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High-Temperature Shape Memory Polymers

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Yoonessi, Mitra↗

Fabrication of Extruded Polyphenylsulfone – Boron Nitride Composite Tapes

Polyphenylsulfone (PPSU) is a high-temperature, chemically resistant thermoplastic with high impact resistance that is often used in interior aircraft cabin components, medical devices, and membranes. The aforementioned properties have led to interest investigating PPSU’s compatibility with hexagonal boron nitride (hBN) platelets as a thermally conductive, electrical composite insulator for high power-density electric machines. Preliminary trials extruding PPSU-hBN composite tapes showed promising dielectric properties and higher thermal conductivity as a function of hBN concentration compared to their neat analog. On the other hand, only few studies have reported on the extrusion process and resulting thermo-mechanical properties for PPSU and its composites made with chopped fiber reinforcement or fillers, none of which contained boron nitride filler. Prospects may exist for this type of material to be incorporated into extrusion-based additive manufacturing techniques to print other composites bearing unique properties useful for aerospace. Loading levels with up to approximately 23 wt% were achieved using micro-size BN platelets without observing any significant affects to PPSU’s glass-transition temperature. This work includes a description of the rheological properties of PPSU, the extrusion parameters for mixing and compounding the PPSU-hBN composite tapes, and the thermal and thermo-mechanical properties of PPSU-hBN composites.

Tiffany Williams↗

Monitoring processing properties of high performance thermoplastics using frequency dependent electromagnetic sensing

An in situ NDE dielectric impedance measurement method has been developed for ascertaining the cure processing properties of high temperature advanced thermoplastic and thermosetting resins, using continuous frequency-dependent measurements and analyses of complex permittivity over 9 orders of magnitude and 6 decades of frequency at temperatures up to 400 C. Both ionic and Debye-like dipolar relaxation processes are monitored. Attention is given to LARC-TPI, PEEK, and poly(arylene ether) resins' viscosity, glass transition temperature, recrystallization, and residual solvent content and evolution properties.

Kranbuehl, D. E.↗

Improved Thermoplastic/Iron-Particle Transformer Cores

A method of fabricating improved transformer cores from composites of thermoplastic matrices and iron-particles has been invented. Relative to commercially available laminated-iron-alloy transformer cores, the cores fabricated by this method weigh less and are less expensive. Relative to prior polymer-matrix/ iron-particle composite-material transformer cores, the cores fabricated by this method can be made mechanically stronger and more magnetically permeable. In addition, whereas some prior cores have exhibited significant eddy-current losses, the cores fabricated by this method exhibit very small eddy-current losses. The cores made by this method can be expected to be attractive for use in diverse applications, including high-signal-to-noise transformers, stepping motors, and high-frequency ignition coils. The present method is a product of an experimental study of the relationships among fabrication conditions, final densities of iron particles, and mechanical and electromagnetic properties of fabricated cores. Among the fabrication conditions investigated were molding pressures (83, 104, and 131 MPa), and molding temperatures (250, 300, and 350 C). Each block of core material was made by uniaxial-compression molding, at the applicable pressure/temperature combination, of a mixture of 2 weight percent of LaRC (or equivalent high-temperature soluble thermoplastic adhesive) with 98 weight percent of approximately spherical iron particles having diameters in the micron range. Each molded block was cut into square cross-section rods that were used as core specimens in mechanical and electromagnetic tests. Some of the core specimens were annealed at 900 C and cooled slowly before testing. For comparison, a low-carbon-steel core was also tested. The results of the tests showed that density, hardness, and rupture strength generally increased with molding pressure and temperature, though the correlation was rather weak. The weakness of the correlation was attributed to the pores in the specimens. The maximum relative permeabilities of cores made without annealing ranged from 30 to 110, while those of cores made with annealing ranged from 900 to 1,400. However, the greater permeabilities of the annealed specimens were not associated with noticeably greater densities. The major practical result of the investigation was the discovery of an optimum distribution of iron-particle sizes: It was found that eddy-current losses in the molded cores were minimized by using 100 mesh (corresponding to particles with diameters less than or equal to 100 m) iron particles. The effect of optimization of particle sizes on eddy-current losses is depicted in the figure.

