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At least 19 records

Evaluation of HFC 245ca and HFC 236ea as foam blowing agents

Hydrochlorofluorocarbon (HCFC) 141b has been selected as the interim blowing agent for use in urethane insulations on NASA's Space Shuttle External Tank. Due to the expected limited commercial lifetime of this material, research efforts at the NASA Thermal Protection Systems Materials Research Laboratory at the Marshall Space Flight Center are now being devoted to the identification and development of alternatives with zero ozone depletion potential. Physical blowing agents identified to date have included hydrocarbons, fluorocarbons, hydrofluoroethers, and more predominantly, hydrofluorocarbons (HFCs). The majority of the HFC evaluations in industry have focused on the more readily available, low boiling candidates such as HFC 134a. Higher boiling HFC candidates that could be handled at ambient conditions and use current processing equipment would be more desirable. This paper will describe results from a research program of two such candidate HFC's performed as a cooperative effort between Martin Marietta Manned Space Systems, the U.S. Environmental Protection Agency, and Oak Ridge National Laboratories. The purpose of this effort was to perform a cursory evaluation of the developmental HFC's 245ca and 236ea as blowing agents in urethane based insulations. These two materials were selected from screening tests of 37 C2, C3, and C4 isomers based on physical properties, atmospheric lifetime, flammability, estimated toxicity, difficulty of synthesis, suitability for dual use as a refrigerant, and other factors. Solubility of the two materials in typical foam components was tested, pour foaming trials were performed, and preliminary data were gathered regarding foam insulation performance.

Sharpe, Jon↗

Rate constants for the reactions of OH with HFC-134a (CF3CH2F) and HFC-134 (CHF2CHF2)

Measurements of rate constants for HFC-134 (CF2HCF2H) relative to CH3CCl3, HFC-125, and HFC-134a are reported. The measurements were made in a slow-flow, temperature controlled photochemical reactor, and were based on relative rates of disappearance of the parent compounds as measured by FTIR spectroscopy. Hydroxyl radicals were generated by 254-nm photolysis of O3 in the presence of water vapor. NASA/JPL rate constants for the reference compounds are used to derive temperature-dependent rate constants of both compounds. Rate constants obtained from the different reference compounds are in excellent agreement. The presently recommended rate constant for HFC-134a is about 25 percent too high.

Demore, W. B.↗

Oxidation Resitant HfC-TaC Rocket Thruster for High Performance Propellants

The purpose of this reasearch effort was to develop high temperature, oxidation resistant thrusters which would lessen the thruster cooling requirements, resulting in increased performance and longer life for onboard propulsion systems for spacecraft. This research effort focussed on developing ceramic matrix composites (CMCs) for this application, and specifically investigated the use of HfC stabilized with TaC. This material composition can potentially operate in a stoichiometric oxygen to hydrogen ratio at a temperature of 5000 deg F (2760 deg C) in a radiatively cooled mode. Various compositions of Hafnium Carbide (HfC) and Tantalum Carbide (TaC) were deposited by chemical vapor deposition (CVD) and tested, in an attempt to identify the composition which offered the best oxidation resistance. Although it was identified that small amounts of TaC appeared to offer improved oxidation resistance over HfC alone, an optimal composition was not identified. A 251bf thruster was fabricated from a novel CMC sandwich construction with a HfC-TaC matrix, and survived two test firings, each of 5 seconds before a failure in the injector caused the run to be aborted. It was not possible to control the relative stoichiometry of the HfC and TaC composition throughout the reactor due to the large difference in the thermodynamics of the HfC and TaC formation from their respective chlorides. This also resulted in an inability to infiltrate TaC into the preform under the experimental conditions investigated. Other material compositions were fabricated and tested and two material systems; HfC-SiC functionally graded to C(sub f)/C and Re functionally graded to C(sub f)/C were selected for further testing. These functionally graded composites have use in a number of propulsion applications presently of interest to NASA and the defense industry. Their ability to withstand extremely hostile thermal environments and the light-weight and high-strength exhibited from the C(sub f)/C composite make these materials particularly suited for these applications. In the Phase III which is presently underway, Re functionally graded to C(sub f)/C is being further developed and tested for application in the thrust cells for the Linear Aerospike Engine for the X33 and RLV.

