1、AIAA S P-086-200 1 Fire, Explosion, Compatibility, and Safety Hazards of Nitrogen Tetroxide AIAA S P-086-200 1 Special Project Report Fire, Explosion, Compatibility, and Safety Hazards of Nitrogen Tetroxide Sponsored by American Institute of Aeronautics and Astronautics Approved January 2001 Abstrac
2、t This Special Project report presents information that designers, builders, and users of nitrogen tetroxide systems can use to avoid or resolve nitrogen tetroxide hazards. Pertinent research is summarized, and the data are presented in a quick-reference form. Further information can be found in the
3、 extensive bib I iog ra p h y. AlAA SP-086-2001 Library of Congress Cataloging-in-Publication Special project report: fire, explosion, compatibility, and safety hazards of nitrogen tetroxidelsponsored by American Institute of Aeronautics and Astronautics p. cm. ISBN 1-56347-495-6 (softcover), ISBN 1
4、-56347-496-4 (PDF) 1. Nitrogen tetroxide I. Title: Fire, explosion, compatibility, and safety hazards of nitrogen tetroxide. II. American Institute of Aeronautics and Astronautics TP290.N53 S65 2001 “AIAA SP-086-2001 629.475 - dc21 2001 022548 CIP Published by American Institute of Aeronautics and A
5、stronautics 1801 Alexander Bell Drive, Reston, VA 20191 Copyright O 2001 American Institute of Aeronautics and Astronautics All rights reserved. No part of this publication may be reproduced in any form, in an electronic retrieval system or otherwise, without prior written permission of the publishe
6、r. Printed in the United States of America. II AlAA SP-086-2001 Contents . Foreword viii Acronyms x Vocabulary xi Trademarks xiv 1 1.1 1.2 1.3 2 2.1 2.2 2.2.1 2.2.2 2.2.3 2.2.4 2.2.5 2.2.6 2.3 2.3.1 2.3.2 2.4 2.4.1 2.4.2 2.4.3 2.4.4 2.4.5 2.4.6 2.4.7 2.5 2.5.1 2.5.2 2.5.3 2.5.4 3 3.1 NTO hazards int
7、roduction 1 Introduction . 1 About this special report 1 Hazard assessment 1 NTO fire and explosion hazards 2 Introduction . 2 2 Mixtures of NTO with Aerozine 50. hydrazine. MMH. and UDMH 3 Mixtures of NTO with flammable gases . 10 Mixtures of NTO with other liquids and solids . 10 Flammability limi
8、ts 13 NTO flash and fire point . 13 Ignition sources and minimum ignition energies . 13 Characteristics of NTO fires . 13 Adiabatic factor 13 Vapor flame speed . 14 NTO explosions 15 Explosion potential 15 Exothermic reactions 15 NTO deflagration 16 Shock sensitive NTO mixtures . 17 Nitration reacti
9、ons . 17 Hypergolic behavior of NTO mixtures Explosive engine residues 20 NTOlcombustible mixture detonations . 21 Hazards assessment 22 Hazard assessment process 22 Initial conditions and criteria 23 Fire hazard assessment example 23 Explosion assessment example . 24 Material compatibility 25 Gener
10、al material compatibility concerns 25 . . 111 AlAA SP-086-2001 3.2 3.2.1 3.2.2 3.2.3 3.3 3.3.1 3.4 3.4.1 3.4.2 3.4.3 3.4.4 3.4.5 3.4.6 3.4.7 3.5 3.6 3.6.1 3.6.2 3.6.3 3.6.4 4 4.1 4.2 4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6 4.3 4.3.1 4.3.2 4.3.3 4.3.4 4.4 4.4.1 Material degradation . 25 General material
11、degadation concerns 25 Material degradation criteria . 25 Factors affecting material degradation 27 Material compatibility data 28 Tem peratu re effect 28 NTO degradation 29 NTO composition changes . 29 NTO degradation criteria 29 Flow decay 29 Titanium stress corrosion cracking 53 Cleaning solvents
