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At least 721 records · Page 40

Chemical Aging of Environmentally Friendly Cleaners

Use of cleaners in the manufacturing area demands bottles that will hold a sufficient amount of material and allow for easy and controlled dispensing by the operator without contamination or material leaching from the bottle. The manufacturing storage conditions are also a factor that may affect cleaner chemical integrity and its potential to leave a residue on the part. A variety of squeeze bottles stored in mild (72 F, 10 % R.H., dark) and harsh (105 F, 50 % R.H., fluorescent lighting) conditions were evaluated to determine the effect of environment and bottle exposure on the chemical composition of TCA (1,1,1 trichloroethane) replacement solvents. Low Density Polyethylene (LDPE) bottles were found to be quite permeable to all the cleaners evaluated in this study indicating this bottle type should not be used in the manufacturing area. Fluorinated Polyethylene (FLPE) bottles showed little cleaner loss and change in cleaner chemical composition over time suggesting these bottles would be acceptable for use. Chemical analysis indicates limonene-containing cleaners show increased non-volatile residue (NVR) content with storage under harsh conditions. Some cleaners use BHT (butylated hydroxytoluene) as stabilizer and to protect against limonene oxidation. Under harsh conditions, BHT was quickly depleted resulting in higher NVR levels.

Evans, K.↗

Addition Polyimides from Non-Mutagenic Diamines

Studies were conducted to find an acceptable non-mutagenic diamine to replace 4,4'-methylenedianiline (MDA), a suspect carcinogen, which is currently being used in PMR-15 polyimide applications. Several diamines containing fluorine and trifluoromethyl substituent groups were synthesized. The diamines were polymerized with the dimethyl ester of 3,3',4,4'-benzophenone tetracarboxylic acid (BTDE), using the monomethyl ester of nadic acid (NE) as an endcap. The effect of diamine structure on rheological properties, glass transition temperature, and thermo-oxidative stability was investigated. Unidirectional laminates were fabricated from selected resins, using carbon fiber as the reinforcement. The results indicate that some of the diamines containing trifluoromethyl groups are non-mutagenic, and have potential to replace MDA in PMR polyimides for long-term applications at temperatures up to 300 C.

Delvigs, Peter↗

Ab Initio Studies of Stratospheric Ozone Depletion Chemistry

An overview of the current understanding of ozone depletion chemistry, particularly with regards the formation of the so-called Antarctic ozone hole, will be presented together with an outline as to how ab initio quantum chemistry can be used to further our understanding of stratospheric chemistry. The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results will be shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗

Ab Initio Studies of Halogen and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗

Vacuum Ultraviolet Radiation and Atomic Oxygen Durability Evaluation of HST Bi-Stem Thermal Shield Materials

Bellows-type thermal shields were used on the bi-stems of replacement solar arrays installed on the Hubble Space Telescope (HST) during the first HST servicing mission (SMI) in December 1993. These thermal shields helped reduce the problem of thermal gradient- induced jitter observed with the original HST solar arrays during orbital thermal cycling and have been in use on HST for eight years. This paper describes ground testing of the candidate solar array bi-stem thermal shield materials including backside aluminized Teflon(R)FEP (fluorinated ethylene propylene) with and without atomic oxygen (AO) and ultraviolet radiation protective surface coatings for durability to AO and combined AO and vacuum ultraviolet (VOV) radiation. NASA Glenn Research Center (GRC) conducted VUV and AO exposures of samples of candidate thermal shield materials at HST operational temperatures and pre- and post-exposure analyses as part of an overall program coordinated by NASA Goddard Space Flight Center (GSFC) to determine the on-orbit durability of these materials. Coating adhesion problems were observed for samples having the AO- and combined AO/UV-protective coatings. Coating lamination occurred with rapid thermal cycling testing which simulated orbital thermal cycling. This lack of adhesion caused production of coating flakes from the material that would have posed a serious risk to HST optics if the coated materials were used for the bi-stem thermal shields. No serious degradation was observed for the uncoated aluminized Teflon(R) as evaluated by optical microscopy, although atomic force microscopy (AFM) microhardness testing revealed that an embrittled surface layer formed on the uncoated Teflon(R) surface due to vacuum ultraviolet radiation exposure. This embrittled layer was not completely removed by AO erosion, No cracks or particle flakes were produced for the embrittled uncoated material upon exposure to VUV and AO at operational temperatures to an equivalent exposure of approximately five years in the HST environment. Uncoated aluminized FEP Teflon(R) was determined to be the most appropriate thermal shield material and was used on the bi-stems of replacement solar arrays installed on HST during SMI in December 1993. The SMI -installed solar arrays air scheduled to be replaced during MST's fourth servicing mission (SM3B) in early 2002.

