Table Of ContentDK4506 Cover 11/17/10 10:43 AM Page 1
C M Y CM MY CY CMY K
CHEMISTRY
MC
O
J A. C O N
OHN ONKLING C K
E L
CHRISTOPHER J. MOCELLA LL IN
A G
Chemistry
C
of Pyrotechnics
h
Basic Principles and Theory e
m
SECOND EDITION
i
s
Primarily driven by advancing technology and concerns for safety, advancement
t
in the world of pyrotechnics and high-energy materials has exploded in the past
r
25 years. The promulgation of new government regulations places new and
y
more stringent restrictions on the materials that may be used in energetic
mixtures. These regulations now mandate numerous training programs and
o
initiate other actions, such as OSHA’s Process Safety Management standard,
intended to eliminate accidents and incidents. Unfortunately, the United States f
lacks an organized, broad-range academic program to cover the science and use
P
of energetic materials and educate the next generation of pyrotechnicians.
y
Designed as a bridge to provide a smooth and confident transition for personnel
r
coming from a chemistry background into the practical world of high-energy
o
materials, Chemistry of Pyrotechnics: Basic Principles and Theory, Second
Edition emphasizes basic chemical principles alongside practical, hands-on t
knowledge in the preparation of energetic mixtures and examines the interactions e
between and adaptations of pyrotechnics to changing technology in areas such c
as obscuration science and low-signature flame emission.
h
Much more than a simple how-to guide, the book discusses chemical and n
pyrotechnic principles, components of high-energy mixtures, and elements of
i
ignition, propagation, and sensitivity. It offers heat compositions, including c
ignition mixes, delays, thermites, and propellants and investigates the production
s
of smoke and sound as well as light and color.
Promoting the growth and expansion of pyrotechnics as a science, Chemistry
ES
of Pyrotechnics: Basic Principles and Theory, Second Edition teaches
DE
practitioners how to apply chemical principles and IC
logic to energetic materials and, thereby, make the DK4506 TO
I
field as productive, useful, and safe as possible. ON
ND
6000 Broken Sound Parkway, NW
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Abingdon, Oxon OX14 4RN, UK
Chemistry
of Pyrotechnics
Basic Principles and Theory
S E
ECOND DITION
Cover photo by Rob Stowers, courtesy of Pyrotecnico. Red, white, and blue bursts
highlight a 4th of July fireworks spectacular.
J A. C C M
OHN ONKLING & HRIS OCELLA
Chemistry
of Pyrotechnics
Basic Principles and Theory
S E
ECOND DITION
Boca Raton London New York
CRC Press is an imprint of the
Taylor & Francis Group, an informa business
CRC Press
Taylor & Francis Group
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© 2010 by Taylor and Francis Group, LLC
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Contents
Preface to the Second Edition—2010 .......................................................................ix
Preface to the First Edition—1985............................................................................xi
Chapter 1 Introduction ..........................................................................................1
A Brief History .....................................................................................4
References ............................................................................................6
Chapter 2 Basic Chemical Principles ....................................................................7
Atoms and Molecules ...........................................................................7
The Mole Concept ..............................................................................15
Electron-Transfer Reactions ...............................................................17
Oxidation-Reduction Theory .........................................................17
The Pyro Valence Method—A Simple Yet Powerful Technique ......19
Balancing an Equation ..................................................................22
Is a Chemical Compound Fuel or Oxygen Rich? ..........................22
What about Methylammonium Perchlorate, CH NH ClO ? .........23
3 3 4
Weight Ratio Calculations .............................................................24
Analyzing a Mixture .....................................................................25
Three-Component Systems ...........................................................25
Pyro Valence Exercises .................................................................26
Additional Pyro Valence Problems ...............................................29
Electrochemistry ................................................................................30
Thermodynamics ................................................................................33
Heat of Reaction ............................................................................34
Rates of Chemical Reactions .............................................................38
Energy-Rich Bonds ............................................................................40
States of Matter ..................................................................................41
Gases..............................................................................................42
Liquids ...........................................................................................43
The Solid State ..............................................................................44
Acids and Bases ..................................................................................46
Instrumental Analysis ........................................................................48
Light Emission ...................................................................................50
Molecular Emission .......................................................................54
Black Body Emission ....................................................................54
The Pyrotechnic Laboratory ..............................................................55
Particle Size ...................................................................................55
Thermal Analysis ..........................................................................56
v
© 2011 by Taylor & Francis Group, LLC
vi Contents
Moisture Analyzer .........................................................................56
Heat Output Measurement .............................................................56
Other Equipment ...........................................................................56
References ..........................................................................................57