Wincheski, Russell A.↗

Readying technology for a super SST

A technology readiness evaluation is made of the configurational, propulsion system, avionics, and materials/manufacturing methods which could be integrated to produce an economically viable SST by the year 2000. Aerodynamically, promising results are noted in the cases of arrow-wing planforms and blended wing/body cross sections, as well as in vortex flaps. In structures, metal matrix composites with high specific strength at high temperatures and thermoplastically formed/diffusion-bonded titanium alloy sandwich structures are identified as being of primary importance. Performance improvement prospects are also noted for engine efficiencies and sonic boom overpressures. The various technologies are envisaged as the bases for a two-engine, two-crew cockpit, 250-seat arrow-winged SST.

Petersen, R. H.↗

Characterization of polybenzimidazole (PBI) film at high temperatures

Polybenzimidazole, a linear thermoplastic polymer with excellent thermal stability and strength retention over a wide range of temperatures, was evaluated for its potential use as the main dielectric in high temperature capacitors. The film was characterized in terms of its dielectric properties in a frequency range of 50 Hz to 100 kilo-Hz. These properties, which include the dielectric constant and dielectric loss, were also obtained in a temperature range from 20 C to 300 C with an electrical stress of 60 Hz, 50 V/mil present. The alternating and direct current breakdown voltages of silicone oil impregnated films as a function of temperature were also determined. The results obtained indicate that while the film remained relatively stable up to 200 C, it exhibited an increase in its dielectric properties as the temperature was raised to 300 C. It was also found that conditioning of the film by heat treatment at 60 C for six hours tended to improve its dielectric and breakdown properties. The results are discussed and conclusions made concerning the suitability of the film as a high temperature capacitor dielectric.

Hammoud, Ahmad N.↗

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.↗

Supportability evaluation of thermoplastic and thermoset composites

Nearly 300 advanced composite components manufactured by Northrop Corporation are flying on U.S. Air Force and U.S. Navy supersonic aircraft as part of a three-year Air Force/Navy/Northrop supportability evaluation. Both thermoplastic and high-temperature thermoset composites were evaluated for their in-service performance on 48 USAF and Navy F-5E fighter and USAFT-38 trainer aircraft in the first large-scale, long-term maintenance evaluation of these advanced materials. Northrop manufactured four types of doors for the project-avionics bay access, oil fill, inlet duct inspection, and a main landing gear door. The doors are made of PEEK (polyetheretherketone) thermoplastic, which is tougher and potentially less expensive to manufacture than conventional composites; and 5250-3 BMI (bismaleimide) thermoset, which is manufactured like a conventional epoxy composite but can withstand higher service temperatures. Results obtained so far indicate that both the BMI and PEEK are durable with PEEK being somewhat better than BMI.

Chanani, G. R.↗

The effects of stress and physical aging on the creep compliance of a polymeric composite

An experimental study was performed to determine the effects of stress and physical aging on the matrix dominated viscoelastic properties of IM7/8320, a high temperature fiber reinforced thermoplastic composite. Established creep/aging test techniques developed for polymers were adapted for testing of the composite material. The transverse and shear compliance for an orthotropic plate were found from creep compliance measurements at constant, sub-Tg temperatures. These compliance terms were shown to be effected by physical aging. Aging time shift factors and shift rates were found to be a function of applied stress.

Gates, Thomas E.↗

Advanced thermoplastic resins, phase 2

High temperature structural resins are required for use on advanced aerospace vehicles as adhesives and composite matrices. NASA-Langley developed polyimide resins were evaluated as high temperature structural adhesives for metal to metal bonding and as composite matrices. Adhesive tapes were prepared on glass scrim fabric from solutions of polyamide acids of the semicrystalline polyimide LARC-CPI, developed at the NASA-Langley Research Center. Using 6Al-4V titanium adherends, high lap shear bond strengths were obtained at ambient temperature (45.2 MPa, 6550 psi) and acceptable strengths were obtained at elevated temperature (14.0 MPa, 2030 psi) using the Pasa-Jell 107 conversion coating on the titanium and a bonding pressure of 1.38 MPa (200 psi). Average zero degree composite tensile and compressive strengths of 1290 MPa (187 ksi) and 883 MPa (128 ksi) respectively were obtained at ambient temperature with unsized AS-4 carbon fiber reinforcement.

Brown, A. M.↗

Semi-interpenetrating polymer network for tougher and more microcracking resistant high temperature polymers

This invention is a semi-interpenetrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide. An improved high temperature matrix resin is provided which is capable of performing at 316 C in air for several hundreds of hours. This resin has significantly improved toughness and microcracking resistance, excellent processability and mechanical performance, and cost effectiveness.

