Boron-based fuel-rich propellant: properties, combustion, and technology aspects

347 Pages·2019·18.022 MB·English

by  Pang, Weiqiang

Boron-Based Fuel-Rich
Propellant
Properties, Combustion, and
Technology Aspects

Boron-Based Fuel-Rich
Propellant
Properties, Combustion, and
Technology  Aspects
WeiQiang Pang
Luigi T. De Luca, XueZhong Fan, Oleg G. Glotov,
FengQi Zhao
CRC Press
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Contents
Preface ...........................................................................................................................................xiii
Foreword ........................................................................................................................................xv
Summary .....................................................................................................................................xvii
Authors .........................................................................................................................................xix
Abbreviations ..............................................................................................................................xxi
1. Basic Formulations and Components of Ramjet Propellants ........................................1
1.1 Fuel-Rich Propellants ...................................................................................................1
1.2 Main Components of Boron-Based Fuel-Rich Solid Rocket Propellant ................2
1.2.1 Binders ...............................................................................................................2
1.2.2 Metal Fuels ........................................................................................................2
1.2.2.1 Boron in Nature ................................................................................4
1.2.2.2 Amorphous and Crystalline Boron ...............................................4
1.2.2.3 Preparation of Amorphous Boron Powder ...................................5
1.2.2.4 Physicochemical Properties of Boron Powders ............................6
1.2.2.5 Boron–Aluminum or Boron–Magnesium Alloy Powder ...........7
1.2.3 Oxidizers and Solid Fillers .............................................................................7
1.2.4 Combustion Catalysts and Stabilizers ..........................................................8
1.2.5 Combustion Stabilizer .....................................................................................9
1.2.6 Bonding Agents ................................................................................................9
1.2.7 Antioxidants ...................................................................................................12
1.3 Main Properties of Boron-Based Fuel-Rich Solid Rocket Propellant ..................13
1.3.1 E nergetic Properties ......................................................................................13
1.3.2 P rocessibility (Rheological and Surface-Interfacial Properties) ..............14
1.3.2.1 Effect of Content .............................................................................16
1.3.2.2 Impact of Particle Properties on Viscosity ..................................16
1.3.3 C ombustion Properties .................................................................................18
1.3.4 P erformance Characteristics of Boron-Based Fuel-Rich Propellants .....19
1.4 Main Problems of Boron-Based Fuel-Rich Solid Rocket Propellant ....................20
1.5 Recent Progress of Boron-Based Fuel-Rich Solid Rocket Propellant ...................22
1.5.1 D evelopment of Modification of Boron Powder ........................................22
1.5.2 C urrent Research Situation of Boron-Based Fuel-Rich Solid Rocket
Propellants ......................................................................................................23
1.6 Prospects of Boron-Based Fuel-Rich Solid Rocket Propellant ..............................28
References ...............................................................................................................................29
2. Surface Modification and Characterization of Boron Powder ....................................33
2.1 Introduction .................................................................................................................33
2.2 Deterioration of Propellant Manufacturing Process Caused by Boron and
Its Mechanism .............................................................................................................34
2.2.1 X PS Analysis ...................................................................................................34
2.2.2 R heological Analysis .....................................................................................34
v
vi Contents
2.2.3 Infrared Analysis ...........................................................................................36
2.2.4 Mechanism of the Deteriorated Process in HTPB Fuel-Rich
Propellant ......................................................................................................37
2.3 Preparation Process of Agglomerated Boron Particles ..........................................38
2.3.1 Pretreatment of Amorphous Boron Powder ..............................................39
2.3.2 Coating of Amorphous Boron Powder .......................................................40
2.3.3 Agglomeration and Prills of Amorphous Boron Powder ........................43
2.4 The Particle Size Distribution and Fractal Dimension Characterization of
Agglomerated Boron Particles ..................................................................................50
