1、, b95534 0003220 57T U Special Copvright Notice o I999 by the American Institute of Aeronautics and Astronautics. All rights reserved. AIAA SP-085-1999 5Special Project Fire, Explosion, Compatibility, and Safety Hazards of Hypergols = Monomethylhydrazine AIAA SP-085-1999 Special Project Report Fire,
2、 Explosion, Compatibility, and Safety Hazards of Hypergols - Monomethylhydrazine Sponsored by American Institute of Aeronautics and Astronautics Approved Abstract This Special Project report presents information that designers, builders, and users of monomethylhydrazine systems can use to avoid or r
3、esolve monomethylhydrazine hazards. Pertinent research is summarized, and the data are presented in a quick-reference form. Further information can be found in the extensive bibliography. AIM SP-085-1999 Special project report: fire, explosion, compatibility, and safety hazards of hypergols - monome
4、thylhydrazine /sponsored by American Institute of Aeronautics and Astronautics. p. cm. Cover title ISBN 1-56347-362-3 (electronic) 1. Methyl hydrazine. 2. Combustion. I. Title: Fire, explosion, compatability, and safety hazards “AIAA SP-085-1999 of hypergols-monomethylhydrazine. II. American Institu
5、te of Aeronautics and Astronautics. TP290.N53 S64 1999 99-042015 Published by American Institute of Aeronautics and Astronautics 1801 Alexander Bell Drive, Reston, VA 22091 Copyright O 1999 American Institute of Aeronautics and Astronaut i cs All rights reserved No part of this publication may be re
6、produced 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 AIM SP-085-1999 Contents Foreword vi Acronyms vi Glossary viii Trademarks . xi . 1 1.1 1.2 2 2.1 2.2 2.2.1 2.2.2 2.2.3 2.3 2.3.1 2.3.2 2
7、.3.3 2.4 2.4.1 2.4.2 2.4.3 2.5 3 3.1 3.1 . 1 3.1.2 3.1.3 3.1.4 3.2 3.2.1 3.2.2 Introduction . 1 About this special report 1 Hazard assessment 2 Fire hazards . 4 Assessing MMH fire hazards . 4 Criteria . 4 Vapor flammability limits 4 Liquid flash and fire points 6 Ignition sources . 6 Effects 8 MMH r
8、eaction products . 9 Vapor flame speed 10 Liquid burning rate 13 Data 14 Vapor . 14 Liquid . 17 Ignition . 18 Assessment example 22 Explosion hazards . 23 MMH deflagration 24 MMH deflagration assessment 24 MMH deflagration criteria 25 MMH deflagration effects 26 MMH deflagration data 27 Exothermic r
9、eaction 28 Exothermic reaction assessment 28 Exothermic reaction criteria . 29 . III AIM SP-085-1999 3.2.3 3.2.4 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.4 3.4.1 3.4.2 4 4.1 4.1 . 1 4.1.2 4.1.3 4.1.4 4.2 4.2.1 4.2.2 4.2.3 4.2.4 4.3 5 5.1 5.1 . 1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.1.7 5.2 Exothermic reaction effec
10、ts . 29 Exothermic reaction data . 31 Detonation 31 Detonation assessment . 31 Detonation criteria . 33 Detonation effects . 36 Detonation data 37 Assessment examples 38 Deflagration assessment example 38 Detonation assessment example . 40 MMH and material compatibility . 40 Material degradation . 4
11、1 Material degradation assessment 41 Material degradation criteria 41 Material degradation effects 41 Material degradation data 42 MMH degradation . 42 MMH degradation assessment 42 MMH degradation criteria 43 MMH degradation effects 44 MMH degradation data 46 Assessment example 58 Safety . 60 MMH t
12、oxicity . 61 Results of MMH exposure . 62 Inhalation 63 Dermal exposure 64 Ingestion . 65 Developmental toxicity 65 Carcinogenicity . 65 Relative toxicity of MMH to other hydrazines 66 MMH exposure guidelines . 66 . iv AIM SP-085-1999 5.2.1 5.2.2 5.2.3 5.2.4 5.2.5 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.4 5.4
13、.1 5.4.2 5.4.3 5.4.4 5.4.5 5.4.6 5.4.7 5.4.8 5.5 Threshold limit values of the American Council of Governmental Industrial Hygienists . 66 Guidelines of the Occupational Safety and Health Administration . 67 Guidelines of the National Institute of Occupational Safety and Health 68 Emergency planning
14、 requirements Spacecraft maximum acceptable concentrations MMH exposure remediation and control . . 69 First aid 69 Personnel protection . 71 Fire fighting Spill cleanup . MMH handling Engineering design . 74 Storage containers 75 Storage areas . 75 Shipping Monitoring equipment Waste disposal . Reg
15、ulatory requirements . . 80 Additional information 81 Assessment example 81 Annex A: Hazard assessment example Annex B: Chemical and physical properties of monomethylhydrazine . Annex C: Rapid compression experimental measurements Annex D: References I01 V AIAA SP-085-1999 Foreword Monomethylhydrazi
16、ne (MMH) is a colorless, corrosive, strongly reducing liquid compound. It is used chiefly in aerospace propulsion and power systems. It is currently used in the Space Shuttle as a fuel for the orbital maneuvering system and reaction control system. Although MMH is immensely useful in aerospace appli
17、cations, there are also drawbacks. For example, MMH vapor in air is flammable and detonable; both liquid and vapor MMH are corrosive, react with many materials, and are susceptible to catalytic decomposition; and MMH is highly toxic. The users and designers of MMH systems must be aware of these haza
18、rds 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 information has been compiled
19、, 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 as new data are obtained.
