High Energy Materials - Jai Prakash Agrawal - E-Book

High Energy Materials E-Book

Jai Prakash Agrawal

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Beschreibung

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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Table of Contents

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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

[email protected]

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.