Metal-Fluorocarbon Based Energetic Materials E-Book

Ernst-Christian Koch

• Herausgeber: Wiley-VCH
• Kategorie: Fachliteratur
• Sprache: Englisch
• Veröffentlichungsjahr: 2012

Seitenzahl: 365

Beschreibung

This exciting new book details all aspects of a major class of pyrolants and elucidates the progress that has been made in the field, covering both the chemistry and applications of these coompounds. Written by a pre-eminent authority on the subject from the NATO Munitions Safety Information Analysis Center (MSIAC), it begins with a historical overview of the development of these materials, followed by a thorough discussion of their ignition, combustion and radiative properties. The next section explores the multiple facets of their military and civilian applications, as well as industrial synthetic techniques. The critical importance of the associated hazards, namely sensitivity, stability and aging, are discussed in detail, and the book is rounded off by an examination of the future of this vital and expanding field. The result is a complete guide to the chemistry, manufacture, applications and required safety precautions of pyrolants for both the military and chemical industries. From the preface: "... This book fills a void in the collection of pyrotechnic literature... it will make an excellent reference book that all researchers of pyrolants and energetics must have..." Dr. Bernard E. Douda, Dr. Sara Pliskin, NAVSEA Crane, IN, USA

Leseprobe

Table of Contents

Related Titles

Title Page

Copyright

Dedication

Foreword

Preface

Acknowledgment

Chapter 1: Introduction to Pyrolants

References

Chapter 2: History

2.1 Organometallic Beginning

2.2 Explosive & Obscurant Properties

2.3 Rise of Fluorocarbons

2.4 Rockets Fired Against Aircraft

2.5 Metal/Fluorocarbon Pyrolants

References

Further Reading

Chapter 3: Properties of Fluorocarbons

3.1 Polytetrafluoroethylene (PTFE)

3.2 Polychlorotrifluoroethylene (PCTFE)

3.3 Polyvinylidene Fluoride (PVDF)

3.4 Polycarbon Monofluoride (PMF)

3.5 Vinylidene Fluoride–Hexafluoropropene Copolymer

3.6 Vinylidene Fluoride–Chlorotrifluoroethylene Copolymer

3.7 Copolymer of TFE and VDF

3.8 Terpolymers of TFE, HFP and VDF

3.9 Summary of Chemical and Physical Properties of Common Fluoropolymers

References

Chapter 4: Thermochemical and Physical Properties of Metals and their Fluorides

References

Chapter 5: Reactivity and Thermochemistry of Selected Metal/Fluorocarbon Systems

5.1 Lithium

5.2 Magnesium

5.3 Titanium

5.4 Zirconium

5.5 Hafnium

5.6 Niob

5.7 Tantalum

5.8 Zinc

5.9 Cadmium

5.10 Boron

5.11 Aluminium

5.12 Silicon

5.13 Calcium Silicide

5.14 Tin

References

Chapter 6: Ignition and Combustion Mechanism of MTV

6.1 Ignition and Pre-Ignition of Metal/Fluorocarbon Pyrolants

6.2 Magnesium–Grignard Hypothesis

References

Chapter 7: Ignition of MTV

References

Chapter 8: Combustion

8.1 Magnesium/Teflon/Viton

8.2 Porosity

8.3 Burn Rate Description

8.4 Combustion of Metal–Fluorocarbon Pyrolants with Fuels Other than Magnesium

8.5 Underwater Combustion

References

Chapter 9: Spectroscopy

9.1 Introduction

9.2 UV–VIS Spectra

9.3 MWIR Spectra

9.4 Temperature Determination

References

Chapter 10: Infrared Emitters

10.1 Decoy Flares

10.2 Nonexpendable Flares

10.3 Metal–Fluorocarbon Flare Combustion Flames as Sources of Radiation

10.4 Infrared Compositions

10.5 Operational Effects

10.6 Outlook

References

Chapter 11: Obscurants

11.1 Introduction

11.2 Metal–Fluorocarbon Reactions in Aerosol Generation

References

Chapter 12: Igniters

References

Chapter 13: Incendiaries, Agent Defeat, Reactive Fragments and Detonation Phenomena

