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- Herausgeber: Wiley-VCH
- Kategorie: Fachliteratur
- Sprache: Englisch
- Veröffentlichungsjahr: 2015
Authored by an insider with over 40 years of High Energy Materials (HEMs) experience in academia, industry and defense organizations, this handbook and ready reference covers all important HEMs from the 1950s to the present with their respective properties and intended purposes. Written at an attainable level for professionals, engineers and technicians alike, the book provides a comprehensive view of the current status and suggests further directions for research and development. An introductory chapter on the chemical and thermodynamic basics allows the reader to become acquainted with the fundamental features of explosives, before moving on to the important safety aspects in processing, handling, transportation and storage of High Energy Materials. With its collation of results and formulation strategies hitherto scattered in the literature, this should be on the shelf of every HEM researcher and developer.
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Table of Contents
Cover
Series page
Title
Copyright
Dedication
Foreword
Preface
Acknowledgments
Abbreviations
1 Salient Features of Explosives
1.1 Introduction
1.2 Definition
1.3 Classification
1.4 Fundamental Features
1.5 Additional Requirements for Military Explosives
1.6 Applications of Explosives
References
2 Status of Explosives
2.1 Historical Aspects
2.2 Status of Current and Future Explosives
2.3 Future Scope for Research
References
3 Processing and Assessment Techniques for Explosives
3.1 Processing Techniques for Explosives
3.2 Formulation Fundamentals
3.3 Assessment of Explosives
References
4 Propellants
4.1 Classification of Propellants
4.2 Liquid Propellants
4.3 Solid Propellants
4.4 Hybrid Propellants
4.5 Thixotropic Propellants
4.6 Performance of Propellants
4.7 Formulation of Gun Propellants
4.8 Ingredients of Gun Propellants
4.9 Ingredients of Solid Rocket Propellants
4.10 Inhibition of Rocket Propellants
4.11 Insulation of Rocket Motors
References
5 Pyrotechnics
5.1 Introduction
5.2 General Features of Pyrotechnics
5.3 Ingredients of Pyrotechnic Formulations
5.4 Important Characteristics of Ingredients for Pyrotechnic Formulations
5.5 Types of Pyrotechnic Formulations
5.6 Performance Assessment of Pyrotechnic Formulations
5.7 Life of Ammunition with Pyrotechnic Devices
5.8 Nanomaterials: Various Aspects and Use in HEM Formulations
5.9 Recent and Future Trends in Pyrotechnics
References
6 Explosive and Chemical Safety
6.1 Safety
6.2 Explosive Safety
6.3 Fire Safety
6.4 Safety Aspects for Transportation of Explosives and Ammunition
6.5 Safety Aspects for Storage of Explosives and Ammunition
6.6 Safety Aspects for Handling of Explosives and Ammunition
6.7 Static Electricity Hazards
6.8 Extremely Insensitive Detonating Substances and Ammunition
6.9 Hazard and Risk Analysis
6.10 Chemical Safety
6.11 Prevention and Elimination of Explosions, Accidents and Fires
References
Index
End User License Agreement
List of Tables
1 Salient Features of Explosives
Table 1.1 Some characteristics of high explosives, low explosives (propellants) and pyrotechnics.
Table 1.2 Oxygen balance of some primary, secondary and tertiary explosives.
Table 1.3 Impact sensitivity of some primary, secondary and tertiary explosives.
Table 1.4 Impact sensitivity and oxidant balance (OB
100
) of some explosives.
Table 1.5 ‘Heats of formation’ of some primary, secondary and tertiary explosives.
Table 1.6 Calculated ‘heats of explosion’ for some primary, secondary and tertiary explosives (considering water as a gas).
Table 1.7 Power index values of some primary and secondary explosives (standard – picric acid).
Table 1.8 General characteristics of ISRO’s different satellite launch vehicles.
Table 1.9 Explosive and binder ingredients used in nuclear weapons.
Table 1.10 Explosive formulations and PBXs used in nuclear weapons.
2 Status of Explosives
Table 2.1 Some salient properties of various types of nitrocellulose.
Table 2.2 Most promising thermally stable explosives and their properties.
Table 2.3 Some important properties of P ic and N if analogs.
Table 2.4 Important properties of some newly reported explosives.
Table 2.5 Some TATB/HMX Based PBX s and their properties.
Table 2.6 TATB based PBXs with different binders and their properties.
Table 2.7 Comparison of calculated performance of CL-20 and HMX based explosives.
Table 2.8 Some formulations and their performance data
a
.
Table 2.9 Some properties of pressed explosives with 92.5% HMX, HMX/TATB and HMX/NTO (Kel-F binder 7% and graphite 0.5%).
Table 2.10 Some properties of composite explosives with 80.6 % HMX, HMX/NTO and HMX/TATB.
Table 2.11 Characteristics of some EIDS s and their responses to UN Series-7 tests.
Table 2.12 Comparative properties of SLA and BLA.
Table 2.13 Sensitivity data for BLASA and ASA compositions.
Table 2.14 Some important properties of BNCP.
Table 2.15 Estimated properties of some well-known explosives vis-à-vis ONC.
Table 2.16 Various properties of AAT, TAGAT and GAT.
3 Processing and Assessment Techniques for Explosives
Table 3.1 Various processing techniques for filling of warheads.
Table 3.2 Some typical HE formulations and their performance parameters.
Table 3.3 Some aluminized explosive formulations and their density and ‘velocity of detonation’.
Table 3.4. Some PBX formulatios and their important properties.
Table 3.5 Various thermoanalytical techniques for thermal analysis
Table 3.6 Thermal data of some explosives.
a
4 Propellants
Table 4.1 Important characteristics of solid gun propellants
Table 4.2 Formulations and properties of some liquid monopropellants.
Table 4.3 Formulations and properties of some liquid monopropellants.
Table 4.4 Some physical, thermal and explosive properties of ADN.
Table 4.5 Typical properties of castor oil.
Table 4.6a Some physical properties of energetic polymeric binders.
Table 4.6b Some thermal and explosive properties of energetic binders for explosives and propellants.
Table 4.7a Some inert/non-energetic plasticizers for explosive and propellant formulations.
Table 4.7b Some energetic plasticizers for explosive and propellant formulations.
Table 4.8 Some stabilizers for single-base, double-base and triple-base propellants.
Table 4.9 Some commercially available anti-oxidants for composite propellants.
Table 4.10 Burn-rate modifiers for double-base rocket propellants.
Table 4.11 Less toxic or non-toxic burn-rate modifiers for DB rocket propellants.
Table 4.12 Specification of butacene 800 prepolymer (SNPE France).
Table 4.13 Effect of iron oxide and butacene 800 on burn rate of composite propellants.
Table 4.14 Burn-rate modifiers for composite propellants.
Table 4.15 Various properties of TEG-based polyester resin.
Table 4.16 Effect of methods of polyesterification on some DEG-based NUPs.
5 Pyrotechnics
Table 5.1 Pyrotechnics: special effects, nomenclature/devices and applications
Table 5.2 Some common fuels and their properties
a
Table 5.3 Some common oxidizers and their properties
a
.
Table 5.4 Some common organic and polymeric additives and their properties
a
.
Table 5.5 Ignition temperatures of some pyrotechnic formulations.
Table 5.6 Salient features of some infrared flares/decoy flares.
Table 5.7 Properties of some commercial polysulfide liquid polymers.
Table 5.8 Classification of delay formulations and their applications.
Table 5.9 Properties of allotropes of phosphorus.
Table 5.10 Comparison of phosphine formation of various grades of red phosphorus (at 25°C and 65% humidity).
Table 5.11 Comparison of different incendiary systems.
Table 5.12 Environmental tests for pyrotechnic stores.
6 Explosive and Chemical Safety
Table 6.1 UN Scheme of Classification of Explosives (Combination of Hazard Division and Compatibility Group).
Table 6.2 UN test series–7 for hazard class/division 1.6 articles.
List of Illustrations
1 Salient Features of Explosives
Figure 1.1 (a) Classification of explosives (according to their end-use). (b) Classification of explosives (according to nature of explosive/ingredient).
Figure 1.2 Detonation vs. burning for high and low explosives.
