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Liquid Jiping Liu

Liquid Explosives

123 Jiping Liu College of Materials Science and Engineering Beijing Institute of Technology Beijing China

ISBN 978-3-662-45846-4 ISBN 978-3-662-45847-1 (eBook) DOI 10.1007/978-3-662-45847-1

Library of Congress Control Number: 2014957400

Springer Heidelberg New York Dordrecht London © Springer-Verlag Berlin Heidelberg 2015 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made.

Printed on acid-free paper

Springer-Verlag GmbH Berlin Heidelberg is part of Springer Science+Business Media (www.springer.com) Preface

As the first book on Liquid Explosives, this book, covering part of the author’s achievements on energetic materials in the past about half a century, presents the results of a wide range of research fields with abundant information and valuable practicality. It also reviews the development of liquid explosives for the first time over the world and focuses on the latest research findings of the explosion mech- anism, properties, and preparation process of liquid explosives. Different from the detonation of condensed explosives, liquid explosives show distinct features to easily form under-compressed detonation. The charging and application of liquid explosives are not influenced by geographical conditions, local topographic feature, and land features. Thus, the application range of liquid explosives is considerably wide. The first word that pops up in the mind would be war, or national-defense, while talking about liquid explosives. The truth is that military use accounts for only a small part. Liquid explosives have been widely used in aerospace, sounding rockets, communications satellites, transportation, mining, construction, seismic prospecting, mineral exploration, channelization, underground blasting, underwater bursting, and channel development. The propellant is the main component of liquid explosives that mainly consist of nitrate , perchlorates, hydrazines, or hydrogen peroxide. To understand the basic properties of these materials is important to optimize the performances of liquid energetic materials, including energy levels, combustion behavior, detonation characteristics, stability, processing characteris- tics, service characteristics, and prolonging storage period. The materials to prepare liquid explosives are well known. Thus, by using the information of technique process, the formulation of liquid explosives can be precisely adjusted to achieve optimized explosion strength and performance. Further improvement of charging conditions and application range would maximize the energy of liquid explosives. The book is organized into seven chapters. The first chapter, Introduction, contains the concept of liquid and its development direction. In Chap. 2, the detonation mechanism of liquid explosive is reviewed. The liquid explosive exhibits the essential property of explosives. However, its detonation characteristics are different from the common explosives. The general detonation theory cannot

v vi Preface completely explain the detonation behaviors and characteristics of liquid explo- sives, such as under-compressed detonation. In an infinite free space, the short- distance over-compression of explosion for liquid explosives is not as high as condensed explosives, but the pulse width of its shock wave is much larger than condensed explosives. The positive pressure lasts a long time, thus the total cor- responding work is high. Particularly in a semi-closed room, accompanied by the release of large amounts of gas, oxygen surrounding the explosion is involved in the detonation reaction, so-called as oxygen uptake characteristic, which is not observed for common condensed explosives. It is intended to guide researchers to gain primary understanding on the detonation characteristics of liquid explosive, so as to provide supports to applications of liquid explosives. In Chap. 3, the for- mulating of liquid explosive recipe is presented and the relationship among energy, detonation parameters, and performance of liquid explosives with different struc- tures is systematically discussed. Chapters 4–6 contain the property and preparation technology of typical liquid explosives of nitroalkanes, nitrate , and azides. New findings in liquid explosives in our work have been addressed based on previous work. For example, the issue that nitroglycerine is sensitive to be exploded even under a slight shake has been solved using modern technology. We also improved the preparation technology of nitrate esters to implement pollution- free green process of nitrification. Great amounts of azide energetic materials, developed in the past decade, have come to light for the first time in this book. Chapter 7 contains seven types of liquid explosive mixtures and their composition, property, preparation process, and performance. Besides the author’s achievements, the book also contains the scientific views and theoretical knowledge for the research and development of liquid explosives over the world. The main aims of the book are to review the current status of liquid explosive research and development, to provide instruction for studying liquid explosives, and to enlighten researchers of energetic materials. Through reviewing the current application level of liquid explosives, the book, basically, has been designed to address the needs of scientists, researchers, and engineers, who are interested in the composition, preparation, property, application, and performance of energetic materials. The author is grateful to Ms. Wenxia Qi for her long-standing assistance in preparing and editing the manuscript, and to the editors at Springer Link for their exceptional patience and efforts. Any suggestions to the book on both academic and expression grounds are welcome, due to the limitations of the author.