13.1 Incendiaries

13.2 Curable Fluorocarbon Resin–Based Compositions

13.3 Document Destruction

13.4 Agent Defeat

13.5 Reactive Fragments

13.6 Shockwave Loading of Metal–Fluorocarbons and Detonation-Like Phenomena

References

Further Reading

Chapter 14: Miscellaneous Applications

14.1 Submerged Applications

14.2 Mine-Disposal Torch

14.3 Stored Chemical Energy

14.4 Tracers

14.5 Propellants

References

Chapter 15: Self-Propagating High-Temperature Synthesis

15.1 Introduction

15.2 Magnesium

15.3 Silicon and Silicides

References

Chapter 16: Vapour-Deposited Materials

References

Chapter 17: Ageing

References

Chapter 18: Manufacture

18.1 Introduction

18.2 Treatment of Metal Powder

18.3 Mixing

18.4 Pressing

18.5 Cutting

18.6 Priming

18.7 Miscellaneous

18.8 Accidents and Process Safety

References

Chapter 19: Sensitivity

19.1 Introduction

19.2 Impact Sensitivity

19.3 Friction and Shear Sensitivity

19.4 Thermal Sensitivity

19.5 ESD Sensitivity

19.6 Insensitive Munitions Testing

19.7 Hazards Posed by Loose In-Process MTV Crumb and TNT Equivalent

References

Chapter 20: Toxic Combustion Products

20.1 MTV Flare Composition

20.2 Obscurant Formulations

20.3 Fluorine Compounds

References

Chapter 21: Outlook

References

Index

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The Author

Dr. Ernst-Christian Koch

NATO Munitions Safety

Information Analysis Center (MSIAC)

Boulevard Leopold III

1110 Brussels

Belgium

Cover

The cover picture depicts the combustion flame of Magnesium/Teflon TM/HycarTM strand (photographed by Andrzej Koleczko, Fraunhofer ICT, Germany) superimposed on the assumed main combustion step between difluorocarbene and magnesium.

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>.

© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

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: 978-3-527-32920-5

ePDF: 978-3-527-64420-9

oBook: 978-3-527-64418-6

ePub: 978-3-527-64419-3

Mobi: 978-3-527-64421-6

Dedicated to my family

Foreword

We have known Dr Ernst-Christian Koch since meeting him during one of the International Pyrotechnics Seminar back in the 1990s. Even back then, we knew that he was more than just a research scientist interested in pyrolants and energetics. Dr Koch demonstrated a passion for pyrolants beyond that of a hobbyist or an employee. His enthusiasm is clearly demonstrated by the impressive number of his patents and publications. Therefore, it comes as no surprise that Dr Koch has channelled his drive for the dissemination of knowledge about pyrolants, and more specifically magnesium-Teflon-Viton (MTV) compositions into a clearly written book. Often, we will receive an email from Dr Koch that directs us to information about a new patent or publication about MTV. His ability to take a small amount of information and extrapolate beyond it is just one facet of his talent as a scientist. It is a pleasure to finally read a book that encompasses some (obviously, not all) of his knowledge in the field of pyrolants.

This book is unique in that its scope is limited to data about the MTV reaction, application of the reactions related to MTV, and metal–halogen reactions that might be substituted for the MTV reaction. The book provides the reader a single source for research results and data on all compositions related to MTV and the application thereof. The breadth of references, figures and tables demonstrate the vast and careful research Dr Koch undertook.

This book fills a void in the collection of pyrotechnic literature because it deals exclusively with research related to MTV-like compositions. Chapter 9 includes pictures that enable the reader to actually envision the combustion reaction of the different metal/fluoride reactions. Chapter 10 and 10.5 Operational Effects chapters are limited, only because of the availability and security constraints beyond the author's control. Chapters delving into previously unconsidered regions and Chapters 11 and 13 are of notable interest in the context of cyberwar and intellectual property disputes. Chapters 18 and 19 are a great compilation of the past and current practices. The history of the incidents involved with MTV manufacturing and the way processing has evolved to help mitigate explosive incidents is presented in a straightforward manner. Chapter 15 exemplifies Dr Koch's ability to look ahead. His citations in this chapter are abundant for a very limited field of research. Once again, the author illustrates his ability to take new information/ideas and to compile them in a useful and informative way.

