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NASA NTRS2009

A Summary of NASA and USAF Hypergolic Propellant Related Spills and Fires

Several unintentional hypergolic fluid related spills, fires, and explosions from the Apollo Program, the Space Shuttle Program, the Titan Program, and a few others have occurred over the past several decades. Spill sites include the following government facilities: Kennedy Space Center (KSC), Johnson Space Center (JSC), White Sands Test Facility (WSTF), Vandenberg Air Force Base (VAFB), Cape Canaveral Air Force Station (CCAFS), Edwards Air Force Base (EAFB), Little Rock AFB, and McConnell AFB. Until now, the only method of capturing the lessons learned from these incidents has been "word of mouth" or by studying each individual incident report. The root causes and consequences of the incidents vary drastically; however, certain "themes" can be deduced and utilized for future hypergolic propellant handling. Some of those common "themes" are summarized below: (1) Improper configuration control and internal or external human performance shaping factors can lead to being falsely comfortable with a system (2) Communication breakdown can escalate an incident to a level where injuries occur and/or hardware is damaged (3) Improper propulsion system and ground support system designs can destine a system for failure (4) Improper training of technicians, engineers, and safety personnel can put lives in danger (5) Improper PPE, spill protection, and staging of fire extinguishing equipment can result in unnecessary injuries or hardware damage if an incident occurs (6) Improper procedural oversight, development, and adherence to the procedure can be detrimental and quickly lead to an undesirable incident (7) Improper materials cleanliness or compatibility and chemical reactivity can result in fires or explosions (8) Improper established "back-out" and/or emergency safing procedures can escalate an event The items listed above are only a short list of the issues that should be recognized prior to handling hypergolic fluids or processing vehicles containing hypergolic propellants. The summary of incidents in this report is intended to cover many more issues than those listed above.

Nufer, Brian M.↗
NASA NTRS2000

Hypergolic Propellant Safety Course

Under the sponsorship of the NASA Safety Training Center at the Johnson Space Center, a hypergolic propellant safety course has been developed. This is a 2-day course on guidelines for hypergolic propellant system design, materials selection, operations, storage, and transportation. Recognizing that numerous fuels and oxidizers can be hypergolic, this course is specific to the hydrazine family of fuels and nitrogen tetroxide and its variants. The objectives of the course are to enable the student to identify and evaluate the hazards of hypergolic propellants, and to understand the methods for controlling those hazards and responding to emergencies. The course covers properties and hazards of the hydrazines and oxidizers; design and operations in hypergolic facilities; materials selection for use in hypergol systems; storage vessels, piping, and component considerations; hypergol detection; fire fighting practices; operating and transportation principles and procedures; and emergency practices and considerations. A hazards analysis methodology is presented. Numerous references are provided and the applicability of certain regulatory documents is discussed. A brief overview of other propellants, including hydrogen peroxide, is given at the end of the course.

Rathgeber, Kurt A.↗
NASA NTRS2009

Lessons Learned Entry: Hypergolic Propellant Related Spills and Fires

The attached report is a compilation of all credible, unintentional hypergolic fluid related spills, fires, and explosions from the Apollo Program, the Space Shuttle Program, Titan Program, and a few other programs. Spill sites include the following government facilities: KSC, JSC, WSTF, VAFB, CCAFS, EAFB, Little Rock AFB, and McConnell AFB. The root causes and consequences of the incidents contained in this document vary drastically; however, certain "themes" can be deduced and utilized for future hypergolic propellant handling. Some of those common "themes" are summarized below: (1) Improper configuration control and complacency can lead to being falsely comfortable with a system (2) Communication breakdown can escalate an incident to a level where injuries occur and/or hardware is damaged (3) Improper propulsion system and ground support system designs can destine a system for failure (4) Improper training of technicians, engineers, and safety personnel can put lives in danger (5) Improper PPE, spill protection, and staging of fire extinguishing equipment can result in unnecessary injuries or hardware damage if an incident occurs (6) Improper procedural oversight, development, and adherence to the procedure can be detrimental and quickly lead to an undesirable incident (7) Improper local cleanliness or compatibility can result in fires or explosions The items listed above are only a short list of the issues that should be recognized prior to handling of hypergolic fluids or processing of vehicles containing hypergolic propellants. The summary of incidents in this report is intended to cover many more issues than those listed above that have been found during nearly the entire spectrum. of hypergolic propellant and/or vehicle processing.

