Chemistry of Pyrotechnics : Basic Principles and Theory

316 Pages·2019·8.325 MB·English

by  Chris Mocella, John A. Conkling

Chemistry of Pyrotechnics

Chemistry of Pyrotechnics
Basic Principles and Theory
Third Edition
John A. Conkling and Christopher J. Mocella
CRC Press
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Contents
Preface to the Third Edition: 2019 ............................................................................xi
Preface to the Second Edition: 2010 ......................................................................xiii
Preface to the First Edition: 1985 ............................................................................xv
Authors ...................................................................................................................xvii
Chapter 1 Introduction ..........................................................................................1
A Primer on Energetic Materials .........................................................1
Black Powder: The Original Pyrotechnic ............................................3
A Brief History and Cultural Significance ...........................................5
Chapter 2 Basic Chemical Principles ....................................................................9
Atoms and Molecules ...........................................................................9
The Mole Concept ..............................................................................17
Electron Transfer Reactions ...............................................................19
Oxidation–Reduction Theory ........................................................19
The Pyro Valence Method: A Simple Yet Powerful Technique ....21
Balancing an Equation ..................................................................24
Is a Chemical Compound Fuel or Oxygen Rich? ..........................25
Weight Ratio Calculations .............................................................26
Analyzing the Pyro Valence of a Mixture .....................................27
Three-Component Systems ...........................................................27
Pyro Valence Exercises .................................................................28
Additional Pyro Valence Problems ...............................................31
Electrochemistry ................................................................................32
Thermodynamics ................................................................................34
Introduction to Thermodynamics ..................................................34
Heat of Reaction ............................................................................36
Rates of Chemical Reactions .............................................................39
Energy-Rich Bonds ............................................................................42
States of Matter ..................................................................................43
Gases..............................................................................................44
Liquids ...........................................................................................45
The Solid State ..............................................................................46
Other Phases of Matter ..................................................................48
Acids and Bases ..................................................................................48
Light Emission ...................................................................................50
Molecular Emission .......................................................................53
“Black Body” Radiation/Emission ................................................54
“Green” Chemistry and Pyrotechnics: An Introduction ....................54
Chemical Principles: A Final Note ....................................................55
v
vi Contents
Chapter 3 Components of Energetic Compositions ............................................57
Introduction ........................................................................................58
Oxidizing Agents................................................................................60
Requirements .................................................................................60
Potassium Nitrate (KNO) .............................................................64
3
Potassium Chlorate (KClO) ..........................................................64
3
Potassium Perchlorate (KClO) .....................................................68
4
Green Pyrotechnics: The Perchlorate Issue ...................................69
Ammonium Perchlorate (NHClO) ..............................................71
4 4
Ammonium Perchlorate in the News ............................................72
Dinitramides: A “Green” Replacement for Perchlorates? .............73
Periodates: A “Green” Replacement for Perchlorates? .................74
5-Aminotetrazole: A “Green” Replacement for Perchlorates? ......75
Strontium Nitrate [Sr(NO)] .........................................................75
32
Barium Nitrate [Ba(NO)] ............................................................76
32
Iron Oxide [FeO and FeO] ........................................................76
2 3 3 4
Other Oxidizers .............................................................................77
Oxidizers without Oxygen .............................................................78
Summary on Oxidizers and Their Use ..........................................78
Oxidizer Selection: A Comparison................................................79
Fuels ...................................................................................................79
Requirements .................................................................................79
Introduction to Metal Fuels ...........................................................81
Aluminum (Al) ..............................................................................83
Magnesium (Mg) ...........................................................................84
Recovery of Demilitarized Magnesium: “Green”
Pyrotechnics Recycling .................................................................85
“Magnalium” (Magnesium–Aluminum Alloy) .............................85
Iron (Fe) .........................................................................................86
Other Metals ..................................................................................86
Introduction to Non-Metallic/Elemental Fuels .............................87
Sulfur .............................................................................................87
Boron .............................................................................................89
Silicon ............................................................................................90
Phosphorus ....................................................................................91
Sulfide Compounds .......................................................................92
Introduction to Organic Fuels ........................................................92
Natural Organic Fuels: Shellac and Red Gum ..............................94
Charcoal ........................................................................................94
Carbohydrates ................................................................................95
Other Organic Fuels ......................................................................96
Binders................................................................................................97
An Overview of Binders ................................................................97
Most Binders Are Also Fuels ......................................................101
Contents vii
Retardants .........................................................................................102
Brief Note on Colored Dyes ........................................................103
Catalysts ...........................................................................................104
Gas Volume Considerations: A Review ...........................................104
Examples .....................................................................................105
Conclusion and Best Practices in Component Selection ..................105
Chapter 4 Pyrotechnic Principles .....................................................................107
Introduction ......................................................................................107
Technical Parameters for Pyrotechnic Behavior ..............................108
Variability of Pyrotechnic Compositions .........................................113
Requirements for a “Good” High-Energy Mixture ..........................119
Preparation of High-Energy Mixtures: An Introduction .................121
Variation from Day to Day ...............................................................122
Possible Areas Where Variation in the Performance and
Sensitivity of Pyrotechnic Mixtures Can Occur During the
Manufacturing Process ................................................................123
Aging Effects on Pyrotechnic Compositions ...................................124