12、 . 53 Corrosion in nitric acid 54 . . Solvent properties of NTO 54 . NTO specifications 55 Assessment examples 56 Example 1 . 56 Example 2 56 Example 3 . 57 Example 4 . 57 Personnel and environmental hazards 58 I ntrod u ct io n 58 Exposure guidelines . 58 Introduction to applicable guidelines 58 Th
13、reshold limit values of the ACGIH 58 Final rule limits of OSHA 59 Recommendation of NIOSH . 60 SARA Title III 60 Spacecraft maximum allowable concentrations (SMAC) 60 Toxicity 61 General toxicity matters 61 Results of exposure to NTO . 61 Teratogenic and reproductive toxicity 64 Carcinogenicity 64 E
14、xposure remediation and control . 64 General Guidelines . 64 iv AlAA SP-086-2001 4.4.2 4.4.3 4.4.4 4.4.5 4.5 4.5.1 4.5.2 4.5.3 4.5.4 4.5.5 4.5.6 4.5.7 4.5.8 4.5.9 4.6 Protection of personnel from exposure to NTO . 64 Treatment of personnel exposed to NTO 65 Fire fighting . 66 Dispersion of NTO vapor
15、s 68 NTO handling 68 General handling considerations 68 Personal protective equipment . 69 Monitoring equipment . 69 Engineering design . 71 Laboratory design 72 Storage of NTO . 73 Shipping NTO . 74 Waste disposal . 74 Regulatory enforcement 75 Assessment example . 76 Annex A: Chemical. physical. a
16、nd thermodynamic properties of NTO and related fluids . 78 Annex B: Analytical spectroscopy of NTO . 90 Annex C: NTO Specifications 94 Bibliography . 97 Index . 107 Fig u res Minimum spontaneous ignition temperatures of liquid hydrazine at various initial temperatures in NTO-air mixtures as a functi
17、on of NTO concentration (Zabetakis 1965) . 4 Minimum spontaneous ignition temperatures of liquid hydrazine in contact with flowing NTO-nitrogen gas mixtures (Zung. Trachencko. and Breen 1968) 5 Effect of reduced pressure on the spontaneous ignition temperature of liquid hydrazine in NTO (Zung. Trach
18、encko. and Breen 1968) . 5 Minimum spontaneous ignition temperatures of liquid hydrazine. MMH. and UDMH in contact with NTO-air mixtures as a function of NTO concentration (Zabetakis 1965) . 6 Minimum spontaneous ignition temperatures of liquid MMH at various initial temperatures in NTO-air mixtures
19、 as a function of NTO concentration (Zabetakis 1965) 7 Minimum spontaneous ignition temperatures of liquid UDMH at various initial temperatures in NTO-air mixtures as a function of NTO concentration (Zabetakis 1965) 8 Minimum spontaneous ignition temperatures of 0.05 mL of liquid UDMH in NTO-air mix
20、tures at different pressures as a function of NTO concentration (Zabetakis 1965) 9 Minimum spontaneous ignition temperatures of vaporized UDMH-air mixtures in contact with 100% NTO at 298 K (77 OF) as a function of UDMH concentration in air (Zabetakis 1965) . 9 V AlAA SP-086-2001 9 10 A . 1 A.2 A.3
21、A.4 A.5 A.6 A.7 B.l B.2 B.3 B.4 Minimum spontaneous ignition temperatures of 0.05 mL of liquid UDMH in NTO-helium- oxygen atmospheres for various helium-oxygen ratios (Zabetakis 1965) . 10 Typical pressure versus time profile for a confined reaction . 16 Fraction dissociation of gaseous N.O. to NO.
22、as a function of temperature for different pressures . 79 Vapor pressure of NTO as a function of temperature 256 K (1 . 1 OF) to 309 K 96.5 OF) 82 Vapor pressure of NTO as a function of temperature 261.9 (1 1.8 OF) to 431.6 K (317 OF) . 83 Vapor pressure of MON propellants containing 1.69%, 2.1 0%.
23、and 2.98% NO 87 Vapor pressure vs . temperature for MON IO. MON 25. and MON 30 I90 K (-11 OF) to 405 K (269 OF) 85 Freezing points of the NTO-nitric oxide system as a function of NO concentration . 86 Boiling points of mixed oxides of nitrogen (N,O, /NO) as a function of the weight percent of N,O, .
