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At least 109 records · Page 6

Phase transformations in SrAl2Si2O8 glass

Bulk glass of SrAl2Si2O8 composition crystallized at temperatures below 1000 C into hexacelsian, a hexagonal phase which undergoes a reversible, rapid transformation to an orthorhombic phase at 758 C, and at higher temperatures crystallized as celsian, a monoclinic phase. The glass transition temperature and crystallization onset temperature were determined to be 883 C and 1086 C, respectively, from DSC at a heating rate of 20 C/min. Thermal expansion of the various phases and density and bend strengths of cold isostatically pressed glass powder bars, sintered at various temperatures, were measured. The kinetics of the hexacelsian-to-celsian transformation for SrAl2Si2O8 were studied. Hexacelsian flakes were isothermally heat treated at temperatures from 1025-1200 C for various times. Avrami plots were determined by quantitatively measuring the amount of monoclinic celsian formed at various times using x ray diffraction. The Avrami constant was determined to be 1.1, suggesting a diffusionless, one dimensional transformation mechanism. The activation energy was determined from an Arrhenius plot of 1n k vs. 1/T to be 125 kilocal/mole. This value is consistent with a mechanism which transforms the layered hexacelsian structure to a three dimensional framework celsian structure and involves the breaking of Si-O bonds.

Drummond, Charles H., III↗

The Vitrification and Determination of the Crystallization Time Scales of a Zr58.5Nb2.8Cu15.6Ni12.8Al10.3 Bulk Metallic Glass Forming Liquid

Zr58.5Nb2.8Cul5.6Nil2.8All0.3 is the first bulk glass forming liquid that does not contain beryllium to be vitrified by purely radiative cooling in the containerless electrostatic levitation process. The measured critical cooling rate is 1.75 K/s. The sluggish crystallization kinetics enable the determination of the time-temperature-transformation (TTT) diagram between the liquidus and the glass transition temperatures. At the nose of the TTT diagram, the shortest time to reach crystallization in an isothermal experiment is 32 seconds. In contrast to other bulk metallic glasses the scatter in the crystallization onset times are small at both high and low temperatures.

Hays, C. C.↗

CHEM-Based Self-Deploying Planetary Storage Tanks

A document proposes self-deploying storage tanks, based on the cold elastic hibernated memory (CHEM) concept, to be used on remote planets. The CHEM concept, described in previous NASA Tech Briefs articles, involves the use of open-cell shape-memory-polymer (SMP) foam sandwich structures to make lightweight, space-deployable structures that can be compressed for storage and can later be expanded, then rigidified for use. A tank according to the proposal would be made of multiple SMP layers (of which at least one could be an SMP foam). The tank would be fabricated at full size in the rigid, deployed condition at ambient temperature, the SMP material(s) having been chosen so that ambient temperature would be below the SMP glass-transition temperature (T(sub g)). The tank would then be warmed to a temperature above T(sub g), where it would be compacted and packaged, then cooled to below T(sub g) and kept there during launch and transport to a distant planet. At the assigned position on the planet, the compacted tank would be heated above T(sub g) by the solar radiation making it rebound to its original size and shape. Finally, the tank would be rigidified through natural cooling to below T(sub g) in the planetary ambient environment.

Sokolowski, Witold↗

Marshall Convergent Spray Formulation Improvement for High Temperatures

The Marshall Convergent Coating-1 (MCC-1) formulation was produced in the 1990s, and uses a standard bisphenol A epoxy resin system with a triamine accelerator. With the increasing heat rates forecast for the next generation of vehicles, higher-temperature sprayable coatings are needed. This work substitutes the low-temperature epoxy resins used in the MCC-1 coating with epoxy phenolic, epoxy novalac, or resorcinolinic resins (higher carbon content), which will produce a higher char yield upon exposure to high heat and increased glass transition temperature. High-temperature filler materials, such as granular cork and glass ecospheres, are also incorporated as part of the convergent spray process, but other sacrificial (ablative) materials are possible. In addition, the use of polyhedral oligomeric silsesquioxanes (POSS) nanoparticle hybrids will increase both reinforcement aspects and contribute to creating a tougher silacious char, which will reduce recession at higher heat rates. Use of expanding epoxy resin (lightweight MCC) systems are also useful in that they reduce system weight, have greater insulative properties, and a decrease in application times can be realized.

