Engineering topics

Johnston, J. Christopher

Publications and source records attributed to Johnston, J. Christopher.

10 records

NASA NTRS2007

Improved Thermal Design of a Compression Mold

An analysis of the heat transfer in a tool for producing neat resin disks was conducted to determine how to bring about a better agreement between the tool temperature and the applied temperature profile. Using the commercial code FLUENT to investigate the relative effects of heat conduction into the tool and heat loss from the tool by convection, it was shown that convective heat transfer appears more important than conduction in controlling the tool performance. Decreasing the height of the tool was predicted to decrease the heat losses by convection. Redesign of the tool based on this analysis resulted in the tool experiencing the applied temperature profile.

Kuczmarski, Maria A.↗

NASA NTRS2005

Tetrahydrophthalic Anhydrides as Addition Curing Polyimide End Caps: Thermal Isomerization of Methylendianiline 3,6-Diphenyltetrahydrophthalic Bisimides

In depth NMR studies confirm that heating a 1:2 mixture of cis, cis, cis 3,6-diphenyltetrahydrophthalic anhydride (end cap 9c) with methylenedianiline at 316 C initially yields the corresponding highly congested cis, cis, cis 3,6-diphenyltetrahydrophthalic bisimide 11, which is converted at this temperature to the observed product, the less hindered trans, cis, trans isomer 12.

Frimer, Aryeh A.↗

NASA NTRS2003

Reevaluation of Tetrahydrophthalic Anhydride as an End Cap for Improved Oxidation Resistance in Addition Polyimides

Several substituted 1,2,3,6-tetrahydrophthalic anhydride end caps - including the 3-phenyl, 3-methoxy, 3-trimethylsilyloxy, and 3,6-diphenyl analogs - were synthesized via the Diels-Alder condensation of the corresponding butadienes and maleic anhydride. These anhydrides, as well as the commercially available 3-hydro and 4-methyl analogs, were each ground together with methylenedianiline in a 2:1 ratio and heated gradually from 204 C to 371 C, with the thermolysis followed by NMR. Generally speaking, a transformation via monoimide to bisimide was observed in the lower temperature range, followed by competition between crosslinking and aromatization. We believe that this competition produces a substantial percentage of aromatic product, with the concomitant lowering of the relative amount of crosslinking and is responsible for improving both thermal oxidative stability of tetrahydrophthalic end capped polyimides and their substantial frangibility. The thermolysis of the tetrahydrophthalimides under inert atmosphere dramatically lowers the amount of aromatization hence, the mechanism for aromatization is an oxidative one.

Meador, Mary Ann B.↗

NASA NTRS1999

On the Oxidative Degradation of Nadic End-Capped Polyimides: Synthesis and Characterization of Model Compounds for End-Cap Degradation Products - 3

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (CP-MAS) NMR. Labeling of selected sites in the polymers with C-13 allowed for direct observation of the transformations arising from oxidation processes. The formation of several degradation products has been proposed to be occurring in the cross-links derived from the nadic end caps on oxidation. Model compounds have been synthesized and characterized by CPMAS NMR with both normal and delayed decoupling to distinguish between protonated and unprotonated carbons. Comparison of these spectra to predicted chemical shifts of proposed products for the aged polymer provides further insight to degradation occurring in the cross-linked moieties.

Meador, Mary Ann B.↗

NASA NTRS1998

Carbon-13 Labeling Used to Probe Cure and Degradation Reactions of High- Temperature Polymers

High-temperature, crosslinked polyimides are typically insoluble, intractible materials. Consequently, in these systems it has been difficult to follow high-temperature curing or long-term degradation reactions on a molecular level. Selective labeling of the polymers with carbon-13, coupled with solid nuclear magnetic resonance spectrometry (NMR), enables these reactions to be followed. We successfully employed this technique to provide insight into both curing and degradation reactions of PMR-15, a polymer matrix resin used extensively in aircraft engine applications.