20、The authors of the NASA manual, dated May 3, 1993 were Stephen S. Woods, Radel L. Bunker, Nathalie B. Martin, Donald B. Wilson, and David L. Baker. AIAA Special Reports are a part of the AIAA Standards Program and frequently serve as precursors to formal consensus documents. This publication is unde
21、r 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, recommended practices, and guides are advisory
22、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 standards publications, the Liquid Propulsion
23、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 publication, the members of the AIAA Liquid Pro
24、pulsion Committee on Standards were: Robert Ash Old Dominion University Kyaw Aung C. T. Avedisian Cornell University Curt Botts Patrick Carrick Phillips Laboratory Georgia Institute of Technology Air Force, 45th Space Wing, Patrick AFB Fred Cutlick Tom Draus Irvin Glassman Princeton University Howar
25、d Julien Chard Keller Hughes Aerospace California Institute of Technology NASA Kennedy Space Center AlliedSigna1 Technical Services Corp. Team Charles Leveritt Army Research Laboratory Dennis Meinhardt Primex Aerospace Company Mark Mueller Aerospace Corporation Gregory Nunz Los Alamos National Labor
26、atory vi AIAA SP-085-1999 A, Ea ACG I H AIT AHJ ASME ASTM C-J CPIA DDT DOT Acronyms Arrhenius parameters American Conference of Governmental and Industrial Hygienists Autoignition temperature Authority Having Jurisdiction American Society of Mechanical Engineers American Society of Testing and Mater
27、ials Chapman-Jouguet Chemical Propulsion Information Agency Deflagration to detonation transition Department of Transportation EPA GI HAZMAT HZ Environmental Protection Agency Gastrointestinal Hazardous Materials Hvd raz ne IDLH LEPC I Immediately Dangerous To Life or Health I Local Emergency Planni
28、ng Committee vi i AIAA SP-085-1999 Glossary Activation Energy (or Apparent Activation Energy): In absolute-rate theory, the energy associated with the formation of an activated complex intermediate between the reactant(s) and product(s) of an elementary reaction. An “apparent” activation energy is u
29、sed as the parameter E, in an Arrhenius function when the exact kinetic mechanism is unknown. Adiabatic: A process in which the system changes state without thermal energy exchange between the system and the surroundings. Adiabatic Compression: Mechanical work transferred to a system under condition
30、s where there is an increase in the internal energy of the material for a static system or an increase in the enthalpy for a dynamic system. If the process is also reversible (in the thermodynamic definition), this change is also isentropic. Adiabatic Factor: The temperature change that occurs when
31、all the limiting reactant is completely consumed (normalized extent of reaction equals 1, when the reaction system is operated adiabatically). This factor is useful for comparing exothermicity or endothermicity of several reactions. Adiabatic Flame Temperature: The temperature of thermodynamic equil
32、ibrium in a reaction or in a set of reactions that occurs in a process operating adiabatically. Arrhenius Function: A mathematical model for defining the temperature dependency of an observed macroscopic kinetic reaction rate-the rate is proportional to exp(-E,/RT), where E, is the apparent activati
33、on energy, R is the ideal gas law constant, and T is the absolute temperature. Authority Having Jurisdiction (AHJ). The AHJ is the organization, office, or individual responsible for “approving” equipment, an installation, or a procedure. The designation is used in a broad manner because jurisdictio
34、n and “approval” agencies vary as do their responsibilities. Where public safety is primary, the AHJ may be a federal, state, local, or other regional department or individual such as a fire chief, fire marshal, chief of a fire prevention bureau, labor department, health department, building officia
35、l, electrical inspector, or others having statutory authority. For insurance purposes, the AHJ may be an insurance inspection department, rating bureau, or other insurance company representative. In many circumstances the AHJ is the property owner or his designated agent. At government installations
