NOT MEASUREMENT SENSITIVE DOE‐HDBK‐1081‐2014 Supersedes DOE‐HDBK‐1081‐94 DOE HANDBOOK PRIMER ON SPONTANEOUS HEATING AND PYROPHORICITY U.S. Department of Energy FSC‐6910 Washington, D.C. 20585 DISTRIBUTION STATEMENT: Approved for public release; distribution is unlimited. This document is available on the Department of Energy Technical Standards Program Web page at: http://www.hss.doe.gov/nuclearsafety/ns/techstds/ Key words: Alkali Metals , Aluminum, Arsine, Calcium, Class D Extinguishing Agents, Coal Storage, Combustible Metals, Diborane, Fire, Hafnium, Heating, Hydrazine, Hydrocarbons, Hypergolic, Hypergolic Reaction, Iron, Lithium, Magnesium, Metals, Microbial Heating, NaK, Organic, Oxidizer, Phosphine, Phosphorus, Plutonium, Potassium, Pyrophoric, Pyrophoricity, Pyrophoric Gases, Pyrophoric Reagents, Silane Specific Area, Sodium, Sodium‐Potassium, Specific Surface Area, Spontaneous, Spontaneous Combustion, Steel, Super Oxides, Thorium, Titanium, Uranium, Water Reactive Metals, Zinc, Zirconium FOREWORD The Primer on Spontaneous Heating and Pyrophoricity is approved for use by all DOE Components. It was developed to help Department of Energy (DOE) facility contractors prevent fires caused by spontaneous ignition. Spontaneously ignitable materials include those that ignite because of a slow buildup of heat (spontaneous heating) and those that ignite in air (pyrophoricity). The scientific principles of combustion and how they affect materials known to be spontaneously combustible are explained. The fire hazards of specific spontaneously heating and pyrophoric materials are discussed as well as techniques to prevent their ignition. Suitable fire extinguishing agents are included for most materials as well as safety precautions for storage and handling. The DOE Primers are fundamental handbooks on safety‐related topics of interest in the DOE Complex and are intended as an educational aid for operations and maintenance personnel and others who may have an interest in this topic. The Primers attempt to supply information in an easily understandable form which will help workers perform their duties in a safe and reliable manner. Persons trained in other technical areas may also find the Primers useful as a guide or as a reference source for further investigation. Beneficial comments (recommendations, additions, deletions) and any pertinent data that may improve this document should be sent to: U.S. Department of Energy Office of Nuclear Safety (HS‐30) 1000 Independence Avenue SW Washington, D.C. 20585 i ACKNOWLEDGEMENTS This DOE Primer was prepared under the sponsorship of the DOE Office of Environment, Health, Safety and Security (AU). The sponsor is responsible for coordinating the development and/or review of the FAQS by subject matter experts to ensure that the technical content of the Standard is accurate and adequate for Department‐wide application. The sponsor would like to acknowledge the following individuals who participated in the development and/or review of this document: Writing Team Coordinators: Jim Bisker, DOE Office of Environment, Health, Safety & Security (AU‐32) Tom Christman, Independent Consultant Writing Team Members: Tom Allison, Savannah River Nuclear Solutions Harvey Goranson, Oak Ridge National Laboratory Jim Landmesser Sr., DOE Office of Environmental Management (EM‐41) Andrew Minister, Battelle Memorial Institute ‐ Pacific Northwest National Laboratory Rob Plonski, Los Alamos National Laboratory ii DOE‐HDBK‐1081‐2014 Primer on Spontaneous Heating and Pyrophoricity TABLE OF CONTENTS OVERVIEW ......................................................................................................................................................... 1 INTRODUCTION ................................................................................................................................................. 2 DEFINITIONS ...................................................................................................................................................... 3 PRINCIPLES OF COMBUSTION ........................................................................................................................... 4 Combustion ................................................................................................................................................... 4 The Fire Tetrahedron .................................................................................................................................... 4 Oxidizing Agent .......................................................................................................................................... 4 Fuel ............................................................................................................................................................ 5 Heat Source ............................................................................................................................................... 6 Uninhibited Chain Reaction ...................................................................................................................... 6 Spontaneous Ignition .................................................................................................................................... 7 Hypergolic and Pyrophoric Reactions ....................................................................................................... 7 Spontaneous Heating ................................................................................................................................ 7 SPONTANEOUS HEATING/IGNITION OF HYDROCARBONS AND ORGANICS ..................................................... 8 Spontaneous Heating/Ignition of Hydrocarbons .......................................................................................... 8 Spontaneous Oxidation and Heating of Coal .............................................................................................. 10 Coal Storage ................................................................................................................................................ 11 PYROPHORIC GASES AND LIQUIDS .................................................................................................................. 13 Pyrophoric Gases ......................................................................................................................................... 13 Arsine ...................................................................................................................................................... 13 Diborane .................................................................................................................................................. 13 Phosphine ................................................................................................................................................ 14 Silane ....................................................................................................................................................... 14 Extinguishing Pyrophoric Gas Fires ......................................................................................................... 14 Pyrophoric Gas Storage and Dispensing Areas ....................................................................................... 14 Pyrophoric Nonmetallic Liquids...................................................................................................................... 15 Hydrazine ................................................................................................................................................ 15 PYROPHORIC NONMETALLIC SOLIDS ............................................................................................................ 16 Phosphorus ................................................................................................................................................. 16 COMBUSTIBLE AND PYROPHORIC METALS ..................................................................................................... 16 Magnesium .................................................................................................................................................. 18 iii DOE‐HDBK‐1081‐2014 Primer on Spontaneous Heating and Pyrophoricity Properties ................................................................................................................................................ 18 Storage and Handling .............................................................................................................................. 18 Process Hazards ...................................................................................................................................... 19 Extinguishing Magnesium Fires ............................................................................................................... 20 Titanium ...................................................................................................................................................... 21 Properties ................................................................................................................................................ 21 Storage and Handling .............................................................................................................................. 21 Process Hazards ......................................................................................................................................