Meador, Mary Ann B.↗

NASA NTRS1998

Void Management in MEPHISTO and Other Space Experiments

The second flight of NASA's Shuttle Flight experiment program known as MEPHISTO suffered from a void in the liquid portion of the sample, even though a piston arrangement was in place to keep the ampoule filled. In preparations for the next flight of the MEPHISTO furnace an animated computer program, called MEPHISTO Volume Visualizer (MVV), was written to help avoid the formation of unwanted voids. A piston system on MEPHISTO has the ability to move approximately 5 mm in compression, to accommodate expansion of the solid during heating; then from the completely compressed position, the piston can move up to 25 mm in towards the sample, effectively making the ampoule smaller and hopefully eliminating any voids. Due to the nature of the piston design and ampoule and sample arrangement, the piston has gotten stuck during normal directional solidification; this creates the risk of a void. To eliminate such a void, the liquid in the hot zones of the furnace can be heated, thereby expanding the liquid and consuming any void. The problem with this approach is that if the liquid is heated too much an overpressure could result, breaking the ampoule and ending the experiment catastrophically. The MVV has been found to be a useful tool in the assessment of the risks associated with the formation of a void and the additional heating of the liquid in the hot zone of this Bridgman type furnace. The MVV software will be discussed and copies available; it is written in the Delphi 2 programming language and runs under Windows 95 and NT. The strategies used in other flight experiments, such as the Isothermal Dendritic Growth Experiment, will also be presented.

deGroh, Henry C., III↗

NASA NTRS1997

Elucidation of the Cross-Link Structure of Nadic-End-Capped Polyimides Using NMR of C-13-Labeled Polymers

Solid NMR of C-13 isotope-labeled samples of PMR-15 was used to follow the cross-linking reaction of the nadic end cap. Some samples were labeled on one of the carbon atoms of the nadic end cap, and others on the methylene carbon atom of the methylenedianiline portion of the polymer. NMR spectra were run on these samples both before and after cross-linking. In this way, direct evidence of the major products of cross-linking under normal cure conditions is provided. The majority (approximately 85%) of the cross-linking derives from olefin polymerization through the double bond of the end cap. Approximately 15% of the products could come from a pathway involving a retro-Diels-Alder reaction. However, all of the products could be explained by a biradical intermediate without a retro-Diels-Alder reaction. Evidence is also presented that the methylene moiety in the methylenedianiline part of the polymer chain also participates in the cross-linking, albeit to a small extent, by a radical transfer reaction. Different cure conditions (higher temperatures, longer times) could change the relative distribution of the products.

Meador, Mary Ann B.↗

NASA NTRS1997

Oxidative Degradation of Nadic-End-Capped Polyimides: Evidence for Reactions Occurring at High Temperatures - 2

The oxidative degradation of PMR (for polymerization of monomeric reactants) polyimides at elevated temperatures was followed by cross-polarized magic angle spinning (Cp-MAS) NMR. C-13 labeling of selected sites in the polymers allowed for direct observation of the transformations arising from oxidation processes. As opposed to model compound studies, the reactions were followed directly in the polymer. The labeling experiments confirm the previously reported oxidation of the methylene carbon to ketone in the methylenedianiline portion of the polymer chain. They also show the formation of two other oxidized species, acid and ester, from this same carbon. In addition, the technique provides the first evidence of the kind of degradation reactions that are occurring in the nadic end caps. Several PMR formulations containing moieties determined to be present after oxidation, as suggested by the labeling study, were synthesized. Weight loss, FTIR, and natural abundance NMR of these derivatives were followed during aging. In this way, weight loss could be related to the observed transformations.

Meador, Mary Ann B.↗

NASA NTRS1988

Preparation for microgravity - The role of the Microgravity Material Science Laboratory

Experiments at the NASA Lewis Research Center's Microgravity Material Science Laboratory using physical and mathematical models to delineate the effects of gravity on processes of scientific and commercial interest are discussed. Where possible, transparent model systems are used to visually track convection, settling, crystal growth, phase separation, agglomeration, vapor transport, diffusive flow, and polymer reactions. Materials studied include metals, alloys, salts, glasses, ceramics, and polymers. Specific technologies discussed include the General Purpose furnace used in the study of metals and crystal growth, the isothermal dendrite growth apparatus, the electromagnetic levitator/instrumented drop tube, the high temperature directional solidification furnace, the ceramics and polymer laboratories and the center's computing facilities.

Johnston, J. Christopher↗

NASA NTRS1988

Preparation for microgravity: The role of the microgravity materials science laboratory

A laboratory dedicated to ground based materials processing in preparation for space flight was established at the NASA Lewis Research Center. Experiments are performed to delineate the effects of gravity on processes of both scientific and commercial interest. Processes are modeled physically and mathematically. Transport model systems are used where possible to visually track convection, settling, crystal growth, phase separation, agglomeration, vapor transport, diffusive flow, and polymers reactions. The laboratory contains apparatus which functionally duplicates apparatus available for flight experiments and other pieces instrumented specifically to allow process characterization. Materials addressed include metals, alloys, salts, glasses, ceramics, and polymers. The Microgravity Materials Science Laboratory is staffed by engineers and technicians from a variety of disciplines and is open to users from industry and academia as well as the government. Examples will be given of the laboratory apparatus typical experiments and results.

Johnston, J. Christopher↗