Dever, Joyce↗

A Sensitive Technique Using Atomic Force Microscopy to Measure the Low Earth Orbit Atomic Oxygen Erosion of Polymers

Polymers such as polyimide Kapton and Teflon FEP (fluorinated ethylene propylene) are commonly used spacecraft materials due to their desirable properties such as flexibility, low density, and in the case of FEP low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low Earth orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen erosion of polymers occurs in LEO and is a threat to spacecraft durability. It is therefore important to understand the atomic oxygen erosion yield (E, the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. Because long-term space exposure data is rare and very costly, short-term exposures such as on the shuttle are often relied upon for atomic oxygen erosion determination. The most common technique for determining E is through mass loss measurements. For limited duration exposure experiments, such as shuttle experiments, the atomic oxygen fluence is often so small that mass loss measurements can not produce acceptable uncertainties. Therefore, a recession measurement technique has been developed using selective protection of polymer samples, combined with postflight atomic force microscopy (AFM) analysis, to obtain accurate erosion yields of polymers exposed to low atomic oxygen fluences. This paper discusses the procedures used for this recession depth technique along with relevant characterization issues. In particular, a polymer is salt-sprayed prior to flight, then the salt is washed off postflight and AFM is used to determine the erosion depth from the protected plateau. A small sample was salt-sprayed for AFM erosion depth analysis and flown as part of the Limited Duration Candidate Exposure (LDCE-4,-5) shuttle flight experiment on STS-51. This sample was used to study issues such as use of contact versus non-contact mode imaging for determining recession depth measurements. Error analyses were conducted and the percent probable error in the erosion yield when obtained by the mass loss and recession depth techniques has been compared. The recession depth technique is planned to be used to determine the erosion yield of 42 different polymers in the shuttle flight experiment PEACE (Polymer Erosion And Contamination Experiment) planned to fly in 2002 or 2003.

deGroh, Kim K.↗

Determination of Highly Accurate Heats of Formation

Two approaches for directly computing a molecular heat of formation based on sophisticated ab initio electronic structure theory axe discussed and example calculations are presented for several molecules of interest in atmospheric chemistry including HNO and CICN. The accuracy of these approaches for a small subset of the molecules is demonstrated by comparison to very accurate experimental data. A third approach for evaluating accurate heats of formation consists of combining experimental and theoretical data. The potential for this method to provide reliable thermochemical data on many molecules using accurate experimental beats of formation for only a small number of species is demonstrated by giving accurate (Delta)H(sup 0, sub f) quantities for a host of fluorine, chlorine, and bromine oxide and nitrogen oxide compounds. Potential pitfalls in all three approaches are discussed.

Lee, Timothy J.↗

Analysis of Metallized Teflon(trademark) Film Materials Performance on Satellites

Laboratory and on-orbit performance data for two common thermal control materials, silver- and aluminum-backed (metallized) fluorinated ethyl-propylene (TER) was collected from a variety of sources and analyzed. This paper demonstrates that the change in solar absorptance, alpha, is a strong function of particulate radiation for these materials. Examination of additional data shows that the atomic oxygen recession rate is a strong function of solar exposure with an induction period of between 25 to 50 equivalent solar hours. The relationships determined in this analysis were incorporated into an electronic knowledge base, the 'Spacecraft Materials Selector,' under NASA contract NAS8-98213.

Pippin, H. Gary↗

Gallium Compounds: A Possible Problem for the G2 Approaches

The G2 atomization energies of fluorine and oxygen containing Ga compounds are greatly in error. This arises from an inversion of the Ga 3d core orbital and the F 2s or O 2s valence orbitals. Adding the Ga 3d orbital to the correlation treatment or removing the F 2s orbitals from the correlation treatment are shown to eliminate the problem. Removing the O 2s orbital from the correlation treatment reduces the error, but it can still be more than 6 kcal/mol. It is concluded that the experimental atomization energy of GaF2 is too large.