Figure 1.3 Parallel and angular plate welding set-ups.
Figure 1.4 Main components of a solid rocket.
Figure 1.5 Main components of a liquid rocket (without storage tanks for fuel and oxidizer).
Figure 1.6 Various satellite launch vehicles of ISRO.
2 Status of Explosives
Figure 2.1 Structures of mono, di and tri amino derivatives of trinitrobenzene (TNB).
Figure 2.2 Structures of TPM or 2,4,6-tris(picrylamino)-1,3,5-triazine series of explosives.
Figure 2.3 Structures of some newly reported explosives.
Figure 2.4 Some high nitrogen content-high energy materials (HNC-HEMs).
Figure 2.5 Structures of AAT, GAT and TAGAT.
Figure 2.6 Structures of some nitroguanyl tetrazines.
3 Processing and Assessment Techniques for Explosives
Figure 3.1 Incremental pressing technique. Based on Reference [3].
Figure 3.2 Hydrostatic pressing technique. Based on Reference [3].
Figure 3.3 Isostatic pressing technique. Based on Reference [3].
Figure 3.4 Apparatus for determining explosion delay and explosion temperature.
Figure 3.5 Schematic of a DTA apparatus.
Figure 3.6 A typical DTA curve (thermogram).
Figure 3.7 Schematic of TG apparatus.
Figure 3.8 A typical TG curve.
Figure 3.9 Schematic of DSC sample holder assembly and instrument.
Figure 3.10 DSC curve of indium metal (standard).
Figure 3.11 BoM impact apparatus. Reprinted from Kohler, J., and Meyer, R. (1993)
Explosives,
4th edn, © 1993, Wiley-VCH Verlag GmbH, Weinheim, Germany.
Figure 3.12 Transparent anvil drop weight apparatus. Reprinted with permission from Field, J.E., Swallowe, G.M., Palmer, S.J.P., Pope, P.H., and Sundarajan, R. (1985) Proc. 8th Symp. (Intl) on Detonation; © 1985, Naval Surface Warfare Center, USA.
Figure 3.13 Instrumented drop weight apparatus. Reprinted with permission from Field, J.E., Swallowe, G.M., Palmer, S.J.P., Pope, P.H., and Sundarajan, R. (1985) Proc. 8th Symp. (Intl) on Detonation; © 1985, Naval Surface Warfare Center, USA
Figure 3.14 Porcelain pestle and plate assembly (BAM friction apparatus).
Figure 3.15 Schematic of electrostatic discharge set-up.
Figure 3.16 Schematic of the detonation process. Reprinted with permission from Suceska, M. (1995)
Test Methods for Explosives,
Ch. 2, © 1995, Springer-Verlag, New York, USA.
Figure 3.17 Set-up for VOD Determination by pin oscillographic technique (POT).
Figure 3.18 Different types of probes.
Figure 3.19 A typical oscillogram for determination of detonation velocity.
Figure 3.20 Dautriche method for determination of detonation velocity. Reprinted from Kohler, J., and Meyer, R. (1993)
Explosives,
4th edn, © 1993, Wiley-VCH Verlag GmbH, Weinheim, Germany.
Figure 3.21 Trauzl/lead block test. Reprinted from Meyer, R.
Explosives,
1987; © 1987, Wiley-VCH Verlag GmbH, Weinheim, Germany.
4 Propellants
Figure 4.1 Classification of propellants in terms of their applications.
Figure 4.2 Classification of propellants based on their physical state.
Figure 4.3 Classification of propellants based on their nature.
Figure 4.4 A Typical hybrid rocket motor.
Figure 4.5 Graphical presentation of burning characteristics of propellants. X-Uncatalysed Propellant and Y-Catalysed Propellant A-B: Super Burn-rate; B-C: Plateau Region; C-D: Mesa Region; and D-E: Post-Plateau Region.
Figure 4.6 Some typical shapes of gun propellants. Reprinted with permission from J. Akhavan,
The Chemistry of Explosives,
2004; © 2004, The Royal Society of Chemistry, UK.
Figure 4.7 Structures of some aliphatic and aromatic polyisocyanates.
Figure 4.8 Prepolymer route for polyurethane elastomer preparation.
Figure 4.9 One-shot process for polyurethane elastomer preparation.
Figure 4.10 Ferrocene derivatives and their important characteristics.
Figure 4.11 Inhibition modes with corresponding pressure-time profiles.
Figure 4.12 Model pressure-time profiles for sustainer propellants at different temperatures. [A: Ambient (+27°C); B: Hot (+50°C) and C: Cold (−40°C)].
Figure 4.13 Assembly for fabrication of inhibitor sleeve.
Figure 4.14 Schematic of a cartridge-loaded/free-standing propellant. Reprinted from G.P.Sutton,
Rocket Propulsion Elements: An Introduction to the Engineering of Rockets,
1992; © 1992, John Wiley and Sons, Chichester, UK.
Figure 4.15 Cured epoxy and phenolic resins.
Figure 4.16 (A) Model structures of crosslinked NUP (I) and NUP(II). (B) Model structure of crosslinked NUP(III).
Figure 4.17 Schematic of a case-bonded propellant. Reprinted from G.P.Sutton,
Rocket Propulsion Elements: An Introduction to the Engineering of Rockets,
1992; © 1992, John Wiley and Sons, Chichester, UK.
5 Pyrotechnics
Figure 5.1 Variation of light output vs diameter. Reprinted with permission from D.R. Dillehay,
J. Pyrotech.,
(19) (Summer 2004) 1–9; © 2004, J. Pyrotechnics Inc, USA.
Figure 5.2 Variation of IBR against fuel.
Figure 5.3 Electromagnetic spectrum.
Figure 5.4 Worldwide applications tree of red phosphorus (1999). Reprinted with permission from S. Hoerold and A. Ratcliff,
J. Pyrotech.,
Issue 13 (Summer 2001) 1–8; © 2001, J. Pyrotechnics Inc, USA.
Figure 5.5 Instrumental set-up for measurement of luminosity/IR intensity.
Figure 5.6 Instrumental set-up for measurement of IR absorption by pyrotechnic smokes.
Figure 5.7 General scheme of sol–gel synthesis. Reprinted from A.E. Gash, R.L. Simpson, Y. Babushkin, A.I. Lyamkin, F. Tepper, Y. Biryukov, A. Vorozhtsov and V. Zarko,
‘Energetic Materials’,
U. Teipel (ed.); © 2005, Wiley-VCH, Weinheim, Germany.
6 Explosive and Chemical Safety
Figure 6.1 Think before handling.* Handling of explosives includes–their synthesis, drying, grinding, sieving, testing, destruction, scaling-up and manufacture, coating/treatment, processing, packing, use, collection, offering for sale, transportation and storage etc. Reprinted from M. Defourneaux and P. Kerner, Minutes of the 25th Explosives Safety Seminar, Vol. IV, 1992, p 1; © 1992, Department of Defense Explosives Safety Board, USA.
Figure 6.2 Symbols for transport of dangerous goods by road. Based on the ‘Transport of Dangerous Goods (Recommendations Prepared by the United Nations Committee of Experts on the Transport of Dangerous Goods)’, United Nations, New York, USA, 1956.
Figure 6.3 Fire division symbols for use on explosive buildings and stacks. Reprinted from DRDO’s ‘Storage and Transport of Explosives Committee (STEC)’ Pamphlet No.6, 1995 (As Amended).
Guide
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High Energy Materials
Propellants, Explosives and Pyrotechnics
Jai Prakash Agrawal
The Author
Dr. Jai Prakash Agrawal
C Chem FRSC (UK)
Former Director of Materials
Defence R&D Organization
DRDO Bhawan, New Delhi, India
Sponsored by the Department of Science and Technology under its Utilization of Scientific Expertise of Retired Scientists Scheme
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
ISBN: 978-3-527-32610-5
This book is dedicated to my revered spiritual teacher
His Holiness Sri Sri Ravi Shankar
Founder, Art of Living and
The International Association for Human Values
Foreword
There are several books dealing with explosives, propellants and pyrotechnics, but much of the latest information on High Energy Materials (HEMs) of recent origin is scattered in the literature as research/review papers. This book is the first of its kind in which the knowledge on materials hitherto accumulated over the past 50 years in the literature has been carefully blended with latest developments in advanced materials, and articulated to highlight their potential from the point of view of end-use.