36、, the AHJ may be the commanding officer or a designated departmental official. Autoignition Temperature: The lowest temperature at which a material will spontaneously ignite. No additional ignition energy (ignition source) is required. Burning Rate: The rate of liquid mass consumption per unit area
37、(kg/(m2.s). Burning Velocity: The velocity at which the liquid level decreases. It is the burning rate/density of the liquid (m/s). Catalyst: A chemical compound or chemical species that alters the rate of a chemical reaction. The catalyst is not altered by the reaction. Cell Size: Refers to the wid
38、th of the characteristic fish scale-shaped cell pattern etched on a smoked foil during a gas-phase detonation. The cell pattern is produced by a detonation (the path of the triple-point intersection of the primary shock wave, the transverse shock wave, and the Mach stem wave. The cell width is used
39、as a parameter for characterizing detonations. viii AIAA SP-085-1999 Chapman-Jouguet (C-J) Detonation: Describes a stable detonation state that is consistent with most experimental measurement. The steady-state solution of the conservation equations at which the Rankine line is tangent to the Hugoni
40、ot curve. Compatibility with MMH: Materials should not corrode, deform, or lose strength when in prolonged contact with MMH. Critical Diameter: The tube diameter necessary for a gaseous detonation to propagate from the tube to an unconfined environment (Equation 3.6, d, = 13h). Critical Energy: The
41、minimum energy required to initiate an unconfined detonation in a specified mixture. Deflagration: A flame moving through a flammable mixture in the form of a subsonic wave (with respect to the unburned mixture). Dermal Exposure: The penetration of a toxic chemical through skin and into the blood st
42、ream. Such exposure can be rapid and difficult for the body to eliminate. Detonable Mixture: The state of a specified mixture that, upon application of the critical energy for the mixture. will initiate and sustain a detonation. This mixture is also flammable. Detonation: Exothermic chemical reactio
43、n coupled to a shock wave that propagates through a detonable mixture. The velocity of the shock wave is supersonic with respect to the unburned gases. After initiation, the thermal energy of the reaction sustains the shock wave, and the shock wave compresses the unreacted material to sustain the re
44、action. Initiation of a detonation can occur with a deflagration to detonation transition (DDT). Diluent: In a mixture, an inert material that reduces the concentration of the remaining materials. Dynamic Parameters: Four parameters (detonability limits, initiation energy, cell size, and critical tu
45、be diameter) used to describe the dynamic characteristics of a detonation. They are in contrast to the static C-J detonation parameters: velocity, detonation temperature, detonation pressure, and detonation density. Equivalence Ratio: The ratio of the actual fuel-oxidizer ratio to the stoichiometric
46、 fuel-oxidizer ratio. Exothermic: The production of thermal energy by a chemical reaction. Explosion: The rapid equilibration of pressure between the system and the surroundings, such that a shockwave is produced. Explosions may occur through mechanical failure of vessels containing high- pressure f
47、luids or through rapid chemical reactions producing large volumes of hot gases. Explosion Potential: A parameter that is useful for comparing an unknown system (reaction) to well- known reactions. It is the product of system volume (constant), adiabatic flame temperature, total moles per unit of mas
48、s in the system at equilibrium, and the ideal gas law constant. Fire: Sustained burning, as manifested by any or all of the following: light, flame, heat, and smoke (ASTM E 176-go).* Fire Point: The lowest temperature at which a flame continuously exists over a liquid surface upon ignition by an ope
49、n flame. *ASTM Fire Test Standards, 3rd Ed. 1990, ASTM, 191 6 Race St., Philadelphia, PA 191 03. ix AIAA SP-085-1999 Flame: A hot, usually luminous zone of gas, or particulate matter in gaseous suspension, or both, that is undergoing exothermic chemical reaction. A flame may be stationary with the flammable mixture fed into the reaction zone, or a flame may propagate through the flammable mixture, as in a deflagration. Flame Speed or Flame Velocity: Refers to the velocity of propagation of the reaction zone through the flammable mixture, as measured by a stationary observer. Usua