Bauschlicher, Charles W., Jr.↗

Techniques for Measuring Low Earth Orbital Atomic Oxygen Erosion of Polymers

Polymers such as polyimide Kapton and Teflon FEP (fluorinated ethylene propylene) are commonly used spacecraft materials due to their desirable properties such as flexibility, low density, and in the case of FEP, a low solar absorptance and high thermal emittance. Polymers on the exterior of spacecraft in the low Earth orbit (LEO) environment are exposed to energetic atomic oxygen. Atomic oxygen reaction with polymers causes erosion, which is a threat to spacecraft durability. It is therefore important to understand the atomic oxygen erosion yield (E, the volume loss per incident oxygen atom) of polymers being considered in spacecraft design. The most common technique for determining E is through mass loss measurements. For limited duration exposure experiments, such as shuttle experiments, where the atomic oxygen fluence is often so low that mass loss measurements can not produce acceptable uncertainties, recession measurements based on atomic force microscopy analyses can be used. Equally necessary to knowing the mass loss or recession depth for determining the erosion yield of polymers is the knowledge of the atomic oxygen fluence that the polymers were exposed to in space. This paper discusses the procedures and relevant issues for mass loss and recession depth measurements for passive atomic oxygen erosion yield characterization of polymers, along with techniques for active atomic oxygen fluence and erosion characterization. One active atomic oxygen erosion technique discussed is a new technique based on optical measurements. Details including the use of both semi-transparent and opaque polymers for active erosion measurement are reviewed.

deGroh, Kim K.↗

XPS Study of Plasma- and Argon Ion-Sputtered Polytetrafluoroethylene

The similarity of plasma-polymerized tetrafluoroethylene (PPTFE) and the fluoropolymer film deposited by rf (radio frequency) plasma sputtering (SPTFE) of polytetrafluoroethylene (PTFE), noted earlier in the literature, has been reconfirmed. FT-IR (Fourier Transform Infrared), XPS (X ray Photoelectron Spectroscopy) and UV (ultraviolet) spectroscopy has been employed in apparently the first study to involve preparation of PPTFE and SPTFE in the same reactor and under comparable low-power plasma conditions. Most of the work concerned the use of He or Ar as sputtering gas, but some runs were also carried out with the other rare gases Ne, Kr and Xe. The C1s XPS spectra of SPTFE films displayed a relatively higher content of CF2 groups, and yielded higher F/C (fluorine / carbon) ratios, than PPTFE films, while the SPTFE films were somewhat more transparent in the UV than PPTFE. The F/C ratios for SPTFE were essentially independent of the rare gas used for sputtering. Increasing rf power from 10 to 50 W for Xe plasma-sputtering of PTFE resulted in successively lower F/C ratios (1.55 to 1.21), accompanied by sputtering of the glass reactor occurring at 40 W and above. Some limited XPS, FT-IR and UV data are presented on Ar ion-sputtered PTFE.

Golub, Morton A.↗

The Effect of Heating on the Degradation of Ground Laboratory and Space Irradiated Teflon(r) FEP

The outer most layer of the multilayer insulation (MLI) blankets on the Hubble Space Telescope (HST) is back surface aluminized Teflon(R) FEP (fluorinated ethylene propylene). As seen by data collected after each of the three servicing missions and as observed during the second servicing mission (SM2), the FEP has become embrittled in the space environment, leading to degradation of the mechanical properties and severe on-orbit cracking of the FEP. During SM2, a sample of aluminized-FEP was retrieved from HST that had cracked and curled, exposing its aluminum backside to space. Because of the difference in optical properties between FEP and aluminum, this insulation piece reached 200 C on-orbit, which is significantly higher than the nominal MLI temperature extreme of 50 C. This piece was more brittle than other retrieved material from the first and third servicing missions (SM1 and SM3A, respectively). Due to this observation and the fact that Teflon thermal shields on the solar array bi-stems were heated on-orbit to 130 C, experiments have been conducted to determine the effect of heating on the degradation of FEP that has been irradiated in a ground laboratory facility or in space on HST. Teflon FEP samples were X-ray irradiated in a high vacuum facility in order to simulate the damage caused by radiation in the space environment. Samples of pristine FEP, X-ray irradiated FEP and FEP retrieved from the HST during SM3A were heat treated from 50 to 200 C at 25 intervals in a high vacuum facility and then tensile tested. In addition, samples were tested in a density gradient column to determine the effect of the radiation and heating on the density of FEP. Results indicate that although heating does not degrade the tensile properties of non-irradiated Teflon, there is a significant dependence of the percent elongation at failure of irradiated Teflon as a function of heating temperature. Irradiated Teflon was found to undergo increasing degradation in the elongation at failure as temperature was increased from room temperature to 200 C. Rate of degradation changes, which were consistent with the glass I transition temperatures for FEP, appeared to be present in both tensile and density data. The results indicate the significance of the on-orbit temperature of Teflon FEP with respect to its degradation in the low Earth orbital space environment.