Chapter 3 Components of High-Energy Mixtures ..............................................59
Introduction ........................................................................................60
Oxidizing Agents................................................................................62
Requirements .................................................................................62
Potassium Nitrate (KNO) .............................................................65
3
Potassium Chlorate (KClO) ..........................................................65
3
Potassium Perchlorate (KClO ) .....................................................69
4
The Perchlorate Issue—2010 .........................................................69
Ammonium Perchlorate (NH ClO ) ..............................................71
4 4
Ammonium Perchlorate in the News ............................................72
Strontium Nitrate [Sr(NO)] .........................................................72
32
Barium Nitrate [Ba(NO)] ............................................................73
32
Other Oxidizers .............................................................................73
Oxidizer Selection: A Comparison................................................75
Fuels ...................................................................................................75
Requirements .................................................................................75
Metals ............................................................................................77
Aluminum (Al) ..............................................................................78
Magnesium (Mg) ...........................................................................79
Magnalium (Magnesium-Aluminum Alloy) .................................80
Iron ................................................................................................80
Other Metals ..................................................................................80
Nonmetallic Element Fuels ...........................................................81
Sulfur .............................................................................................82
Boron .............................................................................................82
Silicon ............................................................................................83
Phosphorus ....................................................................................83
Sulfide Compounds .......................................................................84
Organic Fuels .................................................................................84
Specific Organic Fuels ...................................................................86
Carbohydrates ................................................................................87
Other Organic Fuels ......................................................................88
Binders................................................................................................89
Most Binders Are Also Fuels ........................................................92
Retardants ...........................................................................................93
Catalysts .............................................................................................93
Gas Volume ........................................................................................94
Conclusion ..........................................................................................94
References ..........................................................................................95
© 2011 by Taylor & Francis Group, LLC
Contents vii
Chapter 4 Pyrotechnic Principles .......................................................................97
Introduction ........................................................................................97
Variability .........................................................................................102
Requirements for a Good High-Energy Mixture .............................108
Preparation of High-Energy Mixtures .............................................109
Process Hazard Analysis ..................................................................111
Variation from Day to Day ...............................................................111
Possible Areas Where Variation in the Performance
and Sensitivity of Pyrotechnic Mixtures Can Occur
During the Manufacturing Process .............................................112
References ........................................................................................112
Chapter 5 Ignition and Propagation ..................................................................115
Ignition Principles ............................................................................116
Summary of Ignition ...................................................................127
Propagation of Burning ....................................................................128
Factors .........................................................................................128
Effect of External Pressure ..........................................................131
Effect of External Temperature ...................................................134
Burning Surface Area ..................................................................135
Summary of Burn Rate ...............................................................136
Combustion Temperature ............................................................136
Propagation Index ........................................................................140
References ........................................................................................141
Chapter 6 Sensitivity .........................................................................................143
Sensitivity Testing ............................................................................143
Spark Sensitivity ...............................................................................146
Friction Sensitivity ...........................................................................148
Impact Sensitivity .............................................................................150
Thermal Sensitivity ..........................................................................152
Redesigning a Composition ..............................................................156
Summary ..........................................................................................157
References ........................................................................................158
Chapter 7 Heat Compositions: Ignition Mixes, Delays, Thermites, and
Propellants ........................................................................................159
Heat Production ................................................................................160
Delay Compositions .........................................................................163
Ignition Compositions and First Fires ..............................................168
Thermite Mixtures ...........................................................................171
Propellants ........................................................................................172
References ........................................................................................178
© 2011 by Taylor & Francis Group, LLC
viii Contents
Chapter 8 Color and Light Production ..............................................................179
Introduction ......................................................................................179
White Light Compositions ...............................................................180
Introduction .................................................................................180
Photoflash Mixtures .....................................................................183
Sparks ...............................................................................................184
Flitter and Glitter ..............................................................................186
Crackle Effects .................................................................................187
Color .................................................................................................188
Introduction .................................................................................188
Oxidizer Selection .......................................................................190
Fuels and Burning Rates .............................................................191
Color Intensifiers .........................................................................192
Red Flame Compositions ............................................................193
Green Flame Compositions .........................................................194
Blue Flame Compositions............................................................196
Purple Flame Compositions ........................................................197
Yellow Flame Compositions ........................................................198
Beyond the Visible Region ...............................................................200
References ........................................................................................201
Chapter 9 Smoke and Sound .............................................................................203
Smoke Production ............................................................................203
Colored Smoke Mixtures .............................................................205
White Smoke Production .............................................................208
HC Replacement Research ..........................................................210
Noise Production ..............................................................................211
Whistles .......................................................................................214
References ........................................................................................215
Appendix A ...........................................................................................................217
Appendix B ...........................................................................................................219
© 2011 by Taylor & Francis Group, LLC
Preface to the Second
Edition—2010
In the twenty-five years that have passed since the first edition of this book was
published, the world of pyrotechnics and high-energy materials has continued to
undergo significant changes. The changes have been driven primarily by concerns
for safety—of personnel working with energetic materials and of the communi-
ties located near facilities producing energetic materials—as well as concerns for
the environment. One result of the pressure for change has been the promulgation
of new government regulations placing restrictions on the materials that may be
used in energetic mixtures, mandating numerous training programs, and initiat-
ing other actions, such as OSHA’s Process Safety Management standard, intended
to eliminate accidents and incidents. And almost all of the personnel who entered
the field of energetic materials in the 1950s and 1960s have now retired and taken
with them their years of hands-on, practical knowledge in the preparation of ener-
getic mixtures.
The International Pyrotechnics Seminars have grown in frequency and signifi-
cance since the first edition of this book was published in 1985. There is now at
least one seminar a year, either in Colorado or a non–United States location, and
the proceedings from these seminars continue to be a great source of information
regarding ongoing pyrotechnic research. In addition, the International Symposium
on Fireworks (ISF) continues to be held every other year in Canada or elsewhere, and
these sessions always produce an interesting blend of technical papers.
The Pyrotechnics Guild International (PGI) has matured into a respected group
of pyrotechnics enthusiasts and researchers who are making significant contribu-
tions in the area of fireworks technology.
A new journal, appropriately named the Journal of Pyrotechnics, has provided a
vehicle for the prompt publication of research and review papers in the broad field
of pyrotechnics.
On the negative side, we in the United States continue to lack any organized,
broad-range academic programs covering the science of energetic materials. The
New Mexico Institute of Technology is offering a program in explosive technology,
and this is a great first step. More and more, the field of pyrotechnics is interacting
with and adapting to changing technology in areas such as obscuration science and
low-signature flame emission. Greater academic interest in the science of pyrotech-
nics would be a valuable asset for this country.
I thank my numerous colleagues and coworkers over the past twenty-five years for
their interesting discussions, helpful comments, and constructive criticism. First on
the list is Joseph Domanico, my friend and colleague with the Summer Pyrotechnic
Seminar program at Washington College since 1984—Joe is truly a unique indi-
vidual with a broad knowledge of the field of energetic materials.
ix
© 2011 by Taylor & Francis Group, LLC