This book contains six chapters. While chapter one of this book introduces the subject in terms of salient/fundamental features of explosives, additional requirements for military explosives and their applications (military, commercial, space, nuclear & others), chapter 2 highlights the status of current and futuristic explosives in the light of their special characteristics. In addition, the future scope of research in this field has also been brought into focus in this chapter.
Chapter 3 essentially covers the important aspects of processing & assessment of explosives & their formulations. The propellants which are extensively used for various military & space applications are described in chapter 4. The major portion of this chapter is devoted to different aspects of high performance & eco-friendly oxidizers (ADN & HNF), novel binders such as butacene, ISRO Polyol and other state-of-the-art energetic binders [GAP, NHTPB; poly (NiMMO), poly (GlyN), etc.], energetic plasticizers (BDNPA/F, Bu-NENA, K-10, etc.) along with other ingredients which are likely to play a crucial role in augmenting the performance of futuristic propellants for various missions. The inhibition of rocket propellants & insulation of rocket motors along with their recent developments are also included in this chapter. Pyrotechnics which form an integral part of explosive and propellant related missions are discussed in chapter 5 whereas Explosive & Chemical safety which is of vital importance to all those working in the area of High Energy Materials (HEMs) is dealt in chapter 6.
Dr. J. P. Agrawal, who is an internationally acknowledged explosive & polymer scientist of repute, is a great writer with a large number of research publications to his credit. His rich experience and the international knowledge in High Energy Materials written in the book are valuable assets for the new generation of High Energy Materials scientists and rocket technologists.
This book is the most comprehensive review of modern High Energy Materials and encompasses their important aspects with special reference to their end-use/applications. The language in the text is very lucid and easy to understand. The readers and researchers will be immensely benefitted by the book.
Dr. A. Sivathanu PillaiDistinguished ScientistCEO & MDBrahmos Aerospace Pvt. Ltd.New Delhi, India
Preface
A new term ‘high energy materials’ (HEMs) was coined by the explosives community for the class of materials known as explosives, propellants and pyrotechnics in order to camouflage research on such materials. In other words, HEMs is a generic term used for this class of materials. HEMs, although generally perceived as the ‘devil’ during war and considered as an ‘evil’ during handling, transportation and storage, have proved to be an ‘angel’ due to their tremendous impact on the economy and industries and their innumerable applications in almost all walks of life. There are several books devoted to explosives, propellants and pyrotechnics but most of these either discuss their science in general or concentrate on some specific topic. Also, none of these books deals with recent developments in detail. While a number of excellent reviews have been published to bridge this knowledge gap, there is still no single text available in the literature on the subject, embedded with recent advances and future trends in the field of HEMs. This book, entitled ‘High Energy Materials: Propellants, Explosives and Pyrotechnics’ is a text which covers the entire spectrum of HEMs, including their current status, in a single volume and its objective is to fill this gap in the literature.
The modus operandi of this book is: (i) to provide the current status of HEMs which have been reported in the form of research/review papers during the last 50 years but are scattered in the literature; (ii) to explore the potential of recently reported HEMs for various applications in the light of additional requirements in the present scenario, that is, cost-effectiveness, recyclability and eco-friendliness; (iii) to identify the likely thrust areas for further research in this area. Thus, the information on HEMs reported during the last 50 years but scattered all over the literature, will be readily available to researchers in a single book. Further, the level at which chemistry is pitched in this book is not as high as in many specialized books focused on a particular aspect of HEMs. Readers interested in better understanding and details of nitration chemistry are referred to the book ‘Organic Chemistry of Explosives’ (J.P. Agrawal and R.D. Hodgson) which provides detailed information on various synthetic routes for a wide range of HEMs and the chemistry involved. By including Chapter 1 on ‘Salient Features of Explosives’ and Chapter 6 on ‘Explosive and Chemical Safety’ along with chapters on Explosives, Propellants and Pyrotechnics, this book will certainly be of interest to both professionals and those with little or no background knowledge of the subject.
This book is split into six well-defined chapters: Salient Features of Explosives, Status of Explosives, Processing and Assessment of Explosives, Propellants, Pyrotechnics, and Explosive and Chemical Safety. Further, the book includes an exhaustive bibliography at the end of each chapter (total references cited are more than 1000). It also provides the status of HEMs reported mainly during the last 50 years, including their prospects for military applications in the light of their physical, chemical, thermal and explosive properties. The likely development areas for further research are also highlighted. Accidents, fires and explosions in the explosive and chemical industries may be eliminated or minimized if the safety measures described in this book are implemented.
I hope that this book will be of interest to everyone involved with HEMs irrespective of their background: R&D laboratories, universities and institutes, production agencies, quality assurance agencies, homeland security, forensic laboratories, chemical industries and armed forces (army, navy and air force). This book will also be of immense use to organizations dealing with the production of commercial explosives and allied chemicals.
To sum up, I have endeavored to bring about a refreshing novelty in my approach to the subject while writing this volume and tried my best to include all relevant information on HEMs which could be of interest to military as well as commercial applications. However, it is just possible that a few interesting HEMs or some relevant information might have been overlooked unwittingly, for which I apologize. Readers are requested to inform me or the publisher about such omissions which would be greatly appreciated and included in the next edition of this book.
Dr. Jai Prakash Agrawal
Pune, India
Acknowledgments
During the course of writing this book, I have found the books and reports or reviews given under ‘Further Reading’ very interesting and invaluable. The writing of this book would have been difficult if it had not been for the text of these books and reports or reviews by pioneers of HEMs. I wish to express my sincere thanks to the authors and publishers of the books, reports and reviews listed under the heading ‘Further Reading’ at the end of this section.
The Department of Science and Technology (DST), Government of India sponsored a project to me under Utilization of Scientific Expertise of Retired Scientists Scheme to write this book, for which I am grateful to them. I would like to thank Dr. A. Subhananda Rao, Director, HEMRL for providing the office and library facilities. I acknowledge with thanks the help and support provided by all officers and staff of the Technical Information Resource Center, HEMRL during the entire period of this project. I also thank Dr. A.L. Moorthy, Director, Defence Scientific Information and Documentation Centre (DESIDOC), Delhi and his colleagues for providing library support.
I am grateful to Mr. K. Venkatesan, Ex-Joint Director, HEMRL and my personal friend for over three decades for his meticulous perusal of the manuscript and valuable contributions to improving its quality. The HEMRL scientists and my former colleagues have helped me in the preparation of this book by providing scientific information for which I am thankful to them: Dr. Mehilal, Dr. R.S. Satpute, Dr. A.K. Sikder, Mr. G.M. Gore, Dr. D.B. Sarwade, Dr. K.S. Kulkarni, Ms. Florence Manuel, Ms. Jaya Nair, Mr. R.S. Palaiah, Dr. G.K. Gautam, Mr. H.P. Sonawane and Ms. S.H. Sonawane, Mr. B.R. Thakur, Mr. J.R. Peshwe, Dr. B.M. Bohra, Mr. S.G. Sundaram, Mr. P.V. Kamat, Dr. R.G.Sarawadekar, Mr. U.S. Pandit, Mr. S.R. Vadali, Mr. C.K. Ghatak, Mr. N.L. Varyani and Dr. A.R. Kulkarni. My thanks are also due to Ms. S.S. Dahitule for typing, Mr. Bhalerao for the artwork and Mr. K.K. Chakravarty, Ms. Ratna Pilankar, Ms. Rashmi Thakur and Mr. P.M. Mhaske for providing miscellaneous support.
