Fire Retardancy of

Polymeric Materials
The third edition of Fire Retardancy of Polymeric Materials provides a single source for all aspects of this highly challenging
field of applied research. This authoritative book covers design and non-fire requirements that drive how these materials
are fire protected.
Detailed study and consideration of chemistry, physics, materials science, economic issues, and fire safety science
is necessary to address considerations of mechanical, thermal, environmental, and end-use requirements on top of fire
protection means that the field requires. This thoroughly revised new edition continues to offer comprehensive coverage of
the scientific approach for those developing fire safe materials. It covers new topics such as bio-based materials, regulatory
issues, recycling, newer flame retardant chemical classes, and more details on how to flame retard materials for specific
market applications.
Written by a team of experts, this book covers the fundamentals of polymer burning and combustion and how to apply
fire protection or flame-retardant chemistries to specific material classes and applications. The book is written for material
scientists and fire safety scientists who seek to develop new fire safe materials or understand why materials burn in our
modern environment.

Features
• Connects fundamentals of material flammability to practical fire safety needs.
• Covers current fire safety requirements and regulations affecting flame retardant selection.
• Provides information on chemical structure-property relationships for flame retardancy.
• Provides practical guidance on how to design fire safe materials for specific fire risk scenarios.
• The new edition is expanded to 32 chapters, and all chapters are updated and revised with the newest information.
 Fire Retardancy of
Polymeric Materials

Third Edition
Alexander B. Morgan and Charles A. Wilkie
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Third edition published 2024
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© 2024 selection and editorial matter, Alexander B. Morgan and Charles A. Wilkie; individual chapters,
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First edition published by CRC Press 2000
Second edition published by CRC Press 2010
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Library of Congress Cataloging-in-Publication Data
Names: Wilkie, Charles A., 1941- editor. | Morgan, Alexander B., editor.
Title: Fire retardancy of polymeric materials / Charles A. Wilkie and Alexander B. Morgan.
Description: Third edition. | Boca Raton ; London : CRC Press, 2024. | Includes bibliographical references and index.
Identifiers: LCCN 2023056620 (print) | LCCN 2023056621 (ebook) | ISBN 9781032457543 (hardback) |
ISBN 9781032462332 (paperback) | ISBN 9781003380689 (ebook)
Subjects: LCSH: Polymers—Fire testing. | Polymers—Fires and fire prevention. | Fire resistant plastics.
Classification: LCC TH9446.5.P65 F56 2024 (print) | LCC TH9446.5.P65 (ebook) |
DDC 620.1/92—dc23/eng/20240128
LC record available at https://lccn.loc.gov/2023056620
LC ebook record available at https://lccn.loc.gov/2023056621
ISBN: 9781032457543 (hbk)
ISBN: 9781032462332 (pbk)
ISBN: 9781003380689 (ebk)
DOI: 10.1201/9781003380689
Contents
Preface.................................................................................................................................................................................xix
Alexander B. Morgan and Charles A. Wilkie
List of Contributors.............................................................................................................................................................xxi

Chapter 1 An Introduction to Materials Flame Retardancy and Fire Protection ............................................................. 1

Alexander B. Morgan and Charles A. Wilkie
1.1 Fire and Society .....................................................................................................................................1
1.2 Definitions of Flame Retardancy .......................................................................................................... 1
1.2.1 Fire Protection ..........................................................................................................................2
1.2.2 Flame Retardancy ....................................................................................................................2
1.2.3 Fire Risk Scenario....................................................................................................................2
1.2.4 Flame Retardant .......................................................................................................................2
1.2.5 Combustibility ..........................................................................................................................2
1.2.6 Thermal Degradation/Decomposition .....................................................................................2
1.2.7 Other Relevant Fire Protection Definitions ..............................................................................3
1.3 Protection from Fire—Modern vs. Historical Viewpoints ...................................................................3
1.4 Changing Perceptions, Regulations, and Customer Demands ..............................................................5
1.5 Flame Retardant Chemistries ................................................................................................................7
1.6 Flame Retardant Research ....................................................................................................................8
1.7 Conclusions and Key Items to Remember .............................................................................................8
References ........................................................................................................................................................9

Chapter 2 Thermal Decomposition of Flame Retardant Polymers ................................................................................ 11