No other known book documents MTV-like compositions in this depth. This book can be considered to be a textbook of everything associated with the MTV composition and, because of the extraordinary amount of documentation of data about MTV-like compositions, it will make an excellent reference book that all researchers of pyrolants and energetics must have.

Dr Bernard Douda and Dr Sara Pliskin

Naval Surface Warfare Center,

Crane, Indiana, USA

Preface

Metal/Fluorocarbon pyrolants, similar to black powder, are very versatile energetic materials with a great many number of applications. Over the last 50 years metal/fluorocarbon-based energetic materials have developed from secret laboratory curiosities into well-acknowledged standard payload materials for high-performance ordnance such as countermeasure flares and both strategical and tactical missile igniters. However, the long-lasting obligation to maintain secrecy over many of these compositions in most countries affected their further development and impeded personnel involved in becoming acquainted with the particular safety and sensitivity characteristics of these materials.

When I first dealt with Magnesium/Teflon™/Viton™ (MTV) in the mid 1990s I became fascinated by these materials. However, trying to learn more about them was difficult because of the above mentioned classification issues. Thus my research aimed at exploring some of the fundamentals of MTV to have good basis to start further development on. Fortunately, in the meantime the Freedom of Information Act both in the United States and United Kingdom brought significant relief to this and has enabled access to formerly classified files. Still the information is not readily retrievable as the actual content of these files is not well documented. Thus, in order to establish a reference base for MTV, I have gathered documents from the public domain over the last 15 years. The present book now is the result of an attempt to present the most relevant information in a reasonable manner.

Even though carefully compiled, I preemptively apologize for any kind of technical errors and omissions which I am afraid cannot be completely avoided. However, I would be glad to receive your critical comments in order to improve future editions of this book.

I hope you enjoy reading the book as much as I enjoyed writing it.

Brussels and Kaiserslautern, October 2011

Ernst-Christian Koch

Acknowledgment

A book like this is never the achievement of a single individual. Thus I wish to express my sincere appreciation for the support I received during my research on metal fluorocarbon based energetic materials and while writing this monograph.

The late Dr. rer. nat. Peter Kalisch (†2010), retired technology and scientific director of the Diehl Stiftung/Nuremberg I gratefully acknowledge for his enduring, constructive and friendly support, and facilitating financial support for research on both combustion synthesis and obscurant properties of magnesium/graphite fluoride pyrolants.

I wish to thank the following individuals (in no certain order) for their advice both oral and written and/or their experimental support on this fascinating topic which has helped me in writing this book.

Dr. Sara Pliskin (NSWC, USA); Dr. Eckhard Lissel, Harald Franzen, Jürgen Wolf (former WIWEB/Heimerzheim); Mrs. Ilonka Ringlein, Alfred Aldenhoven, Heinz Hofmann, Johann Licha, Dr. Arno Hahma (Diehl BGT Defence); Dr. Axel Dochnahl, Daniel Krämer (former Piepenbrock Pyrotechnik/Germany); Dr. Alla Pivkina, Dr. Alexander Dolgoborodov (Semenov Institute/Moscow); Jim Callaway (DSTL/Fort Halstead); Dr. Trevor T. Griffiths (Qinetiq/Fort Halstead); Prof. Steven Son PhD., Aaron B. Mason, Dr. Cole Yarrington (Purdue University/USA); Prof. Michelle Pantoya PhD. (Texas Tech. University/USA); Dr. Harold D. Ladouceur (NRL/USA); Prof. Dr. Takuo Kuwahara (NST/Japan); Rutger Webb, Chris van Driel (TNO/Netherlands); Mrs. Evelin Roth, Mrs. Angelika Raab, Mrs. Heidrun Poth, Mrs. Sara Steinert, Andreas Lity, Sebastian Knapp, Uwe Schaller, Dr. Lukas Deimling, Dr. Manfred Bohn (Fraunhofer-ICT/Germany), Prof. Dr. Thomas Klapötke (LMU Munich/Germany), Dr. Henrik Radies (Rheinmetall/Germany); Patrice Bret (A3P/France); Dr. Jim Chan (Orica/Canada); Dr. Dana Dattelbaum (LANL/USA); Prof. Dr. Jean'ne M. Shreeve (University of Idaho/USA), Prof. Dr. Anton Meller (Göttingen/Germany), Prof. Dr. Richard Kaner (University of California/USA), Prof. Dr. Edward Dreizin (New Jersey Institute of Technology/USA)), Prof. Dr. Wolfgang Kaminsky (Hamburg/Germany), Dr. Dave Dillehay (Cobridge/USA); Dr. Michael Koch (WTD 91/Germany); Dr. Martin Raftenberg (ARL/USA); Bernard Kosowski (MACH I /USA); Dr. Stany Gallier (SNPE/France); Dr. Günther Diewald (former Oerlikon Contraves/Switzerland); Olivier Azzola (Ecole Polytechnique/France); and Patrice Bret (CEHD/France).