Mr. J.C. Kapoor, Director and Dr. S.C. Agarwal, Joint Director, CFEES, Delhi were kind enough to provide literature on safety for which I am thankful to them. Dr. Ross W. Millar, QinetiQ Ltd., Ministry of Defence, UK and Dr. Niklas Wingborg, Swedish Defence Research Agency deserve my special thanks and appreciation for providing a lot of information on energetic binders and oxidizers respectively, followed by technical discussions. The support in terms of providing literature on SFIO by Dr. B.M. Kosowski, MACH I, USA and Butacene 800 by Dr. B. Finck, SNPE, France is also acknowledged with thanks. I thank Mr. M.C. Uttam, Ex.-Dy. Director, VSSC for providing some details about space applications of explosives. I would also like to thank Professor J.E. Field, Dr. S.M. Walley, University of Cambridge, UK, Dr. R.D. Hodgson, Health and Safety Laboratory, UK, Mr. M. Anbunathan, Ex-Chief Controller of Explosives, Nagpur, Dr. S.M. Mannan, Controller of Explosives and Dr. R.P. Singh, Scientist, NCL for providing valuable information and support from time to time.
The author is also grateful to the following copyright owners for their kind permission to reproduce tables and figures from their publications: The Royal Society of Chemistry, J. Pyrotechnics Inc., IPSUSA Seminars Inc., Pergamon Press (now part of Elsevier Ltd.), Springer Science and Business Media, American Defense Preparedness Association, Fraunhofer ICT, Wiley-VCH and United Nations.
A project of this magnitude would not have been accomplished without the unconditional support, encouragement and love of my wife Sushma. This book would not have seen the light of the day in the absence of her untiring help for which I wish to express my profound appreciation. Also, I would like to thank my daughter Sumita, son-in-law Vipul and son Puneet for their understanding and patience throughout the course of writing this book.
Finally my thanks are due to Dr. Martin Preuss, Commissioning Editor (Materials Science), Dr. Martin Graf and their colleagues at Wiley-VCH, Weinheim, Germany for their support and valuable suggestions from time to time.
Dr. Jai Prakash Agrawal
Pune, India
Further Reading
1 Fordham, S. (1966) High Explosives and Propellants, Pergamon Press, Oxford, UK.
2 Suceska, M. (1995) Test Methodsfor Explosives, Springer-Verlag, New York, USA.
3 Kohler, J., and Meyer, R. (1993) Explosives, Wiley-VCH Verlag GmbH, Weinheim, Germany.
4 Sutton, G.P. (1992) Rocket Propulsion Elements: An Introduction to the Engineering of Rockets, John Wiley & Sons, Inc., New York, USA.
5 Bailey, A., and Murray, S.G. (1989) Explosives, Propellants and Pyrotechnics, Land Warfare: Brassey’s New Battlefield Weapons Systems and Technology Series, (eds F. Hartley and R.G. Lee), vol. 2, Brassey’s (UK) Ltd, London, UK.
6 Agrawal, J.P., and Hodgson, R.D. (2007) Organic Chemistry of Explosives, John Wiley & Sons, Ltd, Chichester, UK.
7 Akhavan, J. (2004) The Chemistry of Explosives, The Royal Society of Chemistry, Cambridge, UK.
8 Conkling, J.A. (1985) Chemistry of Pyrotechnics: Basic Principles and Theory, Marcel Dekkar, Inc, New York, USA.
9 Provatas, A. (2000) Energetic polymers and plasticizers for explosive formulations: a review of recent advances. AAMRL Report No. DSTO-TR-0966.
10 Agrawal, J.P. (1998) Recent trends in high energy materials. Prog. Energy Combust. Sci., 24, 1–30.
11 Agrawal, J.P. (2005) Some new high energy materials and their formulations for specialized applications. Prop., Explos., Pyrotech., 30, 316–328.
Abbreviations
AA
Adipic acid
AAT
Ammonium azotetrazolate
ADN
Ammonium dinitramide
ADNBF
7-Amino-4,6-dinitrobenzofuroxan
ADPA
American Defense Preparedness Association (now part of National Defense Industrial Association)
AFX
Air force explosive
AIAA
American Institute of Aeronautics and Astronautics
AMCOM
(US Army) Aviation Missile Command
AMM
Activated monomer mechanism
AMMO
3-Azidomethyl-3-methyloxetane
AN
Ammonium nitrate
ANFO
Ammonium nitrate – Fuel oil
ANTA
3-Amino-5-nitro-1,2,4-triazole (French abbreviation ANT)
AP
Ammonium perchlorate
APC
Ammunition protective coating
APP
Aerospace propulsion products
ARC
Atlantic Research Corporation
ARDE
Armament Research & Development Establishment
ARDEC
(US Army) Armament Research & Development and Engineering Center
ARX
Australian research explosive
ASA
Azide-styphnate-aluminum formulation (based on lead azide, lead styphnate & Al powder)
ASLV
Augmented satellite launch vehicle
ASTM
American Society for Testing & Materials
AT
5-Aminotetrazole
A/T
Anti-tank (missile)
ATCP
Aquotetramine cobalt perchlorate
ATEC
Acetyl triethyl citrate
AWRE
Atomic Weapons Research Establishment, UK
BA
Bonding agent
BAEA
Bis (2-azidoethyl) adipate
BAM
Bundesanstalt fur Materialprufung, Germany
BAMO
3,3-Bis (azidomethyl) oxetane
BCEA
Bis(2-chloroethyl) adipate
BCMO
3,3-Bis(chloromethyl) oxetane
BDNPA
Bis (2,2-dinitropropyl) acetal
BDNPF
Bis (2,2-dinitropropyl) formal
BDNPA/F
Bis (2,2-dinitropropyl) acetal/formal
BDO
1,4-Butanediol
B-GAP
Branched-glycidyl azide polymer
BLA
Basic lead azide
BLASA
Basic lead azide-styphnate-aluminum formulation (based on BLA, lead styphnate & Al powder)
BLS
Basic lead salicylate
BNCP
Tetraamine-cis-bis(5-nitro-2H-tetrazolato-N
2
) cobalt perchlorate
BoE
Bureau of Explosives
BoM
Bureau of Mines
BRM
Burn-rate modifier
BS
Bond strength
BSS
British sieve size
BTAs
Bitetrazole amines
BTATNB
1,3-Bis(1,2,4-triazolo-3-amino)-2,4,6-trinitrobenzene
BTDAONAB
N,N
′-Bis(1,2,4-triazol-3-yl)-4,4′-diamino-2,2′,3,3′,5,5′,6,6′-octanitroazobenzene
BTTN
1,2,4-Butanetriol trinitrate
Bu-NENA
Butyl-
N
-(2-nitroxyethyl) nitramine
BX
Booster explosive
CA
Cellulose acetate
CAB
Cellulose acetate butyrate
CAP
Cellulose acetate propionate
CC
Copper chromite
CCCs
Combustible cartridge cases
CE
Composition exploding
CHDI
1,4-Cyclohexyl diisocyanate
CL-20
2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(HNIW)
CMC
Carboxy methylcellulose
CN
ω-chloroacetophenone
CNAD
Conference of National Armament Director
CNSL
Cashew nut shell liquid
CNTs
Carbon nanotubes
CO
Coconut oil or Castor oil
CP
1-(5-Cyanotetrazolato)pentaamine cobalt(III) perchlorate chloropolyester
CPB
Chloropolyester blend
CPM
Chloropolyester based on mixed glycols
CPX-413
UK’s Extremely Insensitive detonating composition (EIDC) based on NTO, HMX, Poly(NIMMO) & K-10 plasticizer
CR
Dibenz(b,f)-1,4-oxazepine
CS
O
-chlorobenzylidene malononitrile
CTCN
Carbonato tetraamine cobalt(III) nitrate
CTPB
Carboxy-terminated polybutadiene
CV
Closed vessel
CVC
Chemical vapor condensation
CVD
Chemical vapor deposition
CVF
Continuously variable filter
DAAT
z
Diamino azobistetrazine
DAC
Defense Ammunition Centre
DADE/DADNE
1,1-Diamino-2,2-dinitroethylene (FOX-7)
DADNBF
5,7-Diamino-4,6-dinitrobenzofuroxan
DADNPO
3,5-Diamino-2,6-dinitropyridine-
N
-oxide
DANPE
1,5-Diazido-3-nitrazapentane
DANTNP
5-Nitro-4,6-bis(5-amino-3-nitro-1H-l,2,4-triazole-l-yl) pyrimidine
DATB
1,3-Diamino-2,4,6-trinitrobenzene
DB
Double-base
DBP
Dibutyl phthalate
DBTDL
Dibutyl tin dilaurate
DC