Patterson, Mark↗

Evaluated rate constants for selected HCFC's and HFC's with OH and O((sup)1D)

The chemistry of HCFC's and HFC's in the troposphere is controlled by reactions with OH in which a hydrogen atom is abstracted from the halocarbon to form water and a halo-alkyl radical. The halo-alkyl radical subsequently reacts with molecular oxygen to form a peroxy radical. The reactions of HCFC's and HFC's with O(exp1D) atoms are unimportant in the troposphere, but may be important in producing active chlorine of OH in the stratosphere. Here, the rate constants for the reactions of OH and O(exp1D) with many HFC's and HCFC's are evaluated. Recommendations are given for the five HCFC's and three HFC's specified by AFEAS as primary alternatives as well as for all other isomers of C1 and C2 HCFC's and HFC's where rate data exist. In addition, recommendations are included for CH3CCl3, CH2Cl2, and CH4.

Hampson, Robert F.↗

Does a threshold stress for creep exist in HfC-dispersed NiAl?

Recently it was proposed (Jha et al., 1989; Whittenberger et al., 1990) on the basis of constant velocity testing at 1300 K that dispersion strengthened NiAl composites containing about 4 wt pct HfC possess threshold stresses for creep. Further, 1300 K compression testing has been conducted on NiAl+4HfC, and diametrically opposite behavior has been found: for constant load creep tests a normal power law behavior was observed. However, additional constant velocity testing still indicates that the flow stress is essentially independent of strain rate below 10 exp -6/s. Examination of NiAl+4.3HfC specimens deformed under constant velocity conditions revealed that the original hot extruded small grain structure could be converted to large, elongated grains during testing. Such a transformation appears to be responsible for the apparent threshold stress behavior in HfC dispersed NiAl.

Whittenberger, J. D.↗

Elevated-Temperature Deformation Properties of a HfC Modified Ti-48Al-2Mn-2Nb Matrix Particulate Composite

Rapid solidification techniques in combination with HIPing have been used to produce Ti-48Al-2Mn-2Nb and a Ti-48Al-2Mn-2Nb+15 wt% HfC composite. While the composite does contain several second phases within the gamma + alpha(sub 2) matrix, none was identified to be HfC. The elevated-temperature properties were determined by constant velocity compression and constant load tensile testing in air between 1000 and 1173 K. Such testing indicated that the elevated temperature strengths of the HfC-modified aluminide was superior to those of the unreinforced matrix with the best 1100 K temperature slow strain rate properties for both materials being achieved after high-temperature annealing prior to testing. Examination of the microstructures after deformation in combination with the measured stress exponents and activation energies suggest that creep resistance of the HfC-modified form is due to solid-solution strengthening from carbon and hafnium rather than the presence of second phases.

Whittenberger, J. D.↗

Composition effects on mechanical properties of HfC-strengthened molybdenum alloys

The mechanical properties of swaged rod thermomechanically processed from arc-melted Mo-2Re-Hf-C alloys containing as much as 0.9 mol pct HfC have been evaluated. The low temperature ductilities of these alloys were not influenced by the amount of HfC present but by the amount of Hf in excess of stoichiometry. Maximum ductility occurred at 0.2 to 0.3 at. pct excess Hf. At 0.3 to 0.5 mol pct HfC, alloy strength varied directly with the Mo content of extracted carbide particles, both decreasing as the amount of excess Hf increased. Additions of 2 at. pct Re had little effect on strength or ductility. Tensile and creep strengths of Mo-2Re-0.7Hf-0.5C alloy equaled or exceeded those of other high strength Mo alloys.