I thank Mrs. Leslie Belfit, project editor at Wiley-VCH/Weinheim, and Mrs. Rajalakshmi Gnanakumar Laserwords/India for the good cooperation and smooth support with a difficult manuscript.

Further I am very grateful to the following people for giving valuable advice and for taking the burden to review selected chapters of this book: Prof. Dr. Stanisław Cudziło (MUT-Warzaw/Poland); Beat Berger (Armasuisse/Switzerland); Dr. Nigel Davies (University of Cranfield/UK); Neal Brune (Armtech/USA); and Volker Weiser, Dr. Stefan Kelzenberg, Dr. Norbert Eisenreich (Fraunhofer-ICT/Germany).

Finally I wish to thank Dr. Bernard E. Douda for inviting me to become actively involved with the International Pyrotechnics Society. I thank him for his help and the friendly support he provided in response to the many questions I addressed to him over the years. I greatly appreciate his reviewing of parts of this book and his efforts to write a preface together with Dr. Sara Pliskin. It is his report on the “Genesis of IRCM” that has definitely triggered me to write this book.

Thank you Bernie!

Brussels and Kaiserslautern, October 2011

Ernst-Christian Koch

Chapter 1

Introduction to Pyrolants

Energetic materials are characterised by their ability to undergo spontaneous (ΔG < 0) and highly exothermic reactions (ΔH < 0). In addition, the specific amount of energy released by an energetic material is always sufficient to facilitate excitation of electronic transitions, thus causing known luminous effects such as glow, spark and flame. Energetic materials are typically classified according to their effects. Thus, they can be classified into high explosives, propellants and pyrolants (Figure 1.1). Typical energetic materials and some of the salient properties are listed in Table 1.1.

Figure 1.1 Classification of energetic materials.

Table 1.1 Performance Parameters of Selected Energetic Materials.

When initiated, high explosives undergo a detonation. That is a supersonic shockwave supported by exothermic chemical reactions [1–3]. In contrast, propellants and pyrolants undergo subsonic reactions and mainly yield gaseous products as in the case of propellants [4, 5] or predominantly condensed reaction products as in the case of pyrolants. The term pyrolant was originally coined by Kuwahara to emphasise on the difference between these materials and propellants [6]. Thus, the term aims at defining those energetic materials that upon combustion yield both hot flames and large amount of condensed products. Hence, pyrolants often find use where radiative and conductive heat transfer is necessary. Pyrolants also prominently differ from other energetic materials in that they have both very high gravimetric and volumetric enthalpy of combustion and very often densities far beyond 2.0 g cm−3 (see Table 1.1 for examples).

Pyrolants are typically constituted from metallic or non-metallic fuels (e.g. Al, Mg, Ti, B, Si, C(gr) and S8) and inorganic (e.g. Fe2O3, NaNO3, KClO4 and BaCrO4) and/or organic (e.g. C2Cl6 and (C2F4)n) oxidizers or alloying partners (e.g. Ni and Pd). In contrast to propellants, they are mainly fuel rich and their combustion is influenced by afterburn reactions with atmospheric oxygen or other ambient species such as nitrogen or water vapour.

Pyrolants serve a surprisingly broad spectrum of applications such as payloads for mine-clearing torches (Al/Ba(NO3)2/PVC) [7, 8], delays (Ti/KClO4/BaCrO4) [9], heating charges (Fe/KClO4) [10, 11], igniters (B/KNO3) [12, 13], illuminants (Mg/NaNO3) [14, 15], thermites (Al/Fe2O3) [16, 17], obscurants (RP/Zr/KNO3) (RP, red phosphorus) [18], (Al/ZnO/C2Cl6) [20], tracers (MgH2/SrO2/PVC) [21], initiators (Ni/Al) [22] and many more. Recently, pyrolant combustion is increasingly used for the synthesis of new materials.