Pater, Ruth H.↗

Vacuum Powder Injector

Method developed to provide uniform impregnation of bundles of carbon-fiber tow with low-solubility, high-melt-flow polymer powder materials to produce composite prepregs. Vacuum powder injector expands bundle of fiber tow, applies polymer to it, then compresses bundle to hold powder. System provides for control of amount of polymer on bundle. Crystallinity of polymer maintained by controlled melt on takeup system. All powder entrapped, and most collected for reuse. Process provides inexpensive and efficient method for making composite materials. Allows for coating of any bundle of fine fibers with powders. Shows high potential for making prepregs of improved materials and for preparation of high-temperature, high-modulus, reinforced thermoplastics.

Working, Dennis C.↗

A tough high performance composite matrix

This invention is a semi-interpenetrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide. An improved high temperature matrix resin is provided which is capable of performing in the 200 to 300 C range. This resin has significantly improved toughness and microcracking resistance, excellent processability, mechanical performance and moisture and solvent resistances.

Pater, Ruth H.↗

Monitoring Polymer Curing Via Electromagnetic Impedance

New nondestructive in-situ electromagnetic-impedance measurement technique senses cure-processing properties of high-temperature, high-performance thermostat and thermoplastic resins. Continuous frequency-dependent measurement and analysis performed during curing cycle. Monitors and measures molecular properties of polymeric resin in liquid and solid states. Applications include nondestructive means for evaluation of materials, determination of "window" boundaries of curing cycles of thermoplastics and thermoset resins, and for online, closed-loop control of curing cycles.

Freeman, William T.↗

New materials drive high-performance aircraft

This report shows how advanced composite materials and new processing methods are enabling lighter, lower cost aircraft structures. High-temperature polymers research will focus on systems capable of 50,000 to 100,000 hours of operation in the 212-400 F temperature range. Prospective materials being evaluated include high-temperature epoxies, toughened bismaleimides, cyanates, thermoplastics, polyimides and other polymers.

Ruhmann, Douglas C.↗

Interlaminar fracture toughness of thermoplastic composites

Edge delamination tension and double cantilever beam tests were used to characterize the interlaminar fracture toughness of continuous graphite-fiber composites made from experimental thermoplastic polyimides and a model thermoplastic. Residual thermal stresses, known to be significant in materials processed at high temperatures, were included in the edge delamination calculations. In the model thermoplastic system (polycarbonate matrix), surface properties of the graphite fiber were shown to be significant. Critical strain energy release rates for two different fibers having similar nominal tensile properties differed by 30 to 60 percent. The reason for the difference is not clear. Interlaminar toughness values for the thermoplastic polyimide composites (LARC-TPI and polyimidesulfone) were 3 to 4 in-lb/sq in. Scanning electron micrographs of the EDT fracture surfaces suggest poor fiber/matrix bonding. Residual thermal stresses account for up to 32 percent of the strain energy release in composites made from these high-temperature resins.

Hinkley, J. A.↗

Interlaminar fracture toughness of thermoplastic composites

Edge delamination tension and double cantilever beam tests were used to characterize the interlaminar fracture toughness of continuous graphite-fiber composites made from experimental thermoplastic polyimides and a model thermoplastic. Residual thermal stresses, known to be significant in materials processed at high temperatures, were included in the edge delamination calculations. In the model thermoplastic system (polycarbonate matrix), surface properties of the graphite fiber were shown to be significant. Cricital strain energy release rates for two different fibers having similar nominal tensile properties differed by 30 to 60 percent. The reason for the difference is not clear. Interlaminar toughness values for the thermoplastic polyimide composites (LARC-TPI and polyimidesulfone) were 3 to 4 in-lb/sq in. Scanning electron micrographs of the EDT fracture surfaces suggest poor fiber/matrix bonding. Residual thermal stresses account for up to 32 percent of the strain energy release in composites made from these high-temperature resins.

Hinkley, Jeffrey A.↗

Tough high performance composite matrix

This invention is a semi-interpentrating polymer network which includes a high performance thermosetting polyimide having a nadic end group acting as a crosslinking site and a high performance linear thermoplastic polyimide. Provided is an improved high temperature matrix resin which is capable of performing in the 200 to 300 C range. This resin has significantly improved toughness and microcracking resistance, excellent processability, mechanical performance, and moisture and solvent resistances.

Pater, Ruth H.↗