R.↗

Space radiation effects on dimensional stability of composites

The long-term space environment at GEO, consisting of high doses (less than 10 to the 9th rads) of electron radiation and large cyclic (-157 C to +121 C) temperature changes, can significantly affect the dimensional stability of polymer matrix composites. Radiation alters the chemical structure of epoxies by both chain scission and cross-linking. In this paper, an attempt is made to summarize and examine the effects of electron radiation damage on dimensional stability of composites. Microcracking measurements were made for standard 177 C cure Gr/Ep, rubber toughened Gr/Ep, Gr/Polymide, and GR/Thermoplastic composites. Results show that radiation damage can significantly change matrix-dependent mechanical and physical properties of composites, with data explaining how these changes can affect their dimensional stability.

Tenney, Darrel R.↗

Ethynyl-Terminated Imidothioethers And Derived Resins

New toughened epoxies exhibit excellent properties, but temperatures at which used limited. Bismaleimide resins some of base materials being formulated to develop materials used at moderate temperatures. Work conducted on use of acetylenic (ethynyl) group to cross-link and extend chains of oligomers and polymers to obtain materials that perform at high temperatures. Work extended to ethynyl-terminated imidothioethers (ETI's). Tested primarily as adhesives and composite matrices and found to have useful properties in terms of processing, resistance to high temperature, fracture toughness, and resistance to solvents. Also have desirable mechanical properties. Potentially useful for aerospace and nonaerospace applications.

Hergenrother, Paul M.↗

Tough, Microcracking-Resistant, High-Temperature Polymer

Simultaneous synthesis from thermosetting and thermoplastic components yields polyimide with outstanding properties. Involves process in which one polymer cross-linked in immediate presence of other, undergoing simultaneous linear chain extension. New material, LaRC-RP40 synthesized from high-temperature thermosetting imide prepolymer and from thermoplastic monomer. Three significantly improved properties: toughness, resistance to microcracking, and glass-transition temperature. Shows promise as high-temperature matrix resin for variety of components of aircraft engines and for use in other aerospace structures.

Pater, Ruth H.↗

Conceptual definition of a high voltage power supply test facility

NASA Lewis Research Center is presently developing a 60 GHz traveling wave tube for satellite cross-link communications. The operating voltage for this new tube is - 20 kV. There is concern about the high voltage insulation system and NASA is planning a space station high voltage experiment that will demonstrate both the 60 GHz communications and high voltage electronics technology. The experiment interfaces, requirements, conceptual design, technology issues and safety issues are determined. A block diagram of the high voltage power supply test facility was generated. It includes the high voltage power supply, the 60 GHz traveling wave tube, the communications package, the antenna package, a high voltage diagnostics package and a command and data processor system. The interfaces with the space station and the attached payload accommodations equipment were determined. A brief description of the different subsystems and a discussion of the technology development needs are presented.

Biess, John J.↗

Tissue simulating gel for medical research

A tissue simulating gel and a method for preparing the tissue simulating gel are disclosed. The tissue simulating gel is prepared by a process using water, gelatin, ethylene gylcol, and a cross-linking agent. In order to closely approximate the characteristics of the type of tissue being simulated, other material has been added to change the electrical, sound conducting, and wave scattering properties of the tissue simulating gel. The result of the entire process is a formulation that will not melt at the elevated temperatures involved in hyperthermia medical research. Furthermore, the tissue simulating gel will not support mold or bacterial growth, is of a sufficient mechanical strength to maintain a desired shape without a supporting shell, and is non-hardening and non-drying. Substances were injected into the tissue simulating gel prior to the setting-up thereof just as they could be injected into actual tissue, and the tissue simulating gel is translucent so as to permit visual inspection of its interior. A polyurethane spray often used for coating circuit boards can be applied to the surface of the tissue simulating gel to give a texture similar to human skin, making the tissue simulating gel easier to handle and contributing to its longevity.

Companion, John A.↗

Effects of 70-keV electrons on two polyarylene ether ketones

Films prepared from two polyarylene ether ketones with the repeat units -PhC(O)PhC(O)-PhOPhXPhO- where X = C(CH3)2 or CH2 and Ph = C6H4, were bombarded with 70-keV electrons. The effects of irradiation were determined from the fraction of gel formed; the intrinsic viscosities, gel permeation chromatography, and NMR spectroscopy of the soluble portion of the irradiated films; and the changes in the IR spectra of the materials. In a Charlesby-Pinner analysis of the gel fractions of the polyarylene ether ketone with the isopropylidene group, the numbers of scission and cross-linking events per 100 eV (9649 kJ/mol) absorbed were found to be small with G(S) = 0.002 and G(X) = 0.009, respectively.

Kingsbury, Kevin B.↗

Atomic-oxygen induced structural changes in polyphosphazene films and coatings

Various polymers were exposed to atomic oxygen O(3P) and comparisons made of their stability. The rates of reaction and mass removal for polyphosphazenes exposed to atomic oxygen were found to be significantly lower than for other polymers evaluated in this study. Surface analysis of polyphosphazene films indicated that O(3P) induces rearrangements in the phosphorus-nitrogen backbone of the polymer, resulting in cross-linking and cleavage of some pendant groups that are then replaced by oxygen.