Direct current
DCBs
Ditch-cum-bunds
DDM
4,4′-Diaminodiphenyl methane
DDNP(Dinol)
Diazo dinitrophenol
DDS
4,4′-Diaminodiphenyl sulfone
DDT
Deflagration-to-detonation transition
DEAPA
Diethyl aminopropylamine
DEG
Diethylene glycol
DEGDN/DEGN
Diethylene glycol dinitrate
DEP
Diethyl phthalate
DERA
Defence Evaluation Research Agency, UK
DHT
z
Dihydrazino tetrazine
DINA
N
-Nitrodiethanolamine dinitrate
DINGU
1,4-dinitroglycoluril
DIPAM
3,3′-Diamino-2,2′,4,4′,6,6′-hexanitrodiphenyl
DLA
Dextrinated lead azide
DMAZ
2-(Dimethylamino) ethyl azide
DMF
Dimethyl formamide
DMSO
Dimethyl sulfoxide
DNAF/DDF
4,4′-Dinitro-3,3′-diazenofuroxan
DNAN
2,4-Dinitroanisole
DNBF
4,4′-Dinitro-3,3′-bifurazan
DNNC
1,3,5,5-Tetranitro hexahydropyrimidine (French abbreviation)
DNP
Dinitropiperazine
DNPA
Dinitropropyl acrylate
DNPOH
2,2-Dinitropropanol
DNT
Dinitrotoluene
DOA
Dioctyl adipate
DoE
Department of Energy
DOP
Dioctyl phthalate
DOS
Dioctyl sebacate
DP/
P
CJ
Detonation pressure
DPA
Diphenyl amine
DPO
2,5-Dipicryl-l,3,4-oxadiazole
DRA
Defence Research Agency, UK
DRDO
Defence Research & Development Organization, India
DREV
Defence Research Establishment Valcartier, Canada
DSC
Differential scanning calorimetry
DTA
Differential thermal analysis Diethylene triamine
DTG
Derivative thermogravimetric analysis
E
Elongation
Ea
Activation energy
EA
Edgewood Arsenal, MD
EBW
Exploding bridge wire
EC
Ethylcellulose
ECH
Epichlorohydrin
E
D
Explosion delay/Induction period
EDC
Explosive development composition
EED
Electro-explosive devices
EEW
Electro-explosion of wire
EFP
Explosively formed projectiles
EGA
Evolved gas analysis
EGBAA
Ethylene glycol bis(azidoacetate)
EGDN
Ethylene glycol dinitrate
EIDC
Extremely insensitive detonating composition
EIDS
Extremely insensitive detonating substance
EIR
Extreme infrared
EMs
Energetic materials
EO
Ethylene oxide
EP
Elastopolyester
EPA
European Production Agency
EPDM
Ethylene-propylene-diene monomer
E-PS
Epoxy resin-liquid polysulfide(blend)
EPX
A nitramine plasticizer
ERA
Explosive reactive armor
ERDE
Explosives Research & Development Establishment
ERDL
Explosives Research & Development Laboratory, India
ERL
Explosives Research Laboratory
ESA
European Space Agency
ESCA
Electron spectroscopy for chemical analysis
ESD
Electrostatic discharge
Estane-5703
Polyurethane binder of B.F. Goodrich Company, USA
ESTC
Explosives Storage & Transport Committee
E
T
Explosion temperature
ETPE
Energetic thermoplastic elastomer
EURENCO
European Energetics Corporation
F
Force constant (in gun propellant)
FAEs
Fuel–air explosives
FCPM
Flexible chloropolyester based on mixed glycols
FIR
Far Infrared
FLSCs
Flexible linear shaped charges
FM
Symbol for titanium tetrachloride (CWA-Chemical Warfare Agent)
FOI
Swedish Defence Research Agency (old Swedish name is FOA)
F of I
Figure of Insensitivity
FOL
Fuels, oils & lubricants
FOX-7
1,1-Diamino-2,2-dinitroethylene(DADE/DADNE) [FOI eXplosive]
FOX-12
N
-Guanylurea dinitramide(GUDN) [FOI eXplosive]
f.p.
Freezing point
FPC-461
Copolymer of vinyl chloride & chlorotrifluoroethene
FR
Fuel-rich(propellant)
FS
US design for smoke-producing liquid mixture of SO
3
and SO
3
HCl(CWA)
FSAPDS
Fin stabilized armor piercing discarding sabot
GAM
Gelatin, azide, molybdenum disulfide
GAP
Glycidyl azide polymer
GAT
Guanidinium azotetrazolate
GlyN
Glycidyl nitrate
GO
Groundnut oil
GP
General purpose
GPC
Gel permeation chromatography
GSLV
Geo-synchronous satellite launch vehicle
GTO
Geo-synchronous transfer orbit
GUDN
N
-Guanylurea dinitramide (FOX-12)
HAAP
Holston Army Ammunition Plant, USA
HAB
Hexakis(azidomethyl) benzene
HAF
High altitude fuel
HAN
Hydroxyl ammonium nitrate
HAT
1,4,5,8,9,12-hexaazatriphenylene
HAZAN
Hazard analysis
HAZOP
Hazards and operability
HBIW
2,4,6,8,10,12-Hexabenzyl-2,4,6,8,10,12-hexaazaisowurtzitane
HBX
High blast explosive (Torpex type explosives)
HCB
Hexachlorobenzene
HCE
Hexachloroethane
HD
Hazard Division
HDT
Heat deflection temperature
HE
High explosive
HEAT
High explosive anti-tank
HEI
High explosive incendiary
HEMs
High energy materials
HEMRL
High Energy Materials Research Laboratory (Ex-ERDL), India
HESH
High explosive squash head
HHTPB
Hydrogenated hydroxy terminated polybutadiene
HMDI/HDI
Hexamethylene diisocyanate
HMX
High melting explosive or Her Majesty’s explosive
HNAB
2,2′,4,4′,6,6′-Hexanitroazobenzene
HNC
Hexanitrocubane
HNC-HEMs
High nitrogen content – high energy materials
HNDPA
Hexanitrodiphenylamine
HNF
Hydrazinium nitroformate
HNIW
2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20)
H-NMR
Hydrogen(proton) nuclear magnetic resonance
HNS
Hexanitrostilbene
HNTCAB
Hexanitrotetrachloroazobenzene
HP
Halopolyester
HpNC
Heptanitrocubane
HTA
A formulation based on HMX, TNT & Al powder
HTD
High temperature decomposition
HTNR
Hydroxy-terminated natural rubber
HTPB
Hydroxy-terminated polybutadiene
HyMMO
3-Hydroxymethyl-3-methyloxetane
Hytrel
Thermoplastic elastomer manufactured by Du Pont,USA
IBR
Inverse burning rate
ICT
Fraunhofer Institut Chemische Technologie, Germany
IDP
Isodecyl pelargonate
IGC
Inert gas condensation
IHEs
Insensitive high explosives
IM
Insensitive munitions
IMADP
Insensitive Munitions Advanced Development Programme
INSAT
Indian National Satellite
IPA
Isophthalic acid
IPDI
Isophorone diisocyanate
IPS
International Pyrotechnic Seminar
IQD
Inside quantity-distance
IR
Infrared
I-RDX
Insensitive (low sensitivity) RDX
IRFNA
Inhibited red fuming nitric acid
IRS
Indian Remote Sensing
ISAT(A)
Intensified Standard Alternating Trials (different temperatures, & relative humidities and time cycles)
ISAT(B)
I
sp
Specific impulse
ISRO
Indian Space Research Organization
J
Joule
JANNAF
Joint Army-Navy-NASA-Air Force
JASSM
Joint air-to-surface stand-off missile
JSG
Joint Services Guide
K-10
Energetic plasticizer, a mixture of 2,4-dinitroethylbenzene and 2,4,6-trinitroethylbenzene (also known as Rowanite 8001)
Kel-F800
Copolymer of vinylidene and hexafluoropropylene or chlorotrifluoroethylene (Trade name of 3M Company)
LA
Lead azide
LANL
Los Alamos National Laboratory
L/D
Length/diameter(ratio)
LGP
Liquid gun propellant
LLNL
Lawrence Livermore National Laboratory
LOVA
Low vulnerability ammunition
LOX
Liquid oxygen
LPRE
Liquid propellant rocket engine
LS
Lead-2,4,6-trinitroresorcinate(Lead styphnate)
LTD
Low temperature decomposition
LTPB
Lactone-terminated polybutadiene
LX-19
CL-20 based formulation analog of LX-14(HMX/Estane) formulation
MAn
Maleic anhydride
MAPI
Mine anti-personnel inflammable
MAPO
Tris[1-(2-methylaziridinyl) phosphine oxide]
MAPP
Mixture of methyl acetylene, propadiene and propane
MATB
Monoamino-2,4,6-trinitrobenzene
MDF
Mild detonating fuse
MDI
4,4 ′-Methylenediphenyl diisocyanate
ME
Military explosive
MEK
Methyl ethyl ketone (peroxide as a catalyst)
Methyl Tris-X
Methyl analog of Tris-X
MF
Mercury fulminate
MIC
Metastable Intermolecular Composites
MIR
Mid infrared
mJ
milliJoule
MK
Marked
MMH
Monomethyl hydrazine
MMW
Millimeter wave
n
Number average molecular weight
MNT
Mercuric-5-nitrotetrazole Mononitrotoluene
m. p.