Aurelio Bifulco, Sabyasachi Gaan, D. Price, and A. Richard Horrocks
2.1 State of Art and Thermal Decomposition of Polymers....................................................................... 11
2.1.1 Oxidative Decomposition ....................................................................................................... 14
2.2 Decomposition of Individual Polymer Types ...................................................................................... 14
2.2.1 Thermoplastics ....................................................................................................................... 14
2.2.2 Foams ..................................................................................................................................... 17
2.2.3 Thermosets ............................................................................................................................. 19
2.2.4 Natural Polymers.................................................................................................................... 22
2.3 High Temperature Resistant Polymers ................................................................................................ 23
2.4 Polymer Fire ........................................................................................................................................24
2.4.1 Polymer Combustion Cycle ....................................................................................................25
2.5 Conclusions and Future Outlooks........................................................................................................ 31
2.5.1 Author Statement .................................................................................................................... 31
2.5.2 Declaration of Competing Interest ......................................................................................... 31
2.5.3 List of Abbreviations .............................................................................................................. 31
References ...........................................................................................................................................31

Chapter 3 Physical Parameters Affecting Fire Growth .................................................................................................. 36

Alexander B. Morgan, Jose L. Torero, and Guillermo Rein
3.1 Fire Safety ........................................................................................................................................... 36
3.1.1 Objectives of Fire Safety ........................................................................................................ 36
3.1.2 Basic Definition of Fire Growth ............................................................................................. 38
3.2 Fundamentals of Combustion .............................................................................................................. 38
3.2.1 Reactive Gaseous Mixtures .................................................................................................... 38
3.2.2 Premixed and Diffusion Flames ............................................................................................ 39
3.2.3 Burning of Condensed Fuels .................................................................................................. 39

v
vi Contents

3.3 Fundamentals of Fire Dynamics .........................................................................................................40

3.3.1 Open Fires ..............................................................................................................................40
3.3.2 Compartment Fires.................................................................................................................40
3.3.3 Fire Modeling......................................................................................................................... 41
3.4 Material Parameters Controlling the Ignition of Solid Fuels .............................................................. 42
3.4.1 Spontaneous Ignition.............................................................................................................. 42
3.4.2 Induced Ignition ..................................................................................................................... 43
3.5 Material Parameters Controlling Flame Spread.................................................................................. 45
3.5.1 Definition................................................................................................................................ 45
3.5.2 Classification ..........................................................................................................................46
3.5.3 Opposed Flame Spread .......................................................................................................... 47
3.5.4 Co-Current Flame Spread ...................................................................................................... 49
3.5.5 Propagation of a Smouldering Front ...................................................................................... 49
3.6 Mass Burning Rate—Energy Release Rate ........................................................................................ 53
3.6.1 Definition................................................................................................................................ 53
3.6.2 Heat Release Rate (Q) Q ............................................................................................................ 53
3.6.3 Energy Balance at the Material Surface ................................................................................ 53
3.6.4 The Mass Transfer Number (B).............................................................................................. 54
3.7 Material Parameters Controlling Extinction ....................................................................................... 55
3.8 Conclusions.......................................................................................................................................... 55
References ......................................................................................................................................................56

Chapter 4 Halogen-Containing Flame Retardants ......................................................................................................... 58

Sergei Levchik, Sergio Bocchini, Giovanni Camino
4.1 Introduction ......................................................................................................................................... 58
4.2 Mechanism of Gas Phase Action of Halogen Compounds.................................................................. 59
4.3 Gas Phase Mechanism: Synergistic Effect Based on Halogen-Antimony Compounds......................60
4.4 Mechanism of Action of Halogenated Compounds in the Condensed Phase ..................................... 63
4.5 Mechanism of Condensed Phase Action of Synergistic Systems Based on
Halogen-Metal Compounds................................................................................................................. 65
4.6 Main Application of Halogenated Flame Retardants by Families of Polymers..................................66
4.6.1 Styrenic Homopolymer and Copolymers ...............................................................................66
4.6.2 Thermoplastic Polyesters........................................................................................................ 67
4.6.3 Polycarbonate ......................................................................................................................... 67
4.6.4 Polyamides ............................................................................................................................. 67
4.6.5 Polyolefins .............................................................................................................................. 68
4.6.6 Poly(Vinyl Chloride) .............................................................................................................. 68
4.6.7 Thermosetting Resins............................................................................................................. 68
4.6.8 Polyurethanes ......................................................................................................................... 69
4.6.9 Textiles ................................................................................................................................... 69
4.7 Conclusions and Future Trends ........................................................................................................... 69
References ......................................................................................................................................................76