Witzke, W. R.↗

Atmospheric degradation mechanisms of hydrogen containing chlorofluorocarbons (HCFC) and fluorocarbons (HFC)

The current knowledge of atmospheric degradation of hydrogen containing chlorofluorocarbons (HCFC 22 (CHClF2), HCFC 123 (CHCl2CF3), HCFC 124 (CHClFCF3), HCFC 141b (CFCl2CH3), HCFC 142b (CF2ClCH3)) and fluorocarbons (HFC 125 (CHF2CF3), HFC 134a (CH2FCF3), HFC 152a (CHF2CH3)) is assessed. Except for the initiation reaction by OH radicals, there are virtually no experimental data available concerning the subsequent oxidative breakdown of these molecules. However, from an analogy to the degradation mechanisms of simple alkanes, some useful guidelines as to the expected intermediates and final products can be derived. A noteable exception from this analogy, however, appears for the oxi-radicals. Here, halogen substitution induces new reaction types (C-Cl and C-C bond ruptures) which are unknown to the unsubstituted analogues and which modify the nature of the expected carbonyl products. Based on an evaluation of these processes using estimated bond strength data, the following simplified rules with regards to the chlorine content of the HCFC's may be deduced: (1) HCFC's containing one chlorine atom such as 22 and 142b seem to release their chlorine content essentially instantaneous with the initial attack on the parent by OH radicals, and for HCFC 124, such release is apparently prevented; (2) HCFC's such as 123 and 141b with two chlorine atoms are expected to release only one of these instantaneously; and the second chlorine atom may be stored in potentially long-lived carbonyl compounds such as CF3CClO or CClFO.

Zellner, Reinhard↗

Influence of grain size on the creep behavior of HfC-dispersed NiAl

Rapid solidification technology has been utilized to produce a NiAl-4(wt pct)HfC composite containing about 0.3 vol pct HfC as dispersed 50 nm particles. Study of the 1300 K compressive creep properties demonstrated that the initial, small grain size microstructure was unstable under slow strain rate deformation conditions. The grain growth which occurred during testing led to considerable strengthening. Subsequent measurements of the creep properties of the coarse grained specimens revealed that this strength was achieved by a large increase in the activation energy for deformation without any change in the stress exponent. Based on this work, it is concluded that large grain microstructures will be required for optimum elevated temperature creep properties in dispersed NiAl.

Whittenberger, J. D.↗

Preliminary evaluation of tensile and stress-rupture behavior of W + 24 at. pct Re + 0.4 at. pct HfC wire

Results are presented of an evaluation of tensile properties and stress-rupture bahavior of a small-diameter W24ReHfC (W-24Re-0.4(HfC)) wire, which is considered to be an excellent reinforcing fiber candidate for a variety of metal-matrix composites. The results were compared to data of Petrasek (1972) on W4ReHfC (W-4Re-0.4(HfC)) wire. It was found that the room-temperature (RT) tensile strength of the W24ReHfC wire was about 3250 MPa, higher than that of the W4ReHfC (3160 MPa) and WHfC (2250 MPa) wires. Above 1366 K, the W4ReHfC wire had both a greater tensile strength and the stress rupture strength than the W24ReHfC wire.

Yun, H. M.↗

The Use of HFC (CFC Free) Processes at the NASA Stennis Space Center

The search for ozone depleting alternative chemicals was heightened when, in 1990, the more than 65 countries that had signed the Montreal Protocol agreed to phase out completely by the year 2000. In 1992, then-president Bush advanced this date for the United States to January l, 1996. In 1991, it was realized that the planned phase out and eventual elimination of ozone depleting chemicals imposed by the Montreal Protocol and the resulting Clean Air Act (CAA) amendments would impact the cleaning and testing of aerospace hardware at the NASA Stennis Space Center. Because of this regulation, the Test & Engineering Sciences Laboratory has been working on solvent conversion studies to replace CFC-113. Aerospace hardware and test equipment used in rocket propulsion systems require extreme cleanliness levels to function and maintain their integrity. Because the cleanliness of aerospace hardware will be affected by the elimination of CFC-113; alternate cleaning technologies, including the use of fluoridated solvents have been studied as potential replacements. Several aqueous processes have been identified for cleaning moderately sized components. However, no known aqueous alternative exists for cleaning and validating T&ME and complex geometry based hardware. This paper discusses the choices and the methodologies that were used to screen potential alternatives to CFC-113.

Ross, Richard H.↗