2.4.1 Measuring Principle of Fractal Dimension ................................................50
2.4.2 The Particle Size Fractal Dimension of Solid Additives in Solid
Propellants ......................................................................................................51
2.4.3 Fractal Dimension of Surface Roughness and Size Distribution
of Agglomerated Boron Particles and Its Relationship with
Rheological Properties of Fuel-Rich Propellant ........................................56
2.5 Bulk Density of Agglomerated Boron Particles ......................................................59
2.5.1 Bulk Density Measurement of Agglomerated Boron Particles ...............60
2.5.2 Two Types of Bulk Density Comparison of Agglomerated Boron
Particles ...........................................................................................................60
2.5.3 Dispersion Property of Agglomerated Boron Particles ............................62
2.5.4 Effects of Vibration Times on the Tap Bulk Density of
Agglomerated Boron Particles .....................................................................63
2.6 Robustness of Agglomerated Boron Particles .........................................................64
2.6.1 Robustness Test Principle of Agglomerated Boron Particles...................64
2.6.2 Basic Physical Parameters of Agglomerated Boron Particles ..................65
2.6.3 Effects of Different Factors on the Robustness of Agglomerated
Boron Particles................................................................................................65
2.7 Surface Properties of before and after Agglomeration Boron Particles ..............68
2.7.1 Morphology of Agglomerated Boron Particles ..........................................68
2.7.2 Acidity Analysis of Agglomerated Boron Particles ..................................68
2.7.3 X-Ray Analysis of Agglomerated Boron Particles .....................................71
2.7.4 Coating Degree of Agglomerated Boron Particles ....................................71
2.8 Crystal Boron Powder ................................................................................................72
2.8.1 The Physicochemical Properties of Crystal Boron Powder .....................72
2.8.2 XRD Analysis of Crystal Boron Powder .....................................................74
2.8.3 XPS Analysis of Crystal Boron Powder ......................................................74
2.8.4 Surface Acid Property of Crystal Boron Powder.......................................76
2.9 Boron/Magnesium (Aluminum) Composite Powders ..........................................76
2.9.1 Morphology and Particle Size Distribution of B/Mg (Al)
Composite Powders .......................................................................................76
2.9.2 Density of B/Mg (Al) Composite Powders .................................................78
2.9.3 X-Ray Analysis of B/Mg (Al) Composite Powders ....................................78
2.9.4 Surface Acid Degree of B/Mg (Al) Composite Powders ..........................79
References ...............................................................................................................................80
3. The Surface-Interfacial Properties of Boron and Binder System ...............................83
3.1 Problem Statement ......................................................................................................83
3.2 Measuring Principle and Methods ...........................................................................83
3.2.1 Surface-Interfacial Chemical Principle .......................................................83
Contents vii
3.2.2 Measuring Principle of Contact Angle .......................................................85
3.2.3 Calculating Principle of Adhesion Work and Spread Coefficient ..........86
3.2.4 Measuring Method ........................................................................................86
3.3 Surface-Interfacial Properties of ABPs and Binder System ...................................87
3.3.1 Surface Properties of ABPs ...........................................................................88
3.3.2 Calculation of Contact Angle and Surface Free Energy ...........................89
3.3.3 Calculation of Adhesion Work and Spread Coefficient ...........................90
3.3.4 Surface Modification Mechanism of ABPs .................................................91
3.4 Surface-Interfacial (Multi-Interfacial) Properties of Fuel-Rich Solid
Propellant Containing ABPs .....................................................................................96
3.5 Effects of ABP on the Microstructures of Fuel-Rich Solid Propellant .................97
References ...............................................................................................................................98
4. Rheological Properties ......................................................................................................101
4.1 Boron Propellant Slurries .........................................................................................101
4.2 Characterization and Measurement of Rheological Properties of Propellant .....101
4.2.1 Characterization of Rheological Properties .............................................101
4.2.2 Preparation of Samples ...............................................................................102
4.2.3 Measuring Methods ....................................................................................103
4.3 Effects of Different Elements on the Rheological Properties of Fuel-Rich