24、 86 Near infrared spectrum of gaseous N,O, (10-cm pathlength. approximately 130 Pa) . 91 Near infrared spectrum of liquid N,O, (I-cm pathlength) 91 Expanded near infrared spectrum of analytical region for H,O. “0,. and “0, (I-cm pathlength) 92 Mid-infrared spectrum of gaseous MON 3 (10-cm pathlength
25、. approximately 130 Pa) . 92 Tables 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Reactions of NTO and hydrazine diluted in flowing argon 7 Fire hazard testing of liquids exposed to NTO 11 Fire hazards of solids exposed to NTO . 12 Adiabatic factors . 14 Typical explosion potentials . 15 Impact te
26、st results for materials immersed in NTO . 18 NTO constant temperature mechanical impact data . 19 Nonmetallic materials rating criteria . 27 Compatibility of metallic materials with NTO . 30 Test 15 data for metallic materials with MON 3 . 35 Compatibility of nonmetallic materials with NTO . 35 Non
27、metals compatible or acceptable for NTO service 39 Lubricants and miscellaneous nonmetals compatible or acceptable for NTO service . 42 Test 15 data for nonmetallic materials with MON 3 . 44 Compatibility of Kalrez perfluorofluoroelastomers with NTO at ambient temperature . 47 Nonmetals not recommen
28、ded for NTO service . 48 Nonmetals not recommended for NTO service . 51 Variables affecting flow decay in NTO systems 53 WSTF corrosion rates of alloys in 71 % nitric acid (Finly) 55 vi AlAA SP-086-2001 20 21 22 23 24 A . 1 c.1 c.2 Corrosion rates of alloys in NTO containing 0.2% water (/y) . 55 ACG
29、IH threshold limit value guidelines . 59 OSHA final rule limits 60 Seven-day spacecraft maximum allowable concentration 61 Median lethal NO. concentrations for inhalation in animals 63 Dissociation of liquid N.O. to NO. 78 Chemical composition and physical properties . 95 Current space shuttle fluid
30、 use requirements for MON 3 (NASA 1994) . 96 vi i AIAA SP-086-2001 Foreword Nitrogen tetroxide (NTO) is a corrosive, strongly oxidizing liquid compound used chiefly in aerospace propulsion and power systems. It is currently used in the Space Shuttle as an oxidizer for the Orbital Maneuvering System
31、and Reaction Control System. Although NTO is immensely useful in aerospace applications, it has drawbacks. For example, NTO is hypergolic with many materials; liquid and vapor NTO are corrosive and highly toxic. The users and designers of NTO systems must be aware of these hazards and safeguard agai
32、nst them. The goal of this document is to summarize the existing hazards data into one document. The subjects addressed in this document are fire, explosion, compatibility hazards, and overall safety considerations. Although a substantial amount of information has been compiled, testing in several a
33、reas is still being conducted and will continue for several years. In the interest of safety, the need for such a document is immediate. Therefore, this document will be released with the currently compiled information and will be periodically updated as new data are obtained. The authors of the NAS
34、A manual, dated November 15, 2000 were David L. Baker, Dennis D. Davis, Louis A. Dee, Benjamin Greene, Catherine H. Hart, and Stephen S. Woods. AIAA Special Reports are a part of the AIAA Standards Program and frequently serve as precursors to formal consensus documents. This publication is under th
35、e purview of the Liquid Propulsion Committee on Standards, the group responsible for determining the future of the publication and for maintaining it in a technically current state. The AIAA Standards Procedures provide that all approved standards, recommended practices, and guides are advisory only
36、. Their use by anyone engaged in industry or trade is entirely voluntary. There is no agreement to adhere to any AIAA standards publication and no commitment to conform to or be guided by any standards report. In formulating, revising, and approving standards publications, the Liquid Propulsion Comm
37、ittee on Standards will not consider patents that may apply to the subject matter. Prospective users of the publications are responsible for protecting themselves against liability for infringement of patents, or copyrights, or both. At the time of publication, the members of the AIAA Liquid Propuls
38、ion Committee on Standards were: Robert Ash Kyaw Aung C. T. Avedisian David L. Baker Patrick Carrick James E. Cocchiaro Dan Colen Fred Cutlick Tom Draus Chris M. Erickson hin Glassman Howard Julien Chard Keller Charles Leveritt Mark Mueller Elizabeth M. Mull Gregory Nunz Bryan Palaszewski Steven Sch
39、neider Old Dominion University University of Southern California Cornell University NASA Johnson Space Center White Sands Test Facility Phillips Laboratory J HU/Chemical Propulsion Information Agency Lockheed-Martin Propulsion Products Center California Institute of Technology NASA Kennedy Space Cen
40、ter Rocketdyne Division, Boeing North American Princeton University Honeywell Technology Solutions Inc. Hughes Aerospace Army Research Laboratory Aerospace Corporation The Boeing Company Los Alamos National Laboratory NASA Lewis Research Center NASA Lewis Research Center viii AIAA SP-086-2001 Joseph
41、 Shepherd Californina Institute of Technology Timothy Smith Bill St. Cyr Mark Underdown NASA Goddard Stephen Woods Edward J. Wueherer Primex Aerospace NASA Glenn Research Center at Lewis Field NASA Stennis Space Center Honeywell Technology Solutions Inc. The Standards Executive Council accepted the
42、document for publication on January 11,2001 ix AIAA SP-086-2001 Acronyms ACGIH ASME ASTM BEI BPVC CPIA DOD DOT EPA FORP IARC IDLH K C-J Lc50 LD50 LEPC LFL and UFL MIE MMH MMHN MON MSDS mPY NTO NTP NIOSH NIR NO NVR OSHA Pc PEL PPm RCRA RCS REL RQ SARA SCBA SERC SI SMAC STEL TLV N204 N O2 TLD-1 TLV-C
43、TLV-TWA TOMES TRACE American Conference of Governmental and Industrial Hygienists American Society of Mechanical Engineers American Society of Testing and Materials Biological Exposure Indices Boiler and Pressure Vessel Code Chapman-Jouguet Chemical Propulsion Information Agency Department of Defens
44、e Department of Transportation Environmental Protection Agency Fuel-Oxidizer Reaction Product International Agency for Research of Cancer Immediately Dangerous To Life or Health Kelvin Lethal Concentration Lethal Dose Local Emergency Planning Committee Lower and Upper Flammability Limit Minimum Igni
45、tion Energy Monomethylhydrazine Methylhydrazinium Nitrate Mixed Oxides of Nitrogen Material Safety Data Sheet mil per year Nitrogen Tetroxide National Toxicology Program Din itrog e n Tetroxide National Institute of Occupational Safety and Health Near- I nfrared Nitric Oxide Nitrogen Dioxide Nonvola
46、tile Residue Occupational Safety and Health Administration Chamber Pressure Permissible Exposure Limits Parts Per Million Resource Conservation and Recovery Act Reaction Control Subsystem Recommended Exposure Limit Reportable Quantity Superfund Amendments and Reauthorization Act Self-contained Breat
47、hing Apparatus State Emergency Response Commission International System Units Spacecraft Maximum Acceptable Concentration Short Term Exposure Limit Toxic Level Detector 1 Threshold Limit Value Threshold Limit Value - Ceiling Threshold Limit Value - Time Weighted Average Toxicology, Occupational Medi
48、cine, and Environmental Series Toxic Release Analysis of Chemical Emissions X TPQ TQ TSCA UDMH WSTF AIAA SP-086-2001 Threshold Planning Quanity Threshold Quanity Toxic Substances Control Act Unsymetrical dimethylhydrazine White Sands Test Facility xi AIAA SP-086-2001 Vocabulary Adiabatic: A process
49、by which the system changes its thermodynamic state without thermal energy exchange between the system and its surroundings. Aerozine 50: A hydrazine type propellant consisting of a 50% mixture by weight of UDMH and hydrazine. Blast Wave: Pressure pulse following a shock wave caused by velocity imparted by the shock wave to the medium particles. Cyanosis: A condition in which the skin appears blue as a result of too little oxygen in the blood. Deflagration: A flame moving through a flammable mixture in the form of a subsonic wave (with respect to the unburned mixture). Dermal Exp