Melting point
MPD
m
-phenylenediamine
MSIAC
Munitions Safety Information Analysis Center
MTN
Metriol trinitrate
MTV
Magnesium, Teflon, Viton (based decoy flares)
MURAT
Munitions a risques attenues (French)
MV
Muzzle velocity
w
Weight average molecular weight
MW
Multi-walled (carbon nanotubes)
NASA
National Aeronautics and Space Administration, USA
NATO
North Atlantic Treaty Organization
NAWC
Naval Air Warfare Center, USA
NB
Nitramine-base (propellant)
NBC
Nuclear, biological & chemical (warfare)
NC
Nitrocellulose
NDI
1,5-Naphthalene diisocyanate
2-NDPA
2-Nitrodiphenylamine
NENA
Nitroxyethyl nitramine
NEQ
Net explosive quantity
NG
Nitroglycerine
NGB
Nitroglycerine ballistite (ballistite propellant containing high NG)
NHN
Nickel hydrazine nitrate
NHP
Non-halopolyester
NHTPB
Nitrated hydroxy-terminated polybutadiene
Nif
Nitrofurazanyl
NIMIC
NATO Insensitive Munitions Information Center, USA (now MSIAC)
NIR
Near infrared
NMs
Nanomaterials
NMP
1-Methyl-2-pyrrolidinone (
N
-methyl pyrrolidinone)
NMR
Nuclear magnetic resonance
NOL
Naval Ordnance Laboratory, USA
NONA
2,2′,2′′,4,4′,4′′,6,6′,6″-Nonanitroterphenyl
NP
Nitronium perchlorate
NR
Natural rubber
NSWC
Naval Surface Warfare Center, USA
NT
Nitrotetrazole
NTO
3-Nitro-1,2,4-triazol-5-one
NUP
Novel unsaturated polyester
NQ
Nitroguanidine
OAC
Octaazacubane
OB
Oxygen balance
OB
100
Oxidant balance
ONC
Octanitrocubane
ONTA
Oxynitrotriazole
OQD
Outside quantity-distance
PA
Picatinny Arsenal, USA
PADNT
4-Picrylamino-2,6-dinitrotoluene
PAPI
Polyaryl polyisocyanate
PAT
5-Picrylamino-1,2,3,4-tetrazole
PAThX
CL-20 based explosive formulations which are more powerful than the analogous HMX formulations, developed by Picatinny Arsenal, USA
PATO
3-Picrylamino-1,2,4-triazole
PAVA
Pelargonic acid vanillylamide
PAX
Picatinny Arsenal explosive
PB
Polybutadiene
PBAN
Poly(butadiene-acrylic acid-acrylonitrile)
PBNA
N
-Phenyl-β-naphthylamine
PBX
Plastic bonded explosive
P
CJ
Chapman–Jouguet pressure
PDDN
1,2-Propanediol dinitrate
PECH
Poly(epichlorohydrin)
PEG
Polyethylene glycol
PETN
Pentaerythritol tetranitrate
PETRIN
Pentaerythriol trinitrate
PGDN
1,2-Propylene glycol dinitrate
P&I
Process & Instrumentation
PL-1
2,4,6-Tris(3,5-diamino-2′,4′,6′-trinitrophenylamino)-1,3,5-triazine
PNC
Pentanitrocubane
p-NMA
para-nitromethylaniline
PNP
Polynitropolyphenylene
PO
Propylene oxide
PPG
Poly(propylene glycol)
POL
Petrol, oils & lubricants
Poly(AMMO)
Poly(3-azidomethyl-3 methyloxetane)
Poly(BAMO)
Poly[3,3-bis(azidomethyl) oxetane]
Poly(CDN)
Nitrtated cyclodextrin polymers
Poly(GlyN)
Poly(glycidyl nitrate)
Poly(NiMMO)
Poly(3-nitratomethyl-3-methyloxetane)
POT
Pin oscillographic technique(for VOD determination)
PRA
Probabilistic risk assessment
PS
Polysulfide(rubber)
PSAN
Phase stabilized ammonium nitrate
PSLV
Polar Satellite Launch Vehicle
PTFE
Poly(tetrafluoroethylene)
PU
Polyurethane
PVB
Polyvinyl butyral
PVC
Polyvinyl chloride
PVN
Polyvinyl nitrate
PYX
2,6-Bis(picrylamino)-3,5-dinitropyridine
Q-D
Quantity-distance
RARDE
Royal Armament Research & Development Establishment, UK
R-C
Resistance capacitance
RCC
Reinforced cement concrete
RCL
Recoilless
R&D
Research & development
RDX
Research department explosive
RESS
Rapid expansion of supercritical solution
RFNA
Red fuming nitric acid
RH
Relative humidity
ROWANEX
Royal Ordnance Waltham Abbey New Explosive
RP
Red phosphorus
RS-RDX
Reduced sensitivity RDX
SAT
5,5′-Styphnylamino-1,2,3,4-tetrazole
SB
Single-base
SCB
Semiconductor bridge
SCE
Supercritical extraction
SDRA
Swedish Defence Research Agency
SFIO
Superfine iron oxide
SF
5
Pentafluorosulfonyl
SIN
Substance identification number
SLA
Service lead azide
SLV
Satellite launch vehicle Space launch vehicle
SMS
Site mixed slurry
SNPE
Societe Nationale des Poudres et Explosifs, France
SOP
Safe operating procedures
SR
Secret research
SS
Stainless steel
SSO
Sun-synchronous orbit
STA
Simultaneous thermal analysis
STANAG
Standardization Agreement (of NATO)
Stp
Standard temperature and pressure
SW
Single-walled (carbon nanotubes)
Sym. TCB
Symmetrical trichlorobenzene
T
Absolute temperature
TA
Triacetin
TACOT
Tetranitro dibenzo-l,3a,4,4a-tetraazapentalene
TADAIW
Tetraacetyl diamine isowurtzitane
TADBIW
Tetraacetyl dibenzyl isowurtzitane
TADFIW
Tetraacetyl diformal isowurtzitane
TADNIW
Tetraacetyl dinitroso isowurtzitane
TAGAT
Triaminoguanidinium azotetrazolate
TAGN
Triaminoguanidine nitrate
TATB
1,3,5-Triamino-2,4,6-trinitrobenzene
TATNB
1,3,5-Triazido-2,4,6-trinitrobenzene
TB
Triple-base
TBP
Triphenyl bismuth
TBPAn
Tetrabromophthalic anhydride
TCB
Trichlorobenzene
TCP
Tricresyl phosphate
TCPAn
Tetrachlorophthalic anhydride
TCTNB(Sym.)
