Low sensitivity energetic materials [Elektronische Ressource] / vorgelegt von Jan Matthew Welch

Jan Matthew Welch

Informations

• Publié par: ludwig-maximilians-universitat_munchen
• Publié le: 01 janvier 2008
• Nombre de lectures: 17
• Langue: English
• Poids de l'ouvrage: 4 Mo

Extrait

Dissertation zur Erlangung des Doktorgrades
der Fakultät für Chemie und Pharmazie
der Ludwig-Maximilians-Universität München









Low Sensitivity Energetic Materials

















Vorgelegt von
Jan Matthew Welch
Aus
Albany, New York, Vereinigte Staaten von Amerika

2008

Erklärung


Diese Dissertation wurde im Sinne von § 13 Abs. 3 bzw. 4 der Promotionsordnung
vom 29. Januar 1998 von Prof. Dr. Thomas M. Klapötke betreut.


Ehrenwörtliche Versicherung
Diese Dissertation wurde selbständig, ohne unerlaubte Hilfsmittel erarbeitet.
München, den ………………………………………





………………………………………
(Jan M. Welch)






Dissertation eingereicht am:
1. Gutachter Prof. Dr. Thomas M. Klapötke
2. Gutacher Prof. Dr. Jürgen Evers
Mündliche Prüfung am
Acknowledgement
As always (and as it should be) the first person a student should thank is the bill-payer
(better known as a mentor), in this case, Prof. T. M. Klapötke, who for the past 4 years has
done much more than just paying bills and being inordinately patient with a stubborn
foreigner. All that really needs saying at this point is “thank you for the opportunity of a
lifetime.” I’ve tried to seize it with as all the enthusiasm I could. Prof. J. Evers’ boundless
enthusiasm, knowledge, humor and encouragement made a good deal of this work not only
possible but fun to boot. Prof. K. Karaghiosoff managed to brighten even the dullest days
with a never ending supply of stories and good humor. Also, worth mention are
crystallographic aid and NMR assistance at all hours of the day or night on any day of the
week. For helping me get off on the right foot both in the lab and out I owe a great deal to Dr.
M-j Crawford. She is also the only person I know who has managed to share working space
with me for nearly 4 years; that in and of itself speaks volumes. I’m also grateful for advice,
both chemical and career from Dr. B. Krumm as well as encouragement when things got
tough. Dr. Peter Mayer also appears here not only for measuring many of the structures in
this work but also for having patience with an X-ray novice and supplying many of the files
critical to this work more than once. Lastly, but certainly not least, I want to thank Ms. I.
Scheckenbach, without whom I would be, among very many other things, homeless.
There are numerous other, friends, colleagues and family members who played a role in this
work. I’m not even going to try to list all of them as I fear I may inadvertently omit someone
and cause more offense than I already have. So, with that I’ll just say you know who you are
and what you’ve done and I thank you for it!


