Nufer, Brian↗
NASA NTRS1997

Sample Diluter for Detecting Hypergolic Propellants and Other Toxic or Hazardous Gases

Hardware was developed to dilute vapor samples of purged hypergolic propellants (with air) into the range of existing instruments for detection of such toxic vapors. Since these detectors are normally used to monitor at the threshold limit value (TLV), most do not have quantitative capability at percent levels which relate to lower explosion limit (LEL) and fire hazards. For example, the upper limits of Energetic Sciences (ESI) 6000 series detectors used at KSC are 200 parts per million (ppm) for monomethyl hydrazine (MMH) and 500 ppm for nitrogen dioxide (NO2) arising from decomposition of nitrogen tetroxide (N2O4). Orbiter Processing Facility (OPF) personnel servicing Shuttle thrusters need to measure up to 250 ppm MMH and 7,500 ppm NO2 with portable, intrinsically safe instruments. Our objective was to quickly fabricate a sample diluter out of existing materials as a temporary measure while other parallel efforts were conducted to provide a commercial or in-house-developed instrument to detect high propellant levels. A 3 to 1 diluter would bring 500 ppm MMH into the range of the existing fuel ESI, and a 30 to 1 diluter would do the same for NO2. In this way, familiar equipment already available would be used, resulting in minimal paperwork, safety, and training impacts and low cost. An MMH vapor sample-diluter was constructed from a 1/4-inch Kynar tee, along with specially designed lengths of sample and dilution tubing. The sample line was 3 feet of Bev-A-Line 4, 1/4-inch tube leading to the straight run of the tee. The side run of the tee had a 17-inch length of Bev-A-Line 4, 1/4-inch tube, for nominal 3 to 1 dilution. A gas sample bag was prepared and assayed at 113 ppm ppm MMH, and diluted vapor samples were assayed at 39.5 ppm, or a measured dilution of 2.9 to 1. For NO2, a 316 stainless steel (SS) 1/8-inch tee with 49.5 inches of coiled, 1/8-inch outside diameter (OD) 316 SS tubing was used as the sampling end of the dilution system. The side run of the tee was open. The measured dilution ratio, based on the input value of 6,480 ppm NO2, and the average output value of 233 ppm, was 28 to 1. Thus, sample-diluters were successful in diluting concentrated hypergolic propellant vapors, both MMH and N2O4 into the ranges of existing TLV detectors.

Barile, R. G.↗
NASA NTRS1997

Sample Diluter for Detecting Hypergolic Propellants and Other Toxic or Hazardous Gases

Hardware was developed to dilute vapor samples of purged hypergolic propellants (with air) into the range of existing instruments for detection of such toxic vapors. Since these detectors are normally used to monitor at the threshold limit value (TLV), most do not have quantitative capability at percent levels which relate to lower explosion limit (LEL) and fire hazards. For example, the upper limits of Energetic Sciences (ESI) 6000 series detectors used at KSC are 200 parts per million (ppm) for monomethyl hydrazine (MMH) and 500 ppm for nitrogen dioxide (NO2) arising from decomposition of nitrogen tetroxide (N2O4). Orbiter Processing Facility (OPF) personnel servicing Shuttle thrusters need to measure up to 250 ppm MMH and 7500 ppm NO2 with portable, intrinsically safe instruments. Our objective was to quickly fabricate a sample diluter out of existing materials as a temporary measure while other parallel efforts were conducted to provide a commercial or in-house-developed instrument to detect high propellant levels. A 3 to 1 diluter would bring 500 ppm MMH into the range of the existing fuel ESI, and a 30 to 1 diluter would do the same for NO2. In this way, familiar equipment already available would be used, resulting in minimal paperwork, safety, and training impacts and low cost. An MMH vapor sample-diluter was constructed from a 1/4-inch Kynar tee, along with specially designed lengths of sample and dilution tubing. The sample line was 3 feet of Bev-A-Line 4, 1/4 inch tube leading to the straight run of the tee. The side run of the tee had a 17-inch length of Bev-A-Line 4, 1/4-inch tube, for nominal 3 to 1 dilution. A gas sample bag was prepared and assayed at 113 ppm MMH, and diluted vapor sarnples were assayed at 39.5 ppm, or a measured dilution of 2.9 to 1. For NO2, a 316 stainless steel (SS) 1/8-inch tee with 49.5 inches of coiled, 1/8-inch outside diameter (OD) 316 SS tubing was used as the sarnpling end of the dilution system. The side run of the tee was open. The measured dilution ratio, based on the input value of 6,480 ppm NO2 and the average output value of 233 ppm, was 28 to 1. Thus, sample-diluters were successful in diluting concentrated hypergolic propellant vapors, both MMH and N2O4, into the ranges of existing TLV detectors.