Beijing, China, August 2014 Jiping Liu Contents

1 Introduction...... 1 1.1 Liquid Explosives ...... 1 1.2 Composition and Classification of Liquid Explosives ...... 4 1.3 Raw Materials and Formulation of Liquid Explosives...... 4 1.3.1 Oxidizers ...... 5 1.3.2 Combustible Agents...... 8 1.3.3 Additives ...... 9 1.4 Applications of Liquid Explosives ...... 10 1.4.1 Mining and Industrial Applications ...... 10 1.4.2 Military Applications ...... 13 References ...... 14

2 Explosion Features of Liquid Explosive Materials ...... 17 2.1 Explosion Phenomena and Key Factors of Liquid Explosive Materials ...... 17 2.1.1 Heat/Energy Releasing of Liquid Explosive Explosion . . . 18 2.1.2 Rapid Reaction of Liquid Explosive Materials ...... 19 2.1.3 Gas Products in Explosion of Liquid Explosives ...... 20 2.2 The Explosion Changing of Liquid Explosive Materials ...... 21 2.2.1 Combustion of Liquid Explosives ...... 22 2.2.2 Detonation of Liquid Explosives ...... 33 2.3 Explosion Work Ability of Liquid Explosives ...... 48 2.3.1 Work Capacity of Liquid Explosives ...... 48 2.3.2 Improving the Work Ability of Explosives ...... 57 2.3.3 Brisance of Liquid Explosives...... 58 2.4 Explosion Impact of Liquid Explosives...... 65 2.4.1 Explosion Impact of Liquid Explosives in Free Space . . . 65 2.4.2 Explosion of Liquid Explosives on the Ground ...... 82 2.4.3 Explosion of Liquid Explosives in Semienclosed Space...... 88 2.4.4 Explosion Effect of Liquid Explosives Under Water . . . . 97

vii viii Contents

2.5 Toxic Gas Production of Liquid Explosives in Explosion ...... 100 2.5.1 Toxicity of Liquid Explosives...... 100 2.5.2 Toxicity from Explosions of Liquid Explosives...... 100 2.5.3 Countermeasures to Reduce the Toxicity of Liquid Explosive...... 103 References ...... 103

3 Formulation Design of Liquid Explosives ...... 105 3.1 Effect of Oxygen Balance on the Explosive Properties and Design Calculation of the Formulation ...... 105 3.1.1 Design of Oxygen Balance ...... 105 3.1.2 Influence of Oxygen Balance on Explosive Properties . . . 108 3.1.3 Design and Calculation of Liquid Explosive Recipe. . . . . 111 3.2 Design of Explosion Property ...... 112 3.2.1 Design Calculation of Properties and Their Factor Relationship of Liquid Explosive...... 113 3.2.2 Explosion Formation Heat of Explosive ...... 122 3.2.3 Design of Explosion Temperature of Explosive ...... 127 3.2.4 Comprehensive Parametric Design of Liquid Explosives ...... 134 3.3 Design on the Uniformity and Stability of Liquid Explosives . . . 136 3.3.1 Solution-Type Liquid Explosives...... 136 3.3.2 Liquid Explosives with Small Solid Particles ...... 137 References ...... 138

4 Liquid Nitro Explosives ...... 139 4.1 Introduction...... 139 4.2 Properties of Liquid Nitro Explosives ...... 140 4.2.1 Physical Properties of Liquid Nitro Compounds ...... 140 4.2.2 Chemical Properties of Liquid Nitro Compounds...... 142 4.2.3 Explosion Properties of Liquid Nitro Compounds ...... 147 4.3 Liquid Aliphatic Nitro Compounds ...... 147 4.3.1 Properties and Preparation of ...... 147 4.3.2 Properties and Preparation of Dinitromethane ...... 154 4.3.3 Properties and Preparation of Trinitromethane ...... 156 4.3.4 Properties and Preparation of Tetranitromethane ...... 157 4.3.5 Properties of Nitroethane ...... 159 4.3.6 Properties of 1,1-Dinitropropane ...... 160 4.3.7 Properties of 1,3-Dinitropropane ...... 161 4.3.8 Properties of 2-Methyl-2-Nitropropane ...... 162 4.3.9 Properties of 1-Nitrobutane...... 162 4.4 Liquid Nitro Explosives with Heteroatoms ...... 163 4.4.1 Properties of Fluorodinitromethane ...... 163 4.4.2 Properties of Fluorotrinitromethane ...... 164 Contents ix

4.5 Nitroalcohol ...... 164 4.5.1 Properties and Preparation of 2,2-Dinitropropanol ...... 165 4.5.2 Properties of 2-Nitroethanol ...... 173 4.5.3 Properties of 2-Nitro-1-Propanol ...... 174 4.5.4 Properties of 2-Methyl-2-Nitro-1-Propanol ...... 174 4.6 Liquid Nitro Aromatic Compounds ...... 175 4.6.1 Properties and Preparation of Nitrobenzene...... 175 4.6.2 Properties of o-Nitrotoluene ...... 176 4.6.3 Properties and Preparation of 3-Nitrotoluene ...... 177 References ...... 177

5 Preparation and Properties of Liquid Nitrate Ester ...... 181 5.1 Characteristics of Nitrate Esters ...... 181 5.1.1 Structure of Nitrate Esters ...... 181 5.1.2 Physical Properties of Nitrate Esters ...... 182 5.1.3 Hydrolysis of Nitrate Esters ...... 187 5.1.4 Reduction of Nitrate Esters...... 191 5.1.5 Other Reactions of Nitrate Esters...... 192 5.1.6 Chemical Stability of Nitrate Esters ...... 192 5.2 Properties and Preparation of Monohydric Alcohol Nitrate . . . . . 193 5.2.1 Properties and Preparation of Methyl Nitrate...... 193 5.2.2 Property and Preparation of ...... 199 5.2.3 Property and Preparation of n-Propyl Nitrate...... 201 5.2.4 Property and Preparation of Isopropyl Nitrate ...... 203 5.2.5 Property and Preparation of n-Butyl Nitrate ...... 206 5.2.6 Property and Preparation of n-Amyl Nitrate ...... 208 5.2.7 Property and Preparation of Chlorinated Glycerol Nitrate ...... 209 5.2.8 Property and Preparation of Glycerol Nitrate...... 210 5.2.9 Property and Preparation of Glycidyl Nitrate...... 211 5.2.10 Property and Preparation of Dichloroglycerol Nitrate ...... 211 5.3 Property and Preparation of Dibasic Alcohol Nitrates ...... 212 5.3.1 Property and Preparation of Glycol Dinitrate...... 212 5.3.2 Property and Preparation of Diethylene Glycol Dinitrate ...... 216 5.3.3 Property and Preparation of Triethylene Glycol Dinitrate ...... 221 5.3.4 Property and Preparation of Glycerine Dinitrate...... 223 5.3.5 Other Dibasic Alcohol Nitrates ...... 227 5.4 Property and Preparation of Trinitrate Esters ...... 235 5.4.1 Property and Preparation of Nitroglycerine ...... 235 x Contents

5.4.2 Property and Preparation of Nitro Isobutyl Glycerine Trinitrate ...... 251 5.4.3 Property and Preparation of Pentaerythritol Trinitrate . . . . 258 5.4.4 Property and Preparation 1,2,4-Butanetriol Trinitrate . . . . 260 5.5 Property and Preparation of Other Nitrate Esters ...... 262 5.5.1 Property and Preparation D-Sorbitol Hexanitrate ...... 262 5.5.2 Property and Preparation of Polyethenol Nitrate ...... 263 5.5.3 Property and Preparation of Diglycerine Tetranitrate . . . . 263 References ...... 265

6 Azido Liquid Explosives ...... 269 6.1 Properties and Application of Azido Liquid Compounds...... 269 6.1.1 Properties of Azido Compounds ...... 269 6.1.2 Application of Azido Compound Liquids ...... 271 6.2 Properties and Preparation of Azidoalkane ...... 277 6.2.1 Properties and Preparation of Azidomethane ...... 277 6.2.2 Azidoethane ...... 278 6.2.3 Diazidoethane ...... 278 6.2.4 Azidopropane ...... 279 6.2.5 Properties and Preparation of 1,3-Diazidopropane (DANG)...... 279 6.2.6 1,5-Diazido-3-Nitraza Pentane...... 284 6.2.7 Triazidomethane ...... 285 6.2.8 3,3-Bis(Azidomethyl)Oxetane ...... 286 6.2.9 3-Azidomethyl-3-Methyloxetane ...... 286 6.3 Azidoalcohol and Azidoesther ...... 287 6.3.1 2-Azidoethanol ...... 287 6.3.2 Glycerol Triazidoacetate...... 287 6.3.3 Pentaerythritol Tetrakis ...... 288 6.4 Azidonitrate Ester ...... 288 6.4.1 Properties and Preparation of Pentaerylthritol Diazido Dinitrate...... 288 6.4.2 Properties and Preparation of 1,3-Diazido-2-Nitryloxypropane ...... 291 References ...... 294

7 Liquid Explosive Mixtures ...... 297 7.1 Nitro Liquid Explosive Mixtures ...... 299 7.1.1 Nitromethane-Based Liquid Explosives ...... 299 7.1.2 Tetranitromethane-Based Liquid Explosives ...... 310 7.2 Nitrate-Based Liquid Explosives ...... 311 7.2.1 Characteristics of Nitrate-Based Liquid Explosives . . . . . 311 7.2.2 Detonation Velocity of Nitrate-Based Liquid Explosives ...... 313 Contents xi

7.3 Nitrate Nitrogen Oxide Based Liquid Explosives ...... 316 7.3.1 Liquid Explosives...... 316 7.3.2 Liquid Explosives Based on Nitrogen Dioxide ...... 329 7.4 Hydrazine Liquid Explosives...... 330 7.4.1 Hydrazine Liquid Explosives Contain Nitric Acid ...... 330 7.4.2 Hydrazine Nitrate Liquid Explosives Containing Hydrazine Hydrate and Aliphatic Amine ...... 335 7.5 Perchloric Acid Urea Liquid Explosive...... 337 7.6 Liquid Explosives with Hydrogen Peroxide...... 339 7.6.1 Properties of Hydrogen Peroxide Containing Liquid Explosives ...... 339 7.6.2 Explosion Properties of H2O2 and Its Mixtures ...... 341 7.6.3 Toxicity and Control Measure for H2O2 Liquid Explosives ...... 343 References ...... 343