Polymeric Schiff bases. I.
Conjugated, pseudoconjugated and nonconjugated Schiff base polymers synthesized by Schiff base exchange reactions, relating thermal stability to structure
Crivello, J. V.↗
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Polymeric Schiff bases. VIII.
Polyketanils synthesized and evaluated, noting insoluble infusible black polymers closely approximate to polymeric Schiff bases in thermal stability
Dalelio, G. F.↗
Effects of the thermal sterilization procedure on polymeric products
Properties of samples are tested, after thermal exposure, and values are compared with unexposed samples. Thermal stability or compatibility ratings of formulated or compounded organic polymers using trade names are made and degree of change in measured properties is assessed. Products are rated compatible, marginal, or not compatible.
Campbell, B. A.↗
Investigation of Test Methods, Material Properties, and Processes for Solar Cell Encapsulents
The technical activities were directed toward the assessment of encapsulation processes for use with ethylene/vinyl acetate copolymer as the pottant. Potentially successful formulations were prepared by compounding the raw polymer with ultraviolet absorbers and crosslinking agents to give stabilized and curable compositions. The compounded resin was then converted to a more useful form with an extruder to give pottant in sheets that could be more easily used in lamination. After experimenting with various techniques, the vacuum-bag process was found to be an excellent encapsulation method. Miniature single-celled and multi-celled solar modules of both substrate and superstrate designs were prepared by this technique. The resulting modules were of good appearance, were bubble-free, and successfully passed the thermal cycle test.
Source record↗
Hot forming graphite/polyimide structures
Hot forming process has been developed in which structural shapes and panels are fabricated directly from stabilized graphite/polyimide preforms. Process can be used with thermosetting polymers that have high-temperature melt phase just before final cure. This phase allows fibers to move without destroying matrix-to-fiber adhesion. One of key advantages of this process is that prestages preforms are very stable and do not require refrigerated storage.
Baucom, R. M.↗
High-Performance Matrix Resins
State-of-the-art PMR polyimides provide good strength and light weight in wide variety of critical applications. However, improved processability and elevated temperature thermo-oxidative stability are desired in such polyimide systems. Resins, intended for use in advanced composites, adhesives, and neat resin articles, show improvements in both processability and elevatedtemperature stability over state-of-the-art PMR-15 polymers.
Pater, R. H.↗
Development of and fabrication of high resolution gas chromatographic capillary columns
Gas chromatographic columns which are used in the trace gas analyzer (TGA) for the space shuttle are coated with a polyoxyethylene lauryl ether. This stationary phase is of medium polarity and has a temperature limit of 160 C. A polymer for this application which has an improved thermal stability is investigated. The use of fused silica capillary columns with specially bonded phases as well as an introduction system (on column) was also studied.
Zlatkis, A.↗
Synthesis and characterization of polyamide-imides
The synthesis and characterization of polyamide-imides (PAI) derived from four different dianhydrides and three isomers of diaminobenzanilide are discussed with emphasis on the effect of combining an amide linkage in the diamine portion with other bridging groups in the dianhydride portion of the polymer backbone. It is noted that all of the amide-imide polymers exhibit high-glass transition temperatures, high thermooxidative stability, and a relatively good solvent resistance. These aromatic PAIs are characterized by high thermal stability due to chain stiffness, crystallinity, and intermolecular hydrogen bonding, and are considered to be good candidates as high-temperature films, coatings, and fibers for aerospace applications.
Dezern, James F.↗
Polybenzimidazoles Via Aromatic Nucleophilic Displacement
Soluble polybenzimidazoles (PBI's) synthesized by nucleophilic displacement reaction of di(hydroxyphenyl)-benzimidazole monomers with activated aromatic difluoride compounds in presence of anhydrous potassium carbonate. These polymers exhibit good thermal, thermo-oxidative, and chemical stability, and high mechanical properties. Using benzimidazole monomers, more economical, and new PBI's processed more easily than commercial PBI, without loss of desirable physical properties.
Connell, John W.↗
Statistical Design in Isothermal Aging of Polyimide Resins
Recent developments in research on polyimides for high temperature applications have led to the synthesis of many new polymers. Among the criteria that determines their thermal oxidative stability, isothermal aging is one of the most important. Isothermal aging studies require that many experimental factors are controlled to provide accurate results. In this article we describe a statistical plan that compares the isothermal stability of several polyimide resins, while minimizing the variations inherent in high-temperature aging studies.