Fewell, Larry L.↗

Thermal stability of electron-irradiated poly(tetrafluoroethylene) - X-ray photoelectron and mass spectroscopic study

Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species were evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS spectrum that were associated with damage diminished, giving the appearance that the radiation damage had annealed. The observations were interpreted by incorporating mass transport of severed chain fragments and thermal decomposition of severely damaged material into the branched and cross-linked network model of irradiated PTFE. The apparent annealing of the radiation damage was due to covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

Wheeler, Donald R.↗

Polyimides from a methylene-bridged dianhydride

High-molecular weight, high-temperature, highly optically transparent films suitable for electronic and aerospace applications were prepared based on a novel methylene-bridged dianhydride 3,3-prime bis(3,4-dicarboxyphenoxy) diphenylmethane dianhydride (PDMDA). All films had lower dielectric constants and significantly higher optical transparency than the commercial Kapton H film, with air-cured films having slightly higher dielectric constants and lower optical transparency than vacuum films, due to oxidative cross-linking.

Boston, Harold G.↗

Electron-microscopic cytochemical localization of diamine and polyamine oxidases in pea and maize tissues

An electron-microscopic cytochemical method was used to localize diamine oxidase (DAO) in pea and polyamine oxidase (PAO) in maize (Zea mays L.). The method, based on the precipitation of amine-oxidase-generated H2O2 by CeCl3, was shown to be specific for DAO and PAO and permitted their localization in plant tissues with a high degree of resolution. Both enzymes are localized exclusively in the cell wall. Both DAO- and PAO-activity staining is most intense in the middle lamellar region of the wall and in cells exhibiting highly lignified walls. The oxidases could provide H2O2 for peroxidase-mediated cross-linking reactions in the cell wall and may, in this capacity, play a role in the regulation of plant growth.

NASA Program Space Biology↗

Gravitropism of cucumber hypocotyls: biophysical mechanism of altered growth

The biophysical basis for the changes in cell elongation rate during gravitropism was examined in aetiolated cucumber (Cucumis sativus L.) hypocotyls. Bulk osmotic pressures on the two sides of the stem and in the epidermal cells were not altered during the early time course of gravitropism. By the pressure-probe technique, a small increase in turgor (0.3 bar, 30 kPa) was detected on the upper (inhibited) side, whereas there was a negligible decrease in turgor on the lower (stimulated) side. These small changes in turgor and water potential appeared to be indirect, passive consequences of the altered growth and the small resistance for water movement from the xylem, and indicated that the change in growth was principally due to changes in wall properties. The results indicate that the hydraulic conductance of the water-transport pathway was large (.25 h-1 bar-1) and the water potential difference supporting cell expansion was no greater than 0.3 bar (30 kPa). From pressure-block experiments, it appeared that upon gravitropic stimulation (1) the yield threshold of the lower half of the stem did not decrease and (2) the wall on the upper side of the stem was not made more rigid by a cross-linking process. Mechanical measurements of the stress/strain properties of the walls showed that the initial development of gravitropism did not involve an alteration of the mechanical behaviour of the isolated walls. Thus, gravitropism in cucumber hypocotyls occurs principally by an alteration of the wall relaxation process, without a necessary change in wall mechanical properties.

Non-NASA Center↗

Spaceflight effects on biomechanical and biochemical properties of rat vertebrae

The biomechanical and biochemical responses of lumbar vertebral bodies during a 12.5-day spaceflight (Cosmos 1887 biosatellite) were determined for rapidly growing rats (90-day-old, Czechoslovakian-Wistar). By use of age-matched vivarium controls (normal cage environment) and synchronous controls (simulated flight conditions), as well as a basal control group (killed before lift-off on the 1st day of flight), the combined influences of growth and space-flight could be examined. Centra of the sixth lumbar vertebrae (L6) were compressed to 50% strain at a fast strain rate while immersed in physiological buffer (37 degrees C). The body masses of vivarium and synchronous controls were significantly heavier than either the flight or basal controls. The flight group had an L6 vertebral body compressional stiffness that was 39% less than the vivarium controls, 47% less than the synchronous control, and 16% less than the basal controls. In addition, the average initial maximum load of the flight L6 was 22% less than vivarium controls and 18% less than the synchronous controls, whereas the linear compressional load of the flight group averaged 34% less than the vivarium and 25% less than the synchronous groups. The structural properties of the vertebrae from the 12.5-day-younger basal group closely resembled the flight vertebrae. Calcium, phosphorous, and hydroxyproline concentrations were not significantly different among the groups. Nevertheless, the lack of strength and stiffness development in spaceflight, coupled with a smaller proportion of mature hydroxypyridinoline cross-links, suggested that the 12.5 days of spaceflight slowed the maturation of trabecular bone in the vertebral bodies of rapidly growing rats.

Non-NASA Center↗

Polyvinyl pyridine microspheres

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Rembaum, Alan↗

Protein specific polymeric immunomicrospheres

Small, round, bio-compatible microspheres capable of covalently bonding proteins and having a uniform diameter below about 3500 A are prepared by substantially instantaneously initiating polymerization of an aqueous emulsion containing no more than 35% total monomer including an acrylic monomer substituted with a covalently bondable group such as hydroxyl, amino or carboxyl and a minor amount of a cross-linking agent.

Rembaum, Alan↗

Ion-exchange hollow fibers

An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

Rembaum, Alan↗

Coating for gasifiable carbon-graphite fibers

A thin, uniform, firmly adherent coating of metal gasification catalyst is applied to a carbon-graphite fiber by first coating the fiber with a film-forming polymer containing functional moieties capable of reaction with the catalytic metal ions. Multivalent metal cations such as calcium cross-link the polymer such as a polyacrylic acid to insolubilize the film by forming catalytic metal macro-salt links between adjacent polymer chains. The coated fibers are used as reinforcement for resin composites and will gasify upon combustion without evolving conductive airborne fragments.

Harper-Tervet, Jan↗