“You have to ask yourself, ‘are you feeling lucky?’ well are you punk?”
(Clint Eastwood, in ‘Dirty Harry’)
And yes I do, very. 1 General Introduction 1
1.1 Background and Terminology 1
1.2 Chemistry and Energetic Materials 4
1.3 Goals of this Study 9
1.3.1 Chapter 1: Energetic Salts 9
1.3.2 Chapter 2: Temperature dependent studies of FOX-7 10
1.4 References 10
2 Ionic Energetic Materials 11
2.1 Introduction to ionic energetic materials 11
2.2 Results and Discussion 14
2.2.1 Synthesis 14
2.2.2 Vibrational Spectroscopy 17
2.2.3 NMR Spectroscopy 23
2.2.4 X-ray Structures 27
2.2.5 Energetic Properties 64
2.3 Conclusions 75
2.4 Experimental 76
2.4.1 Caution 76
2.4.2 General 76
2.4.3 Bomb Calorimetry 77
2.4.4 X-ray Crystallography 77
2.4.5 Computational Methods 78
2.4.6 Syntheses 79
2.5 References 93
3 FOX-7 101 3.1 Introduction 101
3.2 Results and Discussion 104
3.2.1 DSC 104
3.2.2 Temperature resolved qualitative analysis of bulk material 108
3.2.3 Single crystal X-ray structures 116
3.3 Conclusions 167
3.4 Future Work 169
3.5 Experimental Section 172
3.5.1 Caution 172
3.5.2 General 172
3.5.3 Single Crystal Experiments 173
3.5.4 Powder Diffraction Experiments 174
3.6 References 174
4 Appendices 177
4.1 Chapter 1 177
Brief description of the graph set description of hydrogen-bond patterns 177
4.2 Chapter 2 179
1 General Introduction
1.1 Background and Terminology.
Development of energetic materials, in other words, substances that burn, combust rapidly
or explode under certain conditions constitutes one of mankind’s early scientific
investigations. Although, explosive materials were developed later than other early human
ndtechnologies (2 century BC), combustion and the ability to control it is considered, one of
the defining technological achievements of early humans. The history of energetic materials
1, 2is well chronicled elsewhere and therefore mentioned here only in passing. Early energetic
materials were used primarily for entertainment (fireworks), but their potential in the realm of
armed conflict was also recognized. An understanding and application of energetic materials
in conflict has served, throughout history, as the key technological advantage of one
civilization over another. In modern times, however, the manifold application of energetic
materials reaches well beyond those original uses in entertainment and warfare. Today,
energetic materials find use in mining, construction, demolition, safety equipment (signal
flares, fire suppression systems, etc.), rocketry and space exploration among other civil and
military applications.
Having established the utility and wide area of application of “energetic materials,”
definition of the terms used above is helpful for the sake of clarity. As suggested above,
“energetic materials” can be divided into several classes, namely, explosives, propellants and
pyrotechnics, each of which requires a definition of its own. Explosives are most often
vaguely defined as “a solid or liquid substance (or mixture of substances) which is in itself
capable by chemical reaction of producing gas at such a temperature and pressure and at such
a speed as to cause damage to the surroundings.” Propellants may be defined as substances or
mixtures of substances that burn rapidly or deflagrate (deflagrate is defined specifically
below) releasing a significant volume of gas at a rate sufficient to raise pressure and provide
propulsive force (or impulse). Whereas the purpose of explosives and propellants is the
1
transfer of stored chemical energy to macroscopic kinetic energy, the purpose of pyrotechnic
substances and mixtures is to use this stored chemical energy to generate defined visual and
1, 2acoustic effects.
The primary objectives of this work are in the area of explosives and to a lesser extent
propellants. Therefore, further discussion of pyrotechnics is omitted. However, several more
scientific definitions of terms concerning explosives and propellants may be useful. Firstly,
in order to more precisely define the term “explosives” a definition of an “explosion” is
necessary. Unfortunately, “explosion” is another term lacking a specific, scientific definition.
An explosion is vaguely defined as occurring when a large amount of accumulated energy is
1, 2released suddenly. The source of the energy released maybe physical, chemical or nuclear.
Therefore, rather than defining chemical explosive materials redundantly as those that, under
certain conditions, release their energy suddenly, perhaps it is useful to discuss “explosions”
in terms of the rate at which chemical energy is released.
Detonation is the fastest release of chemical energy and is propagated, not by heat transfer,
but by a supersonic shockwave traveling though the materials. The shockwave propagation is
maintained by the rapid release of chemical energy immediately behind the wave front. The
shockwave exiting the material results in the destructive or propulsive force of the material.
Deflagration reactions proceed through energetic materials at slightly subsonic linear
velocities and are propagated principally by heat transfer. Deflagration can be considered an
intermediate state between detonation and combustion. Combustion or simple burning
reactions occur at slower rates and are defined as complex self-sustaining exothermic
oxidation reactions. Therefore, in this work, chemical explosives are treated as compounds
capable releasing their energy in the form of a detonation and these materials will be
discussed principally in terms of their detonation properties. Propellants on the other hand,
may be explosive materials, but release their energy principally through gas generation as the
1, 2result of a deflagration.
2
As evidenced by their definitions, explosives and propellants have different and varied
applications. Explosive and propellant materials and mixtures can be further classified
depending on eas