Sutter, James K.↗
Stable Polyimides for Terrestrial and Space Uses
Polyimides of a recently developed type have an attractive combination of properties, including low solar absorptivity (manifested as low color) when cast into thin films, resistance to atomic oxygen and ultraviolet radiation, solubility in organic solvents, high glass-transition temperatures, and high thermal stability. The focus of the development work was on polymers that can endure the space environment and that have specific combinations of properties for use on Gossamer spacecraft. Because of their unique combination of properties, these polymers are also expected to find use in a variety of other applications on Earth as well as in space. Examples of other space applications include membranes on antennas, second-surface mirrors, thermal optical coatings, and multilayer thermal insulation. For both terrestrial and space applications, these polyimides can be processed into various forms, including films, fibers, foams, threads, adhesives, and coatings.
Connell, John W.↗
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.↗
Use of the quartz crystal microbalance to determine the monomeric friction coefficient of polyimides
When a thin film of polymer is coated on to a quartz crystal microbalance (QCM), the QCM can be used to detect the rate of increase in weight of the polymer film as the volatile penetrant diffuses into the polymer. From this rate information the diffusion coefficient of the penetrant into the polymer can be computed. Calculations requiring this diffusion coefficient lead to values which approximate the monomeric friction coefficient of the polymer. This project has been concerned with the trial of crystal oscillating circuits suitable for driving polymer coated crystals in an atmosphere of penetrant. For these studies done at room temperature, natural rubber was used as an easily applied polymer that is readily penetrated by toluene vapors, qualities anticipated with polyimides when they are tested at T(g) in the presence of toluene. Three quartz crystal oscillator circuits were tested. The simplest circuit used +/- 5 volt dc and had a transistor to transistor logic (TTL) inverter chip that provides a 180 deg phase shift via a feed back loop. This oscillator circuit was stable but would not drive the crystal when the crystal was coated with polymer and subjected to toluene vapors. Removal of a variable resistor from this circuit increased stability but did not otherwise increase performance. Another driver circuit tested contained a two stage differential input, differential output, wide band video amplifier and also contain a feed back loop. The circuit voltage could not be varied and operated at +/- 5 volts dc; this circuit was also stable but failed to oscillate the polymer coated crystal in an atmosphere saturated with toluene vapors. The third oscillator circuit was of similar construction and relied on the same video amplifier but allowed operation with variable voltage. This circuit would drive the crystal when the crystal was submerged in liquid toluene and when the crystal was coated with polymer and immersed in toluene vapors. The frequency readings obtained when using this oscillating circuit are highly variable. This circuit requires further modification to stabilize frequency readings before its use in studies to determine the diffusion coefficient of penetrant molecules into a polymer film coated on a QCM.
Bechtold, Mary M.↗
A time dependent theory of crazing behavior in polymers
The development of crazing is not only a function of stress, but also a function of time. Under a simple state of tension, a craze opening displacement is closely associated with the viscoelastic behavior of the original bulk polymer medium in which individual crazes initiate and develop. Within each craze region, molecular orientation takes place when conditions permit, and a new phase of rearranged molecules governs its local behavior. Based upon a time-dependent viscoelastic two-dimensional model, using a computer program the craze opening displacement field has been calculated, time-dependent craze length was also computed by taking into consideration the molecular orientation mechanism and large deformations in the craze region. Examples are given for simple viscoelastic media with simplified stress distributions. It is interesting to find out that the occurrence of crazing may be interpreted in terms of the stability or instability of the constitutive behavior of the bulk polymer.
Chern, S. S.↗
Development of Processable PMR-Type Polymides with Star-Branched Structures
In the last two decades, high temperature polyimide matrix composites have found broad applications in aerospace structural components, due to their high specific modulus and high specific strength. As matrix resins, aromatic polyimides exhibit exceptional thermal stability and mechanical properties. However, their rodlike structures often result in poor solubility in most common organic solvents, as well as high melt temperature and melt viscosity, making them difficult to process. To overcome this difficulty, flexible linkages including O, SO2 or CH2 non coplanar biphenyl moieties, bulky lateral substituents, and crankshaft structures are often incorporated into the polymer backbones. Addition-curing of low molecular weight polyimides (resins) is another approach to improve processability. One of the most successfully developed materials has been PMR-15 (Polymerization of Monomer Reactants, molecular weight of 1500 g/mol), because of its good combination of thermal and mechanical properties and ease of processability. However, due to the high melt viscosity of PMR-type resins, use of more economical processing methods, such as resin transfer molding (RTM), is not possible. Recent research has focused on the incorporation of trifunctional monomers into addition-curing polyimides in an attempt to improve the processability of these polymers. The objective of this research is to use an aromatic triamine, 1,3,5 tris (4-aminophenoxy) benzene, to prepare new resin systems with starbranched structures. The glass transition temperatures (Tg's) and thermal oxidative stability TOS) of these polymers are compared to their linear counterparts and PMR-15.