deGroh, Kim K.↗

Properties of M40J Carbon/PMR-II-50 Composites Fabricated with Desized and Surface Treated Fibers. Characterization of M40J Desized and Finished Fibers

To increase performance and durability of high temperature composites for potential rocket engine components, it is necessary to optimize wetting and interfacial bonding between high modulus carbon fibers and high temperature polyimide resins. It has been previously demonstrated that the electro-oxidative shear treatments used by fiber manufacturers are not effective on higher modulus fibers that have fewer edge and defect sites in the surface crystallites. In addition, sizings commercially supplied on most carbon fibers are not compatible with polyimides. This study was an extension of prior work characterizing the surface chemistry and energy of high modulus carbon fibers (M40J and M60J, Torray) with typical fluorinated polyimide resins, such as PMR-II-50. A continuous desizing system which utilizes environmentally friendly chemical- mechanical processes was developed for tow level fiber and the processes were optimized based on weight loss behavior, surface elemental composition (XPS) and morphology (FE-SEM) analyses, and residual tow strength of the fiber, and the similar approaches have been applied on carbon fabrics. Both desized and further treated with a reactive finish were investigated for the composite reinforcement. The effects of desizing and/or subsequent surface retreatment on carbon fiber on composite properties and performance including fiber-matrix interfacial mechanical properties, thermal properties and blistering onset behavior will be discussed in this presentation.

Allred, Ronald E.↗

Radiation Durability of Candidate Polymer Films for the Next Generation Space Telescope Sunshield

The Next Generation Space Telescope (NGST), anticipated to be launched in 2009 for a 10-year mission, will make observations in the infrared portion of the spectrum to examine the origins and evolution of our universe. Because it must operate at cold temperatures in order to make these sensitive measurements, it will use a large, lightweight, deployable sunshield, comprised of several polymer film layers, to block heat and stray light. This paper describes laboratory radiation durability testing of candidate NGST sunshield polymer film materials. Samples of fluorinated polyimides CP1 and CP2, and a polvarylene ether benzimidazole. TOR-LM(TM), were exposed to 40 keV electron and 40 keV proton radiation followed by exposure to vacuum ultraviolet (VUV) radiation in the 115 to 200 nm wavelength range. Samples of these materials were also exposed to VUV without prior electron and proton exposure. Samples of polyimides Kapton HN, Kapton E, and Upilex-S were exposed to electrons and protons only, due to limited available exposure area in the VUV facility. Exposed samples were evaluated for changes in solar absorptance and thermal emittance and mechanical properties of ultimate tensile strength and elongation at failure. Data obtained are compared with previously published data for radiation durability testing of these polymer film materials.

Dever, Joyce↗

High-Performance, Space-Storable, Bi-Propellant Program Status

Bipropellant propulsion systems currently represent the largest bus subsystem for many missions. These missions range from low Earth orbit satellite to geosynchronous communications and planetary exploration. The payoff of high performance bipropellant systems is illustrated by the fact that Aerojet Redmond has qualified a commercial NTO/MMH engine based on the high Isp technology recently delivered by this program. They are now qualifying a NTO/hydrazine version of this engine. The advanced rhenium thrust chambers recently provided by this program have raised the performance of earth storable propellants from 315 sec to 328 sec of specific impulse. The recently introduced rhenium technology is the first new technology introduced to satellite propulsion in 30 years. Typically, the lead time required to develop and qualify new chemical thruster technology is not compatible with program development schedules. These technology development programs must be supported by a long term, Base R&T Program, if the technology s to be matured. This technology program then addresses the need for high performance, storable, on-board chemical propulsion for planetary rendezvous and descent/ascent. The primary NASA customer for this technology is Space Science, which identifies this need for such programs as Mars Surface Return, Titan Explorer, Neptune Orbiter, and Europa Lander. High performance (390 sec) chemical propulsion is estimated to add 105% payload to the Mars Sample Return mission or alternatively reduce the launch mass by 33%. In many cases, the use of existing (flight heritage) propellant technology is accommodated by reducing mission objectives and/or increasing enroute travel times sacrificing the science value per unit cost of the program. Therefore, a high performance storable thruster utilizing fluorinated oxidizers with hydrazine is being developed.

Schneider, Steven J.↗

High Performance Polymers

This report summarizes results from research on high performance polymers. The research areas proposed in this report include: 1) Effort to improve the synthesis and to understand and replicate the dielectric behavior of 6HC17-PEK; 2) Continue preparation and evaluation of flexible, low dielectric silicon- and fluorine- containing polymers with improved toughness; and 3) Synthesis and characterization of high performance polymers containing the spirodilactam moiety.

Venumbaka, Sreenivasulu R.↗

A Novel Approach for Modeling Chemical Reaction in Generalized Fluid System Simulation Program

The Generalized Fluid System Simulation Program (GFSSP) is a computer code developed at NASA Marshall Space Flight Center for analyzing steady state and transient flow rates, pressures, temperatures, and concentrations in a complex flow network. The code, which performs system level simulation, can handle compressible and incompressible flows as well as phase change and mixture thermodynamics. Thermodynamic and thermophysical property programs, GASP, WASP and GASPAK provide the necessary data for fluids such as helium, methane, neon, nitrogen, carbon monoxide, oxygen, argon, carbon dioxide, fluorine, hydrogen, water, a hydrogen, isobutane, butane, deuterium, ethane, ethylene, hydrogen sulfide, krypton, propane, xenon, several refrigerants, nitrogen trifluoride and ammonia. The program which was developed out of need for an easy to use system level simulation tool for complex flow networks, has been used for the following purposes to name a few: Space Shuttle Main Engine (SSME) High Pressure Oxidizer Turbopump Secondary Flow Circuits, Axial Thrust Balance of the Fastrac Engine Turbopump, Pressurized Propellant Feed System for the Propulsion Test Article at Stennis Space Center, X-34 Main Propulsion System, X-33 Reaction Control System and Thermal Protection System, and International Space Station Environmental Control and Life Support System design. There has been an increasing demand for implementing a combustion simulation capability into GFSSP in order to increase its system level simulation capability of a liquid rocket propulsion system starting from the propellant tanks up to the thruster nozzle for spacecraft as well as launch vehicles. The present work was undertaken for addressing this need. The chemical equilibrium equations derived from the second law of thermodynamics and the energy conservation equation derived from the first law of thermodynamics are solved simultaneously by a Newton-Raphson method. The numerical scheme was implemented as a User Subroutine in GFSSP.

Sozen, Mehmet↗

Composition of the Chandra ACIS Contaminant

The Advanced CCD Imaging Spectrometer (ACIS) on the Chandra X-ray Observatory is suffering a gradual loss of low energy sensitivity due to a buildup of a contaminant. High resolution spectra of bright astrophysical sources using the Chandra Low Energy Transmission Grating Spectrometer (LETGS) have been analyzed in order to determine the nature of the contaminant by measuring the absorption edges. The dominant element in the contaminant is carbon. Edges due to oxygen and fluorine are also detectable. We can place stringent limits on nitrogen and high Z elements such as AI, Si, and Mg. Not including H, we find that C, O, and F comprise less than 80%, 7%, and 7% of the contaminant by number, respectively, Nitrogen is less than 3% of the contaminant. We will assess various candidates for the contaminating material and the time dependence. For example, the detailed structure of the absorption edges provides information about the bonding structure of the compound, eliminating aromatic hydrocarbons as the contaminating material.

Marshall, Herman↗