Barile, R. G.↗
NASA NTRS1972

Pulse performance analysis for small hypergolic propellant rocket engines

Small rocket engine tests were conducted for the purpose of obtaining pulse performance data to aid in preliminary design and evaluation of attitude control systems. Both monopropellant and hypergolic bipropellant engines of thrust levels from 5 to 445 N (1 to 100 lb) were tested. The performance data for the hypergolic propellant rockets are compared with theoretical performance calculated from idealized chamber filling and evacuation characteristics. Electromechanical delays in valve response and heat transfer characteristics were found to cause substantial deviation between theoretical performance and test performance. The theoretical analysis is modified to obtain a semiempirical model for hypergolic propellant rockets.

Smith, G. W.↗
NASA NTRS1972

Pulse performance analysis for small hypergolic-propellant rocket engines

Small rocket engine tests were conducted for the purpose of obtaining pulse performance data to aid in preliminary design and evaluation of attitude control systems. Both monopropellant and hypergolic bipropellant engines of thrust levels from 1 to 100 lbs were tested. The performance data for the hypergolic propellant rockets are compared with theoretical performance calculated from idealized chamber filling and evacuation characteristics. Electromechanical delays in valve response and heat transfer characteristics were found to cause substantial deviation between theoretical and test performance. The theoretical analysis is modified to obtain a semi-empirical model for hypergolic propellant rockets which is demonstrated to be reasonably accurate for two different engine configurations over a considerable range of duty cycles.

Smith, G. W.↗
NASA NTRS1999

Reactivities of Precision Cleaning Solvents with Hypergolic Propellants

The reactivities of several selected halogenated precision cleaning solvents with hypergolic propellants has been determined by analysis of the rates of formation of halide ion decomposition products. The solvents were Asahiklin AK 225, Asahiklin AK 225 AES, HFE 7100, HFE 7100 DE, Vertrel XF, Vertrel MCA, Vertrel MCA Plus, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), and trans-1,2-dichloroethylene (DCE). The propellants were hydrazine (HZ), monomethylhydrazine (MMH), and mixed oxides of nitrogen (MON-3). The Vertrel solvents showed significant reactivity with HZ. All of the solvents except DCE exhibited significant reactivity with MMH, particularly HFE 7100 DE and CFC-113. HFE 7100 DE, Vertrel MCA, and Vertrel MCA Plus also showed significant reactivity with MON-3 oxidizer.

Davis, Dennis D.↗
NASA NTRS1977

Handbook on Hypergolic Propellant Discharges and Disposal

The efficiency of all treatment methods formerly or currently used in treating chemical wastes is assessed with emphasis on the disposal of hypergolic propellants. Maximum focus is on the space shuttle propellants MMH and N2O4. Except for hydrogen peroxide oxidizers, all the propellants are nitrogen based and can be potentially reduced to valuable plant nutrients. In theory, all the propellants can be reduced to carbon, hydrogen, nitrogen, and oxygen, except of fuming nitric acid which contains a small amount of fluorine. Appendices cover: (1) a general design criteria for disposal ponds; (2) thermal aspects of reaction in dilute solution; (3) gas bubble growth, detachment, and rise (4) absorption scrubber fundamentals and descriptions; (5) separation of a propellant vapor from a helium stream by permeation; and (6) atmospheric emission limits.

Bowman, T. E.↗