Solid Propellants .......................................................................................................103
4.3.1 Rheological Properties of HTPB Binder ...................................................103
4.3.2 Rheological Properties of ABP/HTPB Slurry ..........................................104
4.3.3 Effects of Different Ingredients on the Rheological Properties of
Fuel-Rich Solid Propellant ..........................................................................107
4.4 Processibility of Boron-Based Fuel-Rich Solid Rocket Propellants ...................117
4.4.1 Designing Principle of Boron-Based Fuel-Rich Solid Rocket
Propellant ......................................................................................................118
4.4.2 Processibility of Fuel-Rich Solid Propellant ............................................118
4.4.3 Formulations of Fuel-Rich Solid Propellant Containing
Agglomerated Boron Particles ...................................................................118
4.4.4 Preparation of Boron Fuel-Rich Solid Propellant Samples ....................119
4.4.5 P rocessibility of Boron Fuel-Rich Solid Propellant Samples .................119
References .............................................................................................................................121
5. Energetic Properties ...........................................................................................................123
5.1 General Description ..................................................................................................123
5.2 Estimation of Energetic Properties of Boron-Based Fuel-Rich Solid
Propellant ...................................................................................................................123
5.2.1 C alculation of Energetic Properties of Fuel-Rich Solid Propellant ......125
5.2.2 T heoretical Calculation and Measurement Methods of
Combustion Heat .........................................................................................128
5.2.3 P ropellant Density Measurements ............................................................129
5.3 Technical Approaches to Increase the Energetic Properties of Fuel-Rich
Solid Propellant .........................................................................................................129
5.3.1 Addition of Metal Fuels ..............................................................................129
5.3.2 Effective Additives .......................................................................................130
5.4 Effect of Formulation Factors on the Energetic Properties of Boron-Based
Fuel-Rich Solid Propellant .......................................................................................131
viii Contents
5.4.1 Binder Type ...................................................................................................131
5.4.2 Boron Fuel .....................................................................................................133
5.4.3 Oxidizers and Solid Fillers .........................................................................138
References .............................................................................................................................145
6. Combustion Properties ......................................................................................................147
6.1 Introduction ...............................................................................................................147
6.2 Characterization and Measurement of Combustion Properties of
Fuel-Rich Solid Propellant .......................................................................................148
6.2.1 Characterized Parameters ..........................................................................148
6.2.1.1 Burning Rate .................................................................................149
6.2.1.2 Burning Rate Pressure Exponent ...............................................149
6.2.1.3 Burning Rate Temperature Sensitivity ......................................149
6.2.2 Measuring Methods ....................................................................................150
6.3 Technical Approaches to Improve the Combustion Properties of
Boron-Based Fuel-Rich Solid Propellant ...............................................................151
6.3.1 Addition of Agents ......................................................................................151
6.3.2 Surface Coating of Boron Powder ..............................................................155
6.3.2.1 Surface Coating by Means of LiF, Fluorine Rubber, and
Silane ..............................................................................................155
6.3.2.2 Surface Coating by Means of Oxidizers or Energetic
Binders ...........................................................................................156
6.3.2.3 Replacing Inert Binder by Energetic Binders ...........................156
6.4 Ignition and Combustion of Boron Powder ..........................................................158
6.4.1 I gnition Model of Boron Powder ...............................................................159
6.4.2 I gnition Model of Agglomerated Boron Particles ...................................159
6.4.3 I gnition Properties of Boron Powder in Different Atmosphere ............161
6.4.3.1 Combustion in the Air .................................................................161
6.4.3.2 Ignition of Boron in an Environment Containing Water