An important group of pyrolants are those constituted from metal powder and halocarbon compounds [19]. The high energy density of metal–halocarbon pyrolants stems from the high enthalpy of formation of the corresponding metal–halogen bond (M–X). Thus, chlorocarbon but mainly fluorocarbon compounds are used as oxidizers.

On the basis of metal fluorocarbon combinations, pyrolants show superior exothermicity compared to many of the aforementioned fluorine-free systems [22]. This advantage is due to the high enthalpy of formation of the metal–fluorine bond not outperformed by any other combination of the respective metal. Thus, the exothermic step

Owing to a great number of metallic elemental fluorophiles (∼70), metal fluorocarbon pyrolants (MFPs) offer a great variability in performance. In addition, many alloys and binary compositions of fluorophiles may also come into play to further tailor the performance of the pyrolant: Mg4Al3, MgH2, MgB2, Mg3N2, Mg(N3)2, Mg2Si and so on [23]. Very often MFPs find use in volume-restricted applications where other materials would not satisfy the requirements – see, for example, payloads for infrared decoy flares (see Chapter 10). Within the scope of this book, the following applications are discussed:

agent defeat payloads

countermeasure flares

cutting torches

heating devices

igniters

incendiaries

material synthesis

obscurants

propellants

reactive fragments

stored chemical energy propulsion systems

tracers

tracking flares

underwater flares.

This book focuses only on specialised pyrotechnic applications; thus, for a more generalised introduction to pyrotechnics, the interested reader is referred to the books by Shidlovski [24], Ellern [25], McLain [26], Conkling [27, 28], Hardt [29] and Kosanke et al. [30].

References

1. Fickett, W. and Davis, W.C. (2000) Detonation – Theory and Experiment, Dover Publications Inc., Mineola, New York.

2. Zukas, J.A. and Walters, W.P. (1998) Explosive Effects and Applications, Springer Publishers, New York.

3. Cooper, P.W. (1996) Explosives Engineering, Wiley-VCH Verlag GmbH, New York.

4. Kubota, N. (2007) Propellants and Explosives, Thermochemical Aspects of Combustion, 2nd completely revised and extended edn, Wiley-VCH Verlag GmbH, Weinheim.

5. Assovskiy, I.G. (2005) Physics of Combustion and Interior Ballistics, Nauka, Moscow.

6. Kuwahara, T. and Ochiai, T. (1992) Burning rate of magnesium/TF pyrolants. Kogyo Kayaku, 53 (6), 301–306.

7. Kannberger, G. (2005) Test and Evaluation of Pyrotechnical Mine Neutralisation Means. ITEP Work Plan Project Nr. 6.2.4, Final Report, Bundeswehr Technical Center for Weapons and Ammunition (WTD 91), Germany.

8. N.N. (2005) Operational Evaluation Test of Mine Neutralization Systems, Institute for Defense Analyses, Alexandria, http://en.wikipedia.org/wiki/Political_divisions_of_the_United_States VA.

9. Wilson, M.A. and Hancox, R.J. (2001) Pyrotechnic delays and thermal sources. J. Pyrotech., 13, 9–30.

10. Callaway, J., Davies, N. and Stringer, M. (2001) Pyrotechnic heater compositions for use in thermal batteries. 28th International Pyrotechnics Seminar, Adelaide Australia, November 4–9, 2001, pp. 153–168.

11. Czajka, B. and Wachowski, L. (2005) Some thermochemical properties of high calorific mixture of Fe-KClO4. Cent. Eur. J. Energetic Mater., 2 (1), 55–68.

12. Klingenberg, G. (1984) Experimental study on the performance of pyrotechnic igniters. Propellants Explos. Pyrotech., 9 (3), 91–107.

13. Weiser, V., Roth, E., Eisenreich, N., Berger, B. and Haas, B. (2006) Burning behaviour of different B/KNO3 mixtures at pressures up to 4 MPa. 37th International Annual ICT Conference, Karlsruhe Germany, June 27–30, p. 125.