Nguyen, Baochau N.↗
Development of Highly-Conductive Polyelectrolytes for Lithium Batteries
Future NASA and Air Force missions require reliable and safe sources of energy with high specific energy and energy density that can provide thousands of charge-discharge cycles at more than 40% depth- of-discharge and that can operate at low temperatures. All solid-state batteries have substantial advantages with respect to stability, energy density, storage fife and cyclability. Among all solid-state batteries, those with flexible polymer electrolytes offer substantial advantages in cell dimensionality and commensurability, low temperature operation and thin film design. The above considerations suggest that lithium-polymer electrolyte systems are promising for high energy density batteries and should be the systems of choice for NASA and US Air Force applications. Polyelectrolytes (single ion conductors) are among most promising avenues for achieving a major breakthrough 'in the applicability of polymer- based electrolyte systems. Their major advantages include unit transference number for the cation, reduced cell polarization, minimal salt precipitation, and favorable electrolyte stability at interfaces. Our research is focused on synthesis, modeling and cell testing of single ion carriers, polyelectrolytes. During the first year of this project we attempted the synthesis of two polyelectrolytes. The synthesis of the first one, the poly(ethyleneoxide methoxy acrylateco-lithium 1,1,2-trifluorobutanesulfonate acrylate, was attempted few times and it was unsuccessful. We followed the synthetic route described by Cowie and Spence. The yield was extremely low and the final product could not be separated from the impurities. The synthesis of this polyelectrolyte is not described in this report. The second polyelectrolyte, comb polysiloxane polyelectrolyte containing oligoether and perfluoroether sidechains, was synthesized in sufficient quantity to study the range of properties such as thermal stability, Li- ion- conductivity and stability toward lithium metal. Also, the batteries containing this polyelectrolyte were assembled and tested. The results are detailed below. The synthesis of another polyelectrolyte similar to polysiloxane polyelectrolyte has been started, however, the synthesis was not completed due to termination of the project.
Shriver, D. F.↗
Survivability of Affordable High Temperature Polymer Matrix Composites for Propulsion Engine Components
PMR-type polyimides are regarded as state of the art high temperature polymers, due to their excellent thermo-mechanical properties and thermo-oxidative stability. One of their drawbacks, however is the inability to process them using cost-effective processing methods such as Resin Transfer Molding (RTM) and Resin Film Infusion (RFI). Development of low viscosity, high temperature polymers has been the subject of intense research. Recently, a new generation of low viscosity polyimides were synthesized by the introduction of twisted biphenyl or binapthyl groups into the backbone. This report details the progress for Year 1, which has involved acquiring samples and initiating Phases I and II of the proposed research. Specifically, studies of the process-property relationships of a series of polymers using oligomers based on 2,3,3' ,4'-biphenyltertracarboxylic dianhydride (PBDA) and a mixture of a diamine, BAX and a triamine, 1,3,5-Tris (4-aminophenoxybenzene), TAB, where the amount of TAB was varied have been initiated. The sample containing 10 percent TAB possesses a slightly higher degree of crystalline order versus that of the 20 percent TAB sample, based on x-ray diffraction studies of the b-staged oligomers. Both systems lose all of the crystalline order upon curing, however. The chemorheology has been studied as a function of the TAB content. While the magnitude of the viscosity is essentially the same for both systems, the cure kinetics of the 10 percent TAB system is faster than that for the 20 percent TAB system. The sample exhibits a melting-recrystallization-remelting behavior before the crosslinking commences. Correlation of other kinetic parameters, such as the activation energies for curing, the Tg and mechanical properties to the structure of these systems is underway. Future studies will involve characterization of mechanical and thermal properties of the pure resins and the fabrication of fiber reinforced composites using these materials.
Dean, Derrick↗
Near Surface Vapor Bubble Layers in Buoyant Low Stretch Burning of Polymethylmethacrylate
Large-scale buoyant low stretch stagnation point diffusion flames over solid fuel (polymethylmethacrylate) were studied for a range of aerodynamic stretch rates of 2-12/ sec which are of the same order as spacecraft ventilation-induced stretch in a microgravity environment. An extensive layer of polymer material above the glass transition temperature is observed. Unique phenomena associated with this extensive glass layer included substantial swelling of the burning surface, in-depth bubble formation, and migration and/or elongation of the bubbles normal to the hot surface. The bubble layer acted to insulate the polymer surface by reducing the effective conductivity of the solid. The reduced in-depth conduction stabilized the flame for longer than expected from theory neglecting the bubble layer. While buoyancy acts to move the bubbles deeper into the molten polymer, thermocapillary forces and surface regression both act to bring the bubbles to the burning surface. Bubble layers may thus be very important in low gravity (low stretch) burning of materials. As bubbles reached the burning surface, monomer fuel vapors jetted from the surface, enhancing burning by entraining ambient air flow. Popping of these bubbles at the surface can expel burning droplets of the molten material, which may increase the fire propagation hazards at low stretch rates.
Olson, Sandra L.↗