1,3,5-Trichloro-2,4,6-trinitrobenzene
TDI
Toluene diisocyanate
TEA
Triethyl aluminum
TEAN
Triethanolamine nitrate
Teflon (PTFE)
Poly(tetrafluoroethylene) (Trade name of Du Pont)
TEG
Triethylene glycol
TEGDN
Triethylene glycol dinitrate
TEM
Transmission electron microscope
TET
Triethylene tetramine
T
g
Glass transition temperature
TGA
Thermogravimetric analysis or thermogravimetry
THF
Tetrahydrofuran
TMD
Theoretical maximum density
TMETN
1,1,1-Trimethylolethane trinitrate
TMHI
1,1,1-Trimethyl hydrazinium iodide
TMOS
Tetramethoxysilane
TMP
Trimethylol propane
TNA
1,3,5,7-Tetranitroadamantane
TNABN
2,5,7,9-Tetranitro-2,5,7,9-tetraazabicyclo [4.3.0] nonane-8-one
TNAD
Trans-l,4,5,8-tetranitro-l,4,5,8-tetraazadecalin
TNAZ
1,3,3-Trinitroazetidine
TNB
Trinitrobenzene
TNC
TetranitrocubaneTetranitrocarbazole
TNDPDS
Tetranitrodiphenyl disulfide
TNGU
1,3,4,6-Tetranitroglycoluril (Sorgunyl, French)
TNO
Tetranitrooxanilide
TNO-PML
TNO-Prins Maurits Laboratory, The Netherlands(now a part of TNO Defence, Security and Safety)
TNPDU
Tetranitro propanediurea
TNPG
Trinitro phloroglucinol
TNT
Trinitrotoluene
TNTO
TNT & NTO based formulations
TOP
Tris(2-ethylhexyl) phosphate
TOP
Total obscuring power
TPE
Thermoplastic elastomer
TPM
N
2
,N
4
,N
6
-Tripicrylmelamine
Tris-X
2,4,6-Tris(2-nitroxyethylnitramino)-1,3,5-triazine
TS
Tensile strength
UDMH
Unsymmetrical dimethylhydrazine
UF
Ultrafine(powder)
UK
United Kingdom
UL
Underwriters Laboratories
UNCOE
United Nations Committee of Experts
UNO
United Nations Organization
USA
United States of America
USSR
Union of Soviet Socialist Republics
UXBs
Unexploded bombs
UXO
Unexploded ordnance
VAAR
Vinyl acetate alcohol resin
Viton-A
Copolymer of vinylidene fluoride and hexafluoropropylene (Trade name of Du Pont)
VNS
Vicarious nucleophilic substitution
VOD
Velocity of detonation
VSSC
Vikram Sarabhai Space Centre
VST
Vacuum stability test
WP
White phosphorus
ZIOC
Zelinsky Institute of Organic Chemistry
Symbols
A
Frequency factor
C
p
Specific heat at constant pressure
C
v
specific heat at constant volume
g
Acceleration due to gravity
I
sp
Specific impulse
n
Pressure exponent/index
R
Universal gas constant
Q
Heat of explosion
ρ
Density
η
b
Ballistic efficiency
η
p
Piezometric efficiency
γ
Specific heat ratio i.e
C
p
/
C
v
α, β, γ, δ, ∈
Polymorphic forms of explosives
1Salient Features of Explosives
1.1Introduction
Explosives are thought to have been discovered in the seventh century by the Chinese and the first known explosive was black powder (also known as gunpowder) which is a mixture of charcoal, sulfur and potassium nitrate. The Chinese used it as an explosive, propellant and also for fireworks. Subsequently, with the development of nitrocellulose (NC) and nitroglycerine (NG) in Europe, a new class of explosives viz. low explosives came into existence. As this new class of explosives burn slowly in a controlled manner giving out a large volume of hot gases which can propel a projectile, these low explosives were termed as propellants. The discovery of high explosives such as picric acid, trinitrotoluene (TNT), pentaerythritol tetranitrate(PETN), cyclotrimethylene trinitramine (research department explosive RDX), cyclotetramethylene tetranitramine (high melting explosive HMX) etc. which are more powerful but relatively insensitive to various stimuli (heat, impact, friction and spark), advocated their use as explosive fillings for bombs, shells and warheads etc. Similarly, by following the principle of gunpowder and in order to meet the requirements of military for special effects (illumination, delay, smoke, sound and incendiary etc.), formulations based on fuels, oxidizers, binders along with additives were developed and classified as pyrotechnics.
These three branches of explosives viz. explosives, propellants and pyrotechnics, were developed independently until the early 1990s and during this time, the number of reported explosives increased exponentially. In order to camouflage research on explosives, propellants and pyrotechnics, a new term ‘high energy materials’ (HEMs) was coined by the explosives community for them. Thus all explosives, propellants and pyrotechnics can be referred to as high energy materials (HEMs) or energetic materials (EMs). In other words, the other name of HEMs/EMs is explosives, propellants and pyrotechnics depending on their formulations and intended use. Nowadays, the term HEMs/EMs is generally used for any material that can attain a highly energetic state mostly by chemical reactions [1].
The ancient civilizations all over the globe used to carry out prodigious mining, quarrying and building projects by the use of forced human labor. The following examples are available in the literature in this regard.
War captives were used to hack out hundreds of miles of mines, irrigation canals and for other constructions by the ancient Egyptians.
The inhabitants of the Aegean Island of Samos tunneled their way through rock for water supply in the sixth century BCE.
A large number of temples and forts were carved out of the rocks in India and the Far East.
Hannibal crossed the Alps by hacking out passageways with chisels and wedges.
Explosives provided ways and means to alleviate this drudgery. It was more efficient and economical to bring down rocks or do mining with the use of gunpowder, the first explosive, than by any other previous means. Explosives are generally associated with a destructive role but their important contributions are very often lost sight of. In fact, it was the power of explosives which made the great industrial revolution possible in Europe and also made the mineral wealth of earth available to mankind. Considerable technological progress in the development and applications of explosives has made it possible to move mountains, tame rivers, mine minerals from deep underground and also link continents and countries by roads and rails through difficult and hazardous terrain. Explosives continue to play an overwhelming role in the progress and prosperity of mankind right from the time of invention of black powder or gunpowder several centuries ago. In fact, some of today’s fantastic engineering projects and exploration of space would have not been possible without the use of explosives [2].
Explosives, in a nutshell, generally perceived as ‘devil’ during war and considered as an ‘evil’ during processing, handling, transportation and storage, have proved to be an ‘angel’ due to their tremendous impact on economy and industries. Explosives have contributed enormously in improving the economy of many countries and their chemistry forms the basis of many well-known treatises [3–6].
1.2Definition
A study of the literature suggests that an explosive may be defined in one of the following ways:
An explosive is a substance which, when suitably triggered, releases a large amount of heat and pressure by way of a very rapid self-sustaining exothermic decomposition reaction. The temperature generated is in the range of 3000–5000 °C and the gases produced expand 12000–15000 times than the original volume. The entire phenomenon takes place in a few microseconds, accompanied by a shock and loud noise.
An explosive is a chemical substance or a mixture of chemical substances, which when subjected to heat, percussion, detonation or catalysis, undergoes a very rapid decomposition accompanied with the production of a large amount of energy. A large volume of gases, considerably greater than the original volume of the explosive, is also liberated.
An explosive is a substance or device which produces, upon release of its potential energy, a sudden outburst of gases thereby exerting high pressure on its surroundings.
Thus there are two important aspects of a chemical reaction which results in an explosion.
1.2.1 Evolution of Heat
The generation of heat in large quantities accompanies every explosive chemical reaction. It is this rapid liberation of heat that causes the gaseous products of reaction to expand and generate high pressures. This rapid generation of high pressures of released gases constitutes explosion. It is worthwhile to point out that liberation of heat with insufficient rapidity does not cause an explosion. For example, although a pound of coal yields five times as much heat as a pound of nitroglycerine, coal cannot be described as an explosive because the rate at which it yields this heat is quite slow.
1.2.2 Rapidity of Reaction
Rapidity of reaction distinguishes an explosive reaction from an ordinary combustion reaction and therefore, an explosive reaction takes place with great speed. Unless the reaction occurs rapidly, thermally expanded gases are dissipated in the medium slowly, so that no explosion results. Again an example of wood or coal fire makes it clear. When a piece of wood or coal burns, there is an evolution of heat and formation of gases, but neither is liberated rapidly enough to cause an explosion.
This means that the fundamental features possessed by an explosive are:
Potential energy by virtue of its chemical constitution.
Rapid decomposition on suitable initiation.
Formation of gaseous products with simultaneous release of a large amount of energy.
In other words, investigation of explosives involves a study of these aspects. For example, an investigation of the potential energy involves study of thermochemistry of the chemical compound in question. Further, the power and sensitiveness of an explosive depend on properties such as ‘heat of formation’ and ‘heat of explosion’. An investigation of the feature (2) involves measurement of the rate of propagation of explosion waves and all phenomena in the proximity of detonating mass of the explosive. This rate of decomposition largely determines the pressure developed and is also the criterion for classification of explosives into ‘high’ and ‘low’ explosives. Lastly, investigation of feature (3) mentioned above involves study of reactions leading to explosion. The rates of individual reactions at different temperatures and pressures and equilibria established among various decomposition products may also be studied to understand the mechanism.
An explosive may be a solid (trinitrotoluene, TNT), liquid (nitroglycerine, NG) or gas (a mixture of hydrogen and oxygen). Also, it may be a single chemical compound (TNT), a mixture of explosive compounds [a mixture of TNT and ammonium nitrate (AN, NH4NO3)] or a mixture of two or more substances, none of which in itself needs be an explosive (gunpowder–mixture of charcoal, sulfur and potassium nitrate). The products of explosion are gases or a mixture of gases and solids or only solids. NG yields only gaseous products whereas black powder yields both gases and solids. On the other hand, all products are solids in the case of cuprous acetylide.
A comparatively fast reaction of a high explosive is called detonation whereas the slower reaction of low explosives is called deflagration or burning. Explosives may undergo burning, deflagration (fast burning: 300–3000 ms−1) or detonation (5000–10 000 ms−1) depending upon the nature of the explosive, mode of triggering, and confinement of the explosive etc. When initiation of decomposition of an explosive is set in by a flame, it simply burns. However, if confined, it burns at a faster rate and the phenomenon may ultimately transform to detonation. The detonation of an explosive can be achieved by the supply of shock energy in a quantum. Combustion is a slow phenomenon. For the combustion to be fast, oxygen should be in close contact with the fuel. A rapid combustion or detonation can be accomplished by close combination of the fuel and oxidizer elements within the same molecule as in the case of NG, TNT and RDX etc. Further, an explosion is considered to be a rapid form of combustion which occurs due to the oxidation of fuels with the participation of oxygen from the air.
1.3Classification
Explosives are used for constructive as well as destructive purposes for both military and civil applications. There are several ways of classifying explosives and a few important ones are:
according to their end-use for example, military explosives for military applications whereas civil explosives for commercial purposes;
according to the nature of explosion for example, mechanical, nuclear or chemical;
according to their chemical structure that is, the nature of bonds present in an explosive.
The classification of explosives is depicted in Figure 1.1 and their brief description is outlined below:
Figure 1.1 (a) Classification of explosives (according to their end-use). (b) Classification of explosives (according to nature of explosive/ingredient).
1.3.1 Military Explosives
Military explosives comprise explosives and explosive compositions or formulations that are used in military munitions (bombs, shells, torpedoes, grenades, missile or rocket warheads). The bulk charges (secondary explosives) in these munitions are insensitive to some extent and are, therefore, safe for handling, storage and transportation. They are set off by means of an explosive train consisting of an initiator followed by intermediates or boosters.
Military explosives must be physically and chemically stable over a wide range of temperatures and humidity for a long period of time. They must be reasonably insensitive to impact, such as those experienced by artillery shells when fired from a gun or when they penetrate steel armor. They are used for a number of applications. They are fired in projectiles and dropped in aerial time bombs without premature explosion. The raw materials necessary to manufacture such explosives must be readily available for production in bulk during wartime.
The chemical explosives are sub-divided into four main types: (i) detonating or high explosives; (ii) deflagrating or low explosives; (iii) pyrotechnics and (iv) civil or commercial explosives.
1.3.1.1 Detonating or High Explosives
These explosives are characterized by very high rates of reaction and generation of high pressures on explosion. They are usually sub-divided into (i) primary or initiatory explosives, (ii) secondary explosives and (iii) tertiary explosives.
Primary high explosives
are very sensitive materials and are easily exploded by the application of fire, spark, impact, friction etc. They are dangerous to handle and are used in comparatively small quantities. They are generally used in primers, detonators and percussion caps. Examples of primary explosives are lead azide (LA), mercury fulminate (MF), silver azide, basic lead azide (BLA) etc.
Secondary high explosives are explosives which are relatively insensitive to both mechanical shock and flame but explode with greater violence when set off by an explosive shock obtained by detonating a small amount of a primary explosive in contact with it. In other words, secondary high explosives require the use of a detonator and frequently a booster. PETN is often considered a benchmark explosive, with explosives that are more sensitive than PETN being classified as primary explosives.
A major difference between primary and secondary explosives arises from the fact that primary explosives are initiated to detonate by burning whereas secondary explosives are initiated to detonate by shock waves. Therefore, the most important property of a primary explosive is its ability to undergo a fast deflagration-to-detonation transition (DDT). Thus, fast DDT is the strength of primary explosives as well as their weakness. All other parameters being equal, the faster the DDT, the better the primary explosive. At the same time, fast DDT shows a weakness because accidental initiation of deflagration results in detonation.
Tertiary explosives (also called blasting agents)
mainly consist of oxidizers such as ammonium nitrate (AN, NH4NO3), ammonium perchlorate (AP, NH
4
ClO
4
), ammonium dinitramide [ADN, NH
4
N (NO
2
)
2
] and mononitrotoluene (MNT) etc. AN and AP are the prime examples. It is more difficult to initiate tertiary explosives by fire, impact or friction and, if initiated, they have a large critical diameter so that the propagation to mass detonation is much less likely than for secondary explosives. Tertiary explosives are so insensitive to shock that they cannot reliably be detonated by practical quantities of primary explosives and require an intermediate explosive booster of secondary explosive instead. These explosives, in pure form without fuel components, also have low explosion energies, only about a third of that of TNT. For the purpose of commercial transportation and storage, both AN and AP are classified as oxidizers and not as explosives. Contrary to the common belief, tertiary explosives have been the cause of some of the largest accidental explosions in history. The 1921 and 1947 AN explosions in Oppau and Texas respectively and the 1988 AP explosion at Henderson (Nevada) have taken by surprise all those locally involved with the material [7–9].
1.3.1.2 Deflagrating or Low Explosives
Low explosives differ from high explosives in their mode of decomposition. They burn slowly and regularly. The action is therefore less shattering. On combustion, low or deflagrating explosives evolve large volume of gases but in a controllable manner. Examples are black powder, smokeless powder and propellants: single-base (SB), double-base (DB), triple-base (TB), composite, composite modified DB, fuel rich etc. Propellants are combustible materials containing within themselves all the oxygen needed for their combustion and their main function is to impart motion to a projectile or missile. These are used for military applications and space exploration. Propellants only burn and do not generally explode or detonate. Propellants are initiated by a flame or spark and are converted from a solid to gaseous state relatively slowly [10].
In other words, high explosives detonate and hence are ideally suitable as shell and bomb fillers in order to give maximum demolition effect at the target. On the other hand, low explosives burn and are ideally suitable as propellant powders to expel projectiles from weapons. A high explosive would blow up the weapon because of its high reaction rate and shattering effect whereas a low explosive would be ineffective in reducing concrete fortifications or in obtaining proper shell fragmentation. TNT and other high explosives make excellent shell fillers and smokeless powder makes an excellent low explosive in the form of a propellant.
It is better to examine this difference between the detonation of a high explosive and the deflagration or burning of a low explosive more closely on a qualitative basis. Consider a point in a high explosive, initiated at one end as shown in Figure 1.2.
Figure 1.2 Detonation vs. burning for high and low explosives.
