Epoxy Adhesive Formulations (Chemical Engineering)

554 Pages·2005·3.58 MB·English

by  Edward M. Petrie

EPOXY
ADHESIVE
FORMULATIONS
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EPOXY
ADHESIVE
FORMULATIONS
Edward M. Petrie
McGRAW-HILL
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DOI: 10.1036/0071455442
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CONTENTS
Preface xiii
Chapter 1. Epoxy Adhesives 1
1.1 Introduction / 1
1.2 Importance of Epoxy Resins / 3
1.3 Importance of Epoxy Adhesives / 6
1.3.1 Advantages and Disadvantages of Adhesive Bonding / 6
1.3.2 The Nature of the Epoxy Adhesive Industry / 8
1.3.3 Epoxy Adhesive Markets / 9
1.4. Formulating Epoxy Adhesives / 18
1.4.1 The Job of the Adhesive Formulator / 18
1.4.2 The Basics of Adhesive Formulation / 19
References / 24
Chapter 2. Epoxy Resin Chemistry 27
2.1 Introduction / 27
2.2 Epoxy Resin Characteristics / 27
2.3 Synthesis of Epoxy Resins / 30
2.3.1 Diglycidyl Ether of Bisphenol A (DGEBA) / 30
2.3.2 Other Epoxy Resins / 32
2.4 Epoxy Curing Mechanisms / 36
2.4.1 Polyaddition Reactions / 37
2.4.2 Homopolymerization Reactions / 38
2.5 Stoichiometry / 38
2.5.1 Amine Concentration / 39
2.5.2 Anhydride Concentration / 41
References / 41
Chapter 3. Important Properties of Epoxy Adhesives 43
3.1 Introduction / 43
3.2 Properties of the Uncured Epoxy System / 44
3.2.1 Vapor Pressure / 45
3.2.2 Viscosity / 45
3.2.3 Wetting / 49
3.2.4 Reactivity / 53
3.3 Properties of the Curing Epoxy System / 54
3.3.1 Preassembly Reactions / 54
3.3.2 Localized Stresses due to Gas or Air Pockets / 55
v
vi CONTENTS
3.3.3 Shrinkage / 57
3.3.4 Thermal Expansion Differences / 59
3.4 Properties of the Cured Epoxy System / 60
3.4.1 The Problem with Rigidity in Epoxy Adhesives / 61
3.4.2 Effect of Crosslink Density / 62
3.4.3 Glass Transition Temperature T / 64
g
3.4.4 Properties Resulting from Elevated versus Room Temperature Cure / 67
References / 68
Chapter 4. Epoxy Resins 71
4.1 Introduction / 71
4.2 Diglycidyl Ether of Bisphenol A Epoxy Resins / 72
4.2.1 Liquid DGEBA Resins / 73
4.2.2 Solid and Semisolid DGEBA Resins / 75
4.2.3 Brominated DGEBA Epoxy Resins / 76
4.3 Epoxy Novolac and Other Epoxy Resins / 77
4.4 Flexible Epoxy Resins / 78
4.5 Waterborne Epoxy Resins / 79
4.6 Epoxy Acrylate Resins / 82
References / 84
Chapter 5. Epoxy Curing Agents and Catalysts 85
5.1 Introduction / 85
5.2 Aliphatic Amines / 88
5.2.1 Primary and Secondary Aliphatic Amines / 88
5.2.2 Modified Aliphatic Amines / 93
5.3 Polyamides and Amidoamines / 95
5.3.1 Polyamides / 95
5.3.2 Amidoamines / 96
5.4 Aromatic Amines / 96
5.4.1 Metaphenylene Diamine / 97
5.4.2 Methylene Dianiline / 98
5.4.3 Other Aromatic Amines / 98
5.5 Anhydrides / 99
5.5.1 Hexahydrophthalic Anhydride / 102
5.5.2 Nadic Methyl Anhydride / 102
5.5.3 Pyromellitic Dianhydride / 102
5.5.4 Other Anhydride Curing Agents / 103
5.6 Catalysts and Latent Curing Agents / 103
5.6.1 Tertiary Amines / 104
5.6.2 BF-Monoethylamine / 104
3
5.6.3 Imidazoles / 105
5.6.4 Dicyandiamide / 106
5.6.5 Other Latent Catalysts / 107
5.7 Mercaptan and Polysulfide Curing Agents / 107
References / 109
Chapter 6. Solvents and Diluents 111
6.1 Introduction / 111
6.2 Solvents / 111
6.3 Diluents / 116
CONTENTS vii
6.3.1 Nonreactive Diluents / 117
6.3.2 Reactive Diluents / 119
References / 122
Chapter 7. Hybrid Resins 123
7.1 Introduction / 123
7.2 Epoxy-Nitrile (Single-Phase) / 125
7.3 Epoxy-Phenolic / 126
7.4 Epoxy-Nylon / 127
7.5 Epoxy-Polysulfide / 130
7.6 Epoxy-Vinyl / 131
7.7 Epoxy-Urethane / 131
7.8 Other Hybrids / 133
References / 136
Chapter 8. Flexibilizers and Tougheners 137
8.1 Introduction / 137
8.2 Improvements in Flexibility / 138
8.2.1 Flexibility through Resin and Curing Agent / 138
8.2.2 Flexibility through Hybrid Formulation / 139
8.2.3 Flexibility through Diluents / 141
8.3 Improvements in Toughness / 146
8.3.1 Reactive Liquid Rubber / 146
8.3.2 Thermoplastic Additives / 148
8.3.3 Inorganic Particles and Preformed Modifiers / 150
8.3.4 Interpenetrating Polymer Network (IPN) Tougheners / 151
References / 152
Chapter 9. Fillers and Extenders 155
9.1 Introduction / 155
9.2 Formulating with Fillers / 155
9.3 Property Modification by Fillers / 160
9.3.1 Materials Cost / 160
9.3.2 Flow Properties / 161
9.3.3 Control of Bond Line Thickness / 169
9.3.4 Coefficient of Thermal Expansion / 169
9.3.5 Shrinkage / 171
9.3.6 Electrical and Thermal Conductivity / 171
9.3.7 Electrical Properties / 174
9.3.8 Specific Gravity / 174
9.3.9 Cohesive Mechanical Properties / 175
9.3.10 Heat and Chemical Resistance / 176
9.3.11 Adhesive Properties / 177
9.3.12 Working Life and Exotherm / 179
9.3.13 Fire Resistance / 179
9.3.14 Color / 182
References / 182
Chapter 10. Adhesion Promoters and Primers 185
10.1 Introduction / 185
10.2 Adhesion Promoters / 186
viii CONTENTS
10.2.1 Organosilane Adhesion Promoters / 186
10.2.2 Organometallic Adhesion Promoters / 191
10.2.3 Other Organometallic Adhesion Promoters / 195
10.3 Primers / 195
10.3.1 Application and Use of Primers / 196
10.3.2 Primers for Corrosion Protection / 198
References / 200
Chapter 11. Room Temperature Curing Epoxy Adhesives 203
11.1 Introduction / 203
11.2 General-Purpose Adhesives / 207
11.2.1 Polyamides and Amidoamines / 207
11.2.2 Aliphatic Amines / 208
11.3 Fast-Curing Systems / 211
11.4 Improving Flexibility / 214
11.5 Improving Toughness / 220
11.6 Improving Environmental Resistance / 223
11.6.1 High-Temperature Resistance / 223
11.6.2 Chemical Resistance / 225
References / 225
Chapter 12. Elevated-Temperature Curing Liquid and
Paste Epoxy Adhesives 227
12.1 Introduction / 227
12.2 Two-Component Adhesive Formulations / 229
12.3 One-Component Adhesive Formulations / 233
12.4 Novel One-Component Adhesive Systems / 236
12.5 Improving Performance Properties / 237
12.5.1 Thermal Resistance / 237
12.5.2 Toughening / 239
References / 241
Chapter 13. Solid Epoxy Adhesive Systems 243
13.1 Introduction / 243
13.2 Solid Adhesive Manufacturing Processes / 244
13.3 Chemistry / 246
13.4 Types of Solid Epoxy Adhesives / 247
13.4.1 Tapes and Films / 247
13.4.2 Powders and Preforms / 251
13.4.3 Thermoplastic Epoxy Films / 252
References / 254
Chapter 14. Unconventional Epoxy Adhesives 255
14.1 Introduction / 255
14.2 Ultraviolet and Electron Beam Cured Epoxy Adhesives / 255
14.2.1 Crosslinking Mechanisms / 257
14.2.2 Formulation of UV and EB Epoxy Adhesives / 260
14.3 Waterborne Epoxy Adhesives / 264
14.3.1 Background and Markets / 265
14.3.2 Preparation of Waterborne Epoxy Raw Materials / 266