Vapor ..............................................................................................162
6.4.3.3 Ignition of Boron Particles in Cl ...............................................163
2
6.4.3.4 Ignition of Boron Particles in an Environment Containing
Fluorine ..........................................................................................164
6.4.3.5 Ignition of Boron Particles in an Environment Containing
Nitrogen .........................................................................................165
6.4.4 Emission Spectrum and Flame Morphology of Boron Powder in
Different Atmosphere .................................................................................165
6.4.4.1 Pure N/Pure O ...........................................................................167
2 2
6.4.4.2 H O/O Mixed Atmosphere ........................................................168
2 2
6.4.4.3 N/O Mixed Atmosphere ...........................................................168
2 2
6.5 Effects of Boron on the Combustion Properties of Fuel-Rich Solid Propellant ....171
6.5.1 Combustion Properties of Boron-Based Fuel-Rich Solid Propellant ....172
6.5.2 T hermal Decomposition of Surface-Modified Boron Particles .............173
6.5.3 C ombustion Properties of Fuel-Rich Solid Propellant Containing
Crystal Boron Powder .................................................................................176
6.5.4 T hermal Decomposition of Fuel-Rich Solid Propellant Containing
Crystal Boron Particles ................................................................................177
6.5.5 C ombustion Properties of Fuel-Rich Solid Propellant Containing
Boron (Magnesium) Composite Particles .................................................179
Contents ix
6.5.6 Solid Motor Tests of Fuel-Rich Solid Propellant Containing
Agglomerated Boron Particles ...................................................................180
6.6 Combustion Mechanism of Fuel-Rich Solid Propellants ....................................183
6.6.1 Combustion Flame Structures ...................................................................183
6.6.1.1 The Combustion Flame Structure of Boron-Based
Fuel-Rich Propellant ....................................................................184
6.6.1.2 Effect of Agglomerated Boron Particles on the
Combustion Flame Structure of Fuel-Rich Propellant ...........185
6.6.1.3 Effect of Coated Materials of AP and LiF on the
Combustion Flame Structure of Fuel-Rich Propellant ...........185
6.6.2 Combustion Wave Temperature ................................................................186
6.6.2.1 The Combustion Wave Structure of Boron-Based
Fuel-Rich Propellant ....................................................................187
6.6.2.2 Effect of Agglomeration on the Combustion Wave
Structure of Boron-Based Fuel-Rich Propellant.......................189
6.6.2.3 Effect of AP Coating on the Combustion Wave Structure
of Boron-Based Fuel-Rich Propellant ........................................192
6.6.2.4 Effect of LiF Coating on the Combustion Wave Structure
of Boron-Based Fuel-Rich Propellant ........................................194
6.6.3 Flameout Surface Analysis .........................................................................196
6.6.4 Primary Combustion Product Analysis ...................................................198
6.6.4.1 Collection of Primary Combustion Products ...........................199
6.6.4.2 Morphology and Particle Size of Primary Condensed
Combustion Products ..................................................................202
6.6.4.3 Chemical Analysis of Condensed Phase Products
Qualitative and Quantitative Aspects .......................................203
6.6.4.4 Preliminary Analysis of Organic and Gaseous Products
in the Primary Combustion Products .......................................212
6.6.5 Combustion Residue Analysis ...................................................................215
6.6.5.1 Experimental Principle of Chemical Analysis of
Combustion Residue ....................................................................215
6.6.5.2 T he Main Components and Determination of
Combustion Residues of Boron-Based Fuel-Rich
Propellants ...................................................................................216
6.6.5.3 Reliability Verification of Method ..............................................223
6.6.5.4 Effect of Coat on the Combustion of Boron in
Fuel-Rich Propellant ....................................................................224
6.7 Influencing Factors on the Primary Combustion Ejection Efficiency of
Boron-Based Fuel-Rich Propellant .........................................................................226
6.7.1 Propellant Formulation and Experimental Scheme ...............................226
6.7.2 Effects of Ingredients on the Efficiency of Fuel-Rich Propellant ..........226
6.7.3 Ejection Apparatus on the Efficiency of Fuel-Rich Propellants ............229
6.8 The Primary Combustion Model of Boron-Based Fuel-Rich
Solid Propellant ....................................................................................................229
6.8.1 Establishment of Physical Model in the Primary Combustion .............230
6.8.2 Establishment of Mathematical Model in the Primary Combustion ...231
6.8.1.1 AP/HTPB System .........................................................................232
6.8.1.2 Agglomerated Boron/AP/HTPB System ...................................233
References .............................................................................................................................236