Scarpa, Jack↗

Failure Criterion For Isotropic Time Dependent Materials Which Accounts for Multi-Axial Loading

The Space Shuttle's Reusable Solid Rocket Motor (RSRM) nozzle program has recently conducted testing to characterize the effects of multi-axial loading, temperature and time on the failure characteristics of TIGA321, EA913NA, EA946 (three filled epoxy adhesives). From the test data a "Multi-Axial, Temperature, and Time Dependent" or MATT failure criterion was developed. It is shown that this criterion simplifies, for constant load and constant load rate conditions, into a form that can be easily used for stress analysis. Failure for TIGA321 and EA913NA are characterized below their glass transition temperature. Failure for EA946 is characterized for conditions that pass through its glass transition. The MATT failure criterion is shown to be accurate for a wide range of conditions for these adhesives.

Richardson, D. E.↗

Effects of hydrothermal exposure on a low-temperature cured epoxy

Thermal mechanical analysis was employed to monitor the penetration temperature of a low-temperature epoxy resin. Both neat resin and E-glass composite samples were examined. The effects of cure temperature variation and moisture content on the apparent glass transition temperature were determined.

Lauver, R. W.↗

Effects of hydrothermal exposure on a low-temperature cured epoxy

Thermal mechanical analysis was employed to monitor the penetration temperature of a low-temperature epoxy resin (EPON 826/D230). Both neat resin and E-glass composite samples were examined. The effects of cure temperature variation and moisture content on the apparent glass transition temperature were determined.

Lauver, R. W.↗

Initial adhesive screening of novel polyamide-imides and their copolymers

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Donald J Progar↗

Initial evaluation of novel polyamide-imides and their copolymers as adhesives

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Progar, Donald J.↗

New developments in thermally stable polymers

Advances in high-temperature polymers since 1985 are discussed with the emphasis on the chemistry. High-temperature polymers refer to materials that exhibit glass-transition temperatures greater than 200 C and have the chemical structure expected to provide high thermooxidative stability. Specific polymers or series of polymers were selected to show how the chemical structure influences certain properties. Poly(arylene ethers) and polyimides are the two principal families of polymers discussed. Recent work on poly(arylene ethers) has concentrated on incorporating heterocyclic units within the polymer backbone. Recent polyimide work has centered on the synthesis of new polymers from novel monomers, several containing the trifluoromethyl group strategically located on the molecule. Various members in each of these polymer families display a unique combination of properties, heretofore unattainable. Other families of polymers are also briefly discussed with a polymer from an AB maleimidobenzocyclobutene exhibiting an especially attractive combination of properties.

Hergenrother, Paul M.↗

Tape-Drop Transient Model for In-Situ Automated Tape Placement of Thermoplastic Composites

Composite parts of nonuniform thickness can be fabricated by in-situ automated tape placement (ATP) if the tape can be started and stopped at interior points of the part instead of always at its edges. This technique is termed start/stop-on-the-part, or, alternatively, tape-add/tape-drop. The resulting thermal transients need to be managed in order to achieve net shape and maintain uniform interlaminar weld strength and crystallinity. Starting-on-the-part has been treated previously. This paper continues the study with a thermal analysis of stopping-on-the-part. The thermal source is switched off when the trailing end of the tape enters the nip region of the laydown/consolidation head. The thermal transient is determined by a Fourier-Laplace transform solution of the two-dimensional, time-dependent thermal transport equation. This solution requires that the Peclet number Pe (the dimensionless ratio of inertial to diffusive heat transport) be independent of time and much greater than 1. Plotted isotherms show that the trailing tape-end cools more rapidly than the downstream portions of tape. This cooling can weaken the bond near the tape end; however the length of the affected region is found to be less than 2 mm. To achieve net shape, the consolidation head must continue to move after cut-off until the temperature on the weld interface decreases to the glass transition temperature. The time and elapsed distance for this condition to occur are computed for the Langley ATP robot applying PEEK/carbon fiber composite tape and for two upgrades in robot performance. The elapsed distance after cut-off ranges from about 1 mm for the present robot to about 1 cm for the second upgrade.

Costen, Robert C.↗

Dynamic mechanical analysis and organization/storage of data for polymetric materials

Dynamic mechanical analysis was performed on a variety of temperature resistant polymers and composite resin matrices. Data on glass transition temperatures and degree of cure attained were derived. In addition a laboratory based computer system was installed and data base set up to allow entry of composite data. The laboratory CPU termed TYCHO is based on a DEC PDP 11/44 CPU with a Datatrieve relational data base. The function of TYCHO is integration of chemical laboratory analytical instrumentation and storage of chemical structures for modeling of new polymeric structures and compounds

Rosenberg, M.↗

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.↗

A Comparison Study: The New Extended Shelf Life Isopropyl Ester PMR Technology versus The Traditional Methyl Ester PMR Approach

Polymerization of Monomeric Reactants (PMR) monomer solutions and carbon cloth prepregs of PMR II-50 and VCAP-75 were prepared using both the traditional limited shelf life methanol based PMR approach and a novel extended shelf life isopropanol based PMR approach. The methyl ester and isopropyl ester based PMR monomer solutions and PMR prepregs were aged for up to four years at freezer and room temperatures. The aging products formed were monitored using high pressure liquid chromatography (HPLC). The composite processing flow characteristics and volatile contents of the aged prepregs were also correlated versus room temperature storage time. Composite processing cycles were developed and six ply cloth laminates were fabricated with prepregs after various extended room temperature storage times. The composites were then evaluated for glass transition temperature (Tg), thermal decomposition temperature (Td), initial flexural strength (FS) and modulus (FM), long term (1000 hours at 316 C) thermal oxidative stability (TOS), and retention of FS and FM after 1000 hours aging at 316 C. The results for each ester system were comparable. Freezer storage was found to prevent the formation of aging products for both ester systems. Room temperature storage of the novel isopropyl ester system increased PMR monomer solution and PMR prepreg shelf life by at least an order of magnitude while maintaining composite properties.

Alston, William B.↗

(abstract) Undercooling Studies of the Bulk Metallic Glass Forming Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy During Containerless Electrostatic Levitation Processing

Bulk glass forming metallic alloys have long been desired for technological applications and for investigation into liquid undercooling, solidification processes, and thermophysical properties. A glass forming alloy Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) was used to investigate the thermal treatments affecting undercooling and vitrification. The experiments were performed using the high temperature high vacuum electrostatic levitator at JPL. A sample approximately 3 mm in diameter was melted, superheated, undercooled, and solidified while levitated in high vacuum. The results show that when the sample was held above its melting temperature for a sufficient period of time to dissolve oxides and then cooled faster than a critical cooling rate, it undercooled to the glass transition temperature, T(sub g), and formed a glassy alloy. The required critical cooling rate for metallic glass formation was obtained to be between 0.9 K per second and 1.2 K per second for the 42.4 mg sample.

levitation vitrification↗

Evaluation of Temperature Gradients During Cure of a Thick Carbon Fiber/Epoxy Composite

The purpose of this study is to evaluate the development of thermal gradients throughout thick (1") carbon fiber composites and determine the effect of internal temperature distribution during cure on the observed mechanical properties in those composites. Composites up to 1.5" thick (56 plies) were fabricated with T700S/TC380 braided prepreg from Tencate following a modified vacuum bag layup procedure to include embedded thermocouples within the plies of the composite. Composite panels were cured in a programmable oven with thermocouple reading embedded throughout the panel thickness. Maximum temperature gradients measured between regions of the composite did not exceed 10 degrees C for any given composite thickness. The most significant temperature variation was measured between the mid-thickness plies and the tool-side surface plies. Although through thickness temperature variation during cure was small, a measureable variation in coupon glass transition temperature was recorded between the tool side plies and the remainder of the part, prior to post cure. Thermal and mechanical behavior of coupons taken from segments through the thickness of the part were comparable following a post-cure cycle.

Miller, Sandi↗

Dynamic mechanical characterization of cure of a polyimide-graphite fiber composite (PMR 15/Celion 6000)

Dynamic mechanical studies of thermosetting PMR 15 polyimide/Celion 6000 composites were used to characterize cure behavior. Variation in composite shear modulus with cure time for laminates partially cured under 3.45 MPa pressure was compared with that of laminates fully cured under pressure to select a partially cured system whose behavior corresponded with that of the pressure-cured composites. An empirical kinetic model was developed that relates relative composite shear moduli to cure time and temperature. This model, coupled with standard statistical techniques, was used in the determination of an overall activation energy, E = 145 kj/mole (35 kcal/mole) and order of reaction, n, for the cure reaction(s). The empirical relationship defining dynamic modulus as a function of time and temperature remained linear well into the glassy region. Changes in dynamic glass-transition temperature and in the breadth of the transition peaks with cure time are discussed. Shear modulus and damping were found to be more sensitive measures of relative extent of cure than Fourier transform infrared spectroscopy.

Hurwitz, F. I.↗

Composites of vinyl polystyrylpyridine/bismaleimide-aliphatic ether copolymers

An aliphatic ether bismaleimide was prepared and coreacted with a polyvinylstyrylpyridine (VPSP) oligomer. Studies showed that a controlled ratio of aliphatic to aromatic units in the polymer backbone improved both processibility and interlaminar shear properties for the carbon-fiber composite system. This modified resin was readily soluble in tetrahydrofuran, allowing for better fiber impregnation and thus enhancing adhesive properties and reproducibility. DSC studies have shown a lower cure temperature for the copolymer than for the neat aliphatic bismaleimide, and a glass transition temperature of 260 C, which is more than adequate for most applications. Limited measurements indicated an improvement in toughness (impact resistance).

Heimbuch, Alvin H.↗