14. Beardell, A.J. and Anderson, D.A. (1972) Factors affecting the stoichiometry of the magnesium-sodium nitrate combustion reaction. 3rd International Pyrotechnics Seminar, Colorado Springs, CO, 21–25 August, pp. 445–459.

15. Singh, H., Somayajulu, M.R. and Rao, B. (1989) A study on combustion behaviour of magnesium – sodium nitrate binary mixtures. Combust. Flame, 76 (1), 57–61.

16. Fischer, S.H. and Grubelich, M.C. (1998) Theoretical energy release of thermites, intermetallics, and combustible metals. 24th International Pyrotechnics Seminar, Monterey CA, July 27–31, pp. 231–286.

17. Weiser, V., Roth, E., Raab, A., del Mar Juez-Lorenzo, M., Kelzenberg, S. and Eisenreich, N. (2010) Thermite type reactions of different metals with iron-oxide and the influence of pressure. Propellants Explos. Pyrotech., 35 (3), 240–247.

18. Koch, E.-C. (2008) Special materials in pyrotechnics: V. Military applications of phosphorus and its compounds. Propellants Explos. Pyrotech., 33 (3), 165–176.

19. Koch, E.-C. (2010) Handbook of Combustion, Wiley-VCH Verlag GmbH, pp. 355–402.

20. Ward, J.R. (1981) MgH2 and Sr(NO3)2 pyrotechnic composition. US Patent 4, 302,259, USA.

21. Gash, A.E., Barbee, T. and Cervantes, O. (2006) Stab sensitivity of energetic nanolaminates. 33rd International Pyrotechnics Seminar, Fort Collins CO, July 16–21, pp. 59–70.

22. Cudzilo, S. and Trzcinski, W.A. (2001) Calorimetric studies of metal/polytetrafluoroethylene pyrolants. Pol. J. Appl. Chem., 45, 25–32.

23. Koch, E.-C., Weiser, V. and Roth, E. (2011) Combustion behaviour of binary pyrolants based on MgH2, MgB2, Mg3N2, Mg2Si, and polytetrafluoroethylene. EUROPYRO 2011, Reims, France, May 16–19.

24. Shidlovski, A.A. (1965) Fundamentals of Pyrotechnics.

25. Ellern, H. (1968) Military and Civilian Pyrotechnics, Chemical Publishing Company, New York.

26. McLain, J.H. (1980) Pyrotechnics from the Viewpoint of Solid State Chemistry, The Franklin Institute Press, Philadelphia, PA.

27. Conkling, J. (1985) Chemistry of Pyrotechnics – Basic Principles and Theory, Marcel Dekker, Inc., Basel.

28. Conkling, J. and Mocella, C.J. (2011) Chemistry of Pyrotechnics – Basic Principles and Theory, CRC Press, Boca Raton, FL.

29. Hardt, A. (2001) Pyrotechnics, Pyrotechnica Publications, Post Falls, ID.

30. Kosanke, K., Kosanke, B., Sturman, B., Shimizu, B., Wilson, A.M., von Maltitz, I., Hancox, R.J., Kubota, N., Jennings-White, C., Chapman, D., Dillehay, D.R., Smith, T. and Podlesak, M. (2004) Pyrotechnic Chemistry, Pyrotechnic Reference Series, Journal of Pyrotechnics Inc., Whitewater, CO.

Chapter 2

History

2.1 Organometallic Beginning

Although the unambiguous discovery of metal–fluorocarbon-based energetic materials did not occur until the mid-twentieth century, the way to these materials began nearly 100 years earlier. To begin with, in 1849, the British chemist Edward Frankland (1825–1899) (Figure 2.1), who was working with Robert Bunsen in Marburg/Germany, made attempts to isolate the ethyl radical, ·C2H5. Therefore, he treated iodoethane, C2H5I, with a surplus of zinc powder [2]. However, he did not get the radical but obtained a mixture of zinc(II) iodide and diethylzinc(0), Zn(C2H5)2 (Eq. 2.1). This was the first ever reported reaction of an electropositive metal with a halocarbon compound:

Figure 2.1 Edward Frankland [1].

2.1

In 1855, the Alsatian chemist Charles Adolphe Wurtz (1817–1884) observed the high reactivity of alkali metals with aliphatic halides (Eqs. 2.2a, 2.2b) and developed a C–C-coupling method that was later named after him [3]: