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1、AIAA S P-086-200 1 Fire, Explosion, Compatibility, and Safety Hazards of Nitrogen Tetroxide Copyright American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction
2、 or networking permitted without license from IHS -,-,- 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 Abstract This Special Project report presen
3、ts 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 extensive bib I iog ra p h y. Copyr
4、ight American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- AlAA SP-086-2001 Library of Congress Cata
5、loging-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 1-56347-496-4 (PDF) 1. Nitrogen tetroxide I. Title: Fire, explosion, comp
6、atibility, 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 Astronautics 1801 Alexander Bell Drive, Reston, VA 20191 Copyright O 2001
7、 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 publisher. Printed in the United States of America. II Copyright American Instit
8、ute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- AlAA SP-086-2001 Contents . Foreword viii Acronyms x Vocabula
9、ry 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 introduction 1 Introduction . 1 About this special report 1 Hazard assessment 1 NTO fire and explosion hazards
10、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 limits 13 NTO flash and fire point . 13 Ignition sources and minimum ignition energies . 13 Characteristics of N
11、TO 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 reactions . 17 Hypergolic behavior of NTO mixtures . . Explosive engine residues 20 NTOlcombustible mixture detona
12、tions . 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 General material compatibility concerns 25 . . . . 111 Copyright American Institute of Aeronautics and Astron
13、autics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- 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
14、.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 degadation concerns 25 Material degradation criteria . 25 Factors affecting material degradation 27 Material compatibility data 28 Tem p
15、eratu re effect 28 NTO degradation 29 NTO composition changes . 29 NTO degradation criteria 29 Flow decay 29 Titanium stress corrosion cracking 53 Cleaning solvents . 53 Corrosion in nitric acid 54 . . . . . . Solvent properties of NTO 54 . NTO specifications 55 Assessment examples 56 Example 1 . 56
16、 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 Threshold limit values of the ACGIH 58 Final rule limits of OSHA 59 Recommendation of NIOSH . 60 SARA Title III 60 Spacecraft maxi
17、mum allowable concentrations (SMAC) 60 Toxicity 61 General toxicity matters 61 Results of exposure to NTO . 61 Teratogenic and reproductive toxicity 64 Carcinogenicity 64 Exposure remediation and control . 64 General Guidelines . 64 . . iv Copyright American Institute of Aeronautics and Astronautics
18、 Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- 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
19、.9 4.6 Protection of personnel from exposure to NTO . 64 Treatment of personnel exposed to NTO 65 Fire fighting . 66 Dispersion of NTO vapors 68 NTO handling 68 General handling considerations 68 Personal protective equipment . 69 Monitoring equipment . 69 Engineering design . 71 Laboratory design 7
20、2 Storage of NTO . 73 Shipping NTO . 74 Waste disposal . 74 Regulatory enforcement 75 Assessment example . 76 Annex A: Chemical. physical. and thermodynamic properties of NTO and related fluids . 78 Annex B: Analytical spectroscopy of NTO . 90 Annex C: NTO Specifications 94 Bibliography . 97 Index .
21、 107 Fig u res Minimum spontaneous ignition temperatures of liquid hydrazine at various initial temperatures in NTO-air mixtures as a function of NTO concentration (Zabetakis 1965) . 4 Minimum spontaneous ignition temperatures of liquid hydrazine in contact with flowing NTO-nitrogen gas mixtures (Zu
22、ng. Trachencko. and Breen 1968) 5 Effect of reduced pressure on the spontaneous ignition temperature of liquid hydrazine in NTO (Zung. Trachencko. 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 co
23、ncentration (Zabetakis 1965) . 6 Minimum spontaneous ignition temperatures of liquid MMH at various initial temperatures in NTO-air mixtures as a function of NTO concentration (Zabetakis 1965) 7 Minimum spontaneous ignition temperatures of liquid UDMH at various initial temperatures in NTO-air mixtu
24、res as a function of NTO concentration (Zabetakis 1965) 8 Minimum spontaneous ignition temperatures of 0.05 mL of liquid UDMH in NTO-air mixtures at different pressures as a function of NTO concentration (Zabetakis 1965) 9 Minimum spontaneous ignition temperatures of vaporized UDMH-air mixtures in c
25、ontact with 100% NTO at 298 K (77 OF) as a function of UDMH concentration in air (Zabetakis 1965) . 9 V Copyright American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo
26、reproduction or networking permitted without license from IHS -,-,- AlAA SP-086-2001 9 10 A . 1 A.2 A.3 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
27、 pressure versus time profile for a confined reaction . 16 Fraction dissociation of gaseous N . O . to NO. 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 tempera
28、ture 261.9 (1 1.8 OF) to 431.6 K (317 OF) . 83 Vapor pressure of MON propellants containing 1.69%, 2.1 0%. and 2.98% NO 87 Vapor pressure vs . temperature for MON I O . 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 concentra
29、tion . 86 Boiling points of mixed oxides of nitrogen (N,O, /NO) as a function of the weight percent of N , O , . 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
30、 analytical region for H,O. “0,. and “0, (I-cm pathlength) 92 Mid-infrared spectrum of gaseous MON 3 (10-cm pathlength. 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 t
31、o NTO 11 Fire hazards of solids exposed to NTO . 12 Adiabatic factors . 14 Typical explosion potentials . 15 Impact test results for materials immersed in NTO . 18 NTO constant temperature mechanical impact data . 19 Nonmetallic materials rating criteria . 27 Compatibility of metallic materials with
32、 NTO . 30 Test 15 data for metallic materials with MON 3 . 35 Compatibility of nonmetallic materials with NTO . 35 Nonmetals 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 MO
33、N 3 . 44 Compatibility of Kalrez perfluorofluoroelastomers with NTO at ambient temperature . 47 Nonmetals not recommended 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
34、 vi Copyright American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- AlAA SP-086-2001 20 21 22 23 24
35、A . 1 c.1 c.2 Corrosion rates of alloys in NTO containing 0.2% water (/y) . 55 ACGIH 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
36、 NO. 78 Chemical composition and physical properties . 95 Current space shuttle fluid use requirements for MON 3 (NASA 1994) . 96 vi i Copyright American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Res
37、ale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- 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 a
38、s an oxidizer for the Orbital Maneuvering System 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
39、must be aware of these hazards and safeguard against 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 in
40、formation has been compiled, testing in several areas 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
41、 as new data are obtained. The authors of the NASA 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
42、consensus documents. This publication is under the 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, re
43、commended practices, and guides are advisory only. 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 s
44、tandards publications, the Liquid Propulsion Committee 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 pu
45、blication, the members of the AIAA Liquid Propulsion 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 h i n Glassman Howard Julien Chard Keller Charles Leveritt Mark Mueller Elizabet
46、h M. Mull Gregory Nunz Bryan Palaszewski Steven Schneider 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 Califo
47、rnia Institute of Technology NASA Kennedy Space Center 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
48、 Lewis Research Center viii Copyright American Institute of Aeronautics and Astronautics Provided by IHS under license with AIAA Licensee=IHS Employees/1111111001, User=Wing, Bernie Not for Resale, 04/18/2007 02:36:33 MDTNo reproduction or networking permitted without license from IHS -,-,- AIAA SP-086-2001 Joseph Shepherd Californina Institute of Technology Timothy Smith Bill St. Cyr Mark Underdown NASA Goddard Stephen Woods Edward J. Wueherer Primex Aerospace NASA Glenn Research