Liquid Nitro Explosives

354 Pages·2014·11.75 MB·English

Jiping Liu
Liquid
Explosives
Liquid Explosives
Jiping Liu
Liquid Explosives
123
Jiping Liu
College ofMaterials Science
andEngineering
Beijing InstituteofTechnology
Beijing
China
ISBN 978-3-662-45846-4 ISBN 978-3-662-45847-1 (eBook)
DOI 10.1007/978-3-662-45847-1
LibraryofCongressControlNumber:2014957400
SpringerHeidelbergNewYorkDordrechtLondon
©Springer-VerlagBerlinHeidelberg2015
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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
explosivesarenotinfluencedbygeographicalconditions,localtopographicfeature,
and land features. Thus, the application range of liquid explosives is considerably
wide.
Thefirstwordthatpopsupinthemindwouldbewar,ornational-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,mineralexploration,channelization,undergroundblasting,underwater
bursting,andchanneldevelopment.Thepropellantisthemaincomponentofliquid
explosivesthatmainlyconsistofnitrateester,perchlorates,hydrazines,orhydrogen
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,servicecharacteristics,andprolongingstorageperiod.Thematerialstoprepare
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,
containstheconceptofliquidexplosiveanditsdevelopmentdirection.InChap.2,
the detonation mechanism of liquid explosive is reviewed. The liquid explosive
exhibitstheessentialpropertyofexplosives.However,itsdetonationcharacteristics
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
gainprimaryunderstandingonthedetonationcharacteristicsofliquidexplosive,so
as to provide supports to applications of liquid explosives. In Chap. 3, the for-
mulatingofliquidexplosiverecipeispresentedandtherelationshipamongenergy,
detonation parameters, and performance of liquid explosives with different struc-
turesissystematicallydiscussed.Chapters4–6containthepropertyandpreparation
technology of typical liquid explosives of nitroalkanes, nitrate esters, and azides.
New findings in nitrate ester liquid explosives in our work have been addressed
basedonpreviouswork.Forexample,theissuethatnitroglycerineissensitivetobe
explodedevenunderaslight shake hasbeensolvedusingmoderntechnology. 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.
Chapter7containsseventypesofliquidexplosivemixturesandtheircomposition,
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
overtheworld.Themainaimsofthebookaretoreviewthecurrentstatusofliquid
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 Nitromethane . . . . . . . . . . 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 Ethyl Nitrate. . . . . . . . . . . . 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