Pyrotechnic Principles: A Final Note ..............................................125
Chapter 5 Pyrotechnic Laboratories and Analysis ...........................................127
Introduction ......................................................................................128
The Pyrotechnic Laboratory ............................................................128
Storage .........................................................................................129
Safety: Personal Protective Equipment and Common Practices ....131
Composition Production ...................................................................132
Sizing Particles and Powders .......................................................133
Measuring Chemicals ..................................................................135
Mixing the Compositions ............................................................136
Using the Laboratory Hood “Firing Range” ....................................137
Setting Up the Lab Hood/Firing Range ......................................137
Igniting the Composition .............................................................138
Cleanup and a Final Note on Safety ............................................139
Analysis and Pyrotechnics ...............................................................139
Introduction to Analysis of Pyrotechnic Compositions ..............139
Thermal Analysis ........................................................................140
Heat Output Measurement ...........................................................144
Spectroscopy ................................................................................144
Microscopy ..................................................................................145
Moisture Analyzer .......................................................................145
Other Equipment and Techniques ...............................................145
Process Hazard Analysis ..................................................................146
Laboratories and Analysis: A Final Note .........................................146
viii Contents
Chapter 6 Ignition and Propagation ..................................................................147
Introduction to Ignition Principles ...................................................148
Ignition Techniques .....................................................................148
Ignition: Initial and Continuing Events .......................................149
Combustion, Deflagration, and Detonation .................................149
Ignition Factors: Part 1 ................................................................150
Lattice Structure, Motion, Reactivity, and “The Tammann
Temperature” ...............................................................................152
Ignition Factors: Part 2 ................................................................153
Ignition Temperatures ..................................................................157
Methods for Determining Ignition Temperatures .......................158
Summary of Ignition ...................................................................161
Propagation of Burning ....................................................................161
Introduction and Measuring Propagation ....................................161
Effects from Component Selection ..............................................162
Effects from Mass Ratio and Stoichiometry ...............................163
Effect from Other Factors: Heat Transfer, Loading Density,
and Moisture ................................................................................164
Effect of External Pressure and Confinement .............................165
Effect of External Temperature ...................................................168
Burning Surface Area ..................................................................169
Deflagration-to-Detonation Transitions (DDT) ...........................170
Summary of Burn Rate ...............................................................171
Combustion Flame Temperature ......................................................171
Propagation Index.............................................................................175
Ignition and Propagation: A Final Note ...........................................176
Chapter 7 Sensitivity .........................................................................................177
Sensitivity Testing: An Introduction ................................................177
Ignition Sensitivity: A Statistical Event .......................................178
Sensitivity Testing: Safety Concerns ...........................................179
Variability in Sensitivity Testing Results ....................................180
Spark Sensitivity ...............................................................................181
Friction Sensitivity ...........................................................................184
Impact Sensitivity .............................................................................186
Thermal Sensitivity ..........................................................................189
Thermal Sensitivity Overview .....................................................189
Divergent Sensitivity Changes .....................................................192
Shock Sensitivity: A Brief Note .......................................................193
Redesigning a Composition for Sensitivity Considerations .............194
Pyrotechnic Sensitivity: Summary ...................................................195
Chapter 8 Heat Compositions: Ignition Mixes, Delays, and Thermites ...........197
Heat Production ................................................................................198
Contents ix
Igniters and Delays: Terminology ....................................................198
Ignition Compositions and First Fires ..............................................201
Delay Compositions .........................................................................204
Thermodynamics and Delay Compositions ................................206
Stoichiometry and Delay Compositions ......................................207
“Green Pyrotechnics” for Delay Systems ....................................209
Thermite and Thermate Mixtures ....................................................210
Heat Compositions: Summary .........................................................212
Chapter 9 Propellants: A Brief Overview .........................................................213
Propellants: An Introduction ............................................................214
The Original Propellant: Black Powder ...........................................215
Smokeless Powders ...........................................................................216
Propellants for Launch Vehicles.......................................................220
Projectile vs. Rocket Propellants ......................................................221
Modern Approaches in Propellants ..................................................222
Chapter 10 Light and Color Production ..............................................................225
Introduction ......................................................................................225
White-Light Compositions ...............................................................226
Overview of White-Light Production ..........................................226
Illuminating Compositions and Flares ........................................227
“Photoflash” Mixtures ................................................................230
“Green Pyrotechnics” for Photoflash Compositions ...................231
Spark Production ..............................................................................231
Strobes and “Twinklers” ..................................................................233
Other Light Effects: Flitter and Glitter ............................................234
Colored-Light Production .................................................................235
Overview of Colored-Light Production .......................................235
Oxidizer Selection ......................................................................238
Fuels and Burning Rates ............................................................239
The Veline Color Series ...............................................................240
Color Intensification with Chlorine .............................................240
Red Flame Compositions: Classic Strontium-Based Systems .....242
Red Flame Compositions: Lithium-Based Alternatives ..............243
Green Flame Compositions: Classic Barium-Based Systems .....245
Green Flame Compositions: “Green Pyrotechnics” with
Boron-Based Compositions .........................................................248
Blue Flame Compositions: Classic Copper Chloride-Based
Systems ........................................................................................248
Blue Flame Compositions: “Green Pyrotechnics” with
Copper Iodide and Copper Bromide ...........................................251
Purple Flame Compositions .......................................................251
Yellow Flame Compositions: Sodium .........................................252