Chapter 5 Phosphorus-Containing Flame Retardants .................................................................................................... 81

Svetlana Tretsiakova-McNally and Paul Joseph
5.1 Background.......................................................................................................................................... 81
5.2 Elemental Phosphorus and Its Compounds ......................................................................................... 81
5.3 Phosphorus-Based Inorganic Additive Flame Retardants................................................................... 82
5.3.1 Red Phosphorus...................................................................................................................... 82
5.3.2 Ammonium Phosphates ......................................................................................................... 82
5.4 Organophosphorus Additive Flame Retardants .................................................................................. 83
5.4.1 Phosphates and Phosphonates ................................................................................................ 83
5.4.2 Halogenated Phosphates and Phosphonates ........................................................................... 83
5.4.3 Dimeric, Oligomeric, and Cyclic Phosphates and Phosphonates...........................................84
Contents vii

5.4.4 Phosphine Oxides ................................................................................................................... 85

5.5 Reactive Flame Retardants.................................................................................................................. 85
5.6 Step-Reaction Polymers ...................................................................................................................... 85
5.6.1 Polyesters and Polycarbonates................................................................................................ 85
5.6.2 Polyamides ............................................................................................................................. 86
5.7 Chain-Reaction Polymers.................................................................................................................... 87
5.7.1 Acrylics .................................................................................................................................. 87
5.7.2 Polystyrene ............................................................................................................................. 87
5.7.3 Polyolefins .............................................................................................................................. 87
5.8 Thermosets .......................................................................................................................................... 88
5.8.1 Epoxy Resins .......................................................................................................................... 88
5.8.2 Polyurethanes ......................................................................................................................... 88
5.8.3 Unsaturated Polyesters ........................................................................................................... 89
5.9 Surface Grafting .................................................................................................................................. 89
5.10 Mechanisms of Flame Retardance: General Considerations .............................................................. 89
5.10.1 Mechanisms of Flame Retardance by Phosphorus Compounds ............................................90
5.11 Concluding Remarks and Future Trends.............................................................................................92
5.12 Acknowledgments ............................................................................................................................... 93
References ......................................................................................................................................................93

Chapter 6 Flame Retardant Fillers ..................................................................................................................................97

Charles A. Wilkie, A. Richard Horrocks, and Peter Hornsby
6.1 Introduction .........................................................................................................................................97
6.2 An Initial Look at the Flame-Retardant Mechanism ..........................................................................97
6.3 Flame Retardant Filler Types ............................................................................................................ 100
6.3.1 Aluminum Hydroxide .......................................................................................................... 100
6.3.2 Magnesium Hydroxide (Mg(OH)2)....................................................................................... 101
6.3.3 Basic Magnesium Carbonates .............................................................................................. 101
6.3.4 Boehmite .............................................................................................................................. 101
6.3.5 Calcium Sulfate Dihydrate (Gypsum) .................................................................................. 102
6.3.6 Hydrotalcites ........................................................................................................................ 102
6.3.7 Halloysite Nanotubes ........................................................................................................... 102
6.3.8 Inert Fillers ........................................................................................................................... 102
6.4 Scope of Application ......................................................................................................................... 103
6.5 A More Detailed Look at the Mechanism ......................................................................................... 104
6.5.1 Thermal Effects from the Filler ........................................................................................... 104
6.5.2 Filler-Polymer Interactions ................................................................................................... 105
6.5.3 Vapor Phase Action .............................................................................................................. 105
6.6 Smoke Suppression ............................................................................................................................ 106
6.7 Enhancing the Efficiency of Fire Retardant Fillers........................................................................... 106
6.7.1 Synergism ............................................................................................................................. 107
6.7.2 Nano-Size Fire Retardant Fillers ......................................................................................... 109
6.8 Conclusions........................................................................................................................................ 110
References ....................................................................................................................................................111

Chapter 7 Intumescence-Based Flame Retardant ......................................................................................................... 116

Serge Bourbigot
7.1 Introduction ....................................................................................................................................... 116
7.2 Fundamentals of Intumescence ......................................................................................................... 117
7.2.1 Chemistry of Intumescence.................................................................................................. 118
7.2.2 Rheology of Intumescence................................................................................................... 119
7.2.3 Thermal Behavior of Intumescence ..................................................................................... 120
7.3 Intumescence on the Market ............................................................................................................. 120
7.4 Reaction to Fire of Intumescent Materials ........................................................................................ 122
viii Contents

7.4.1 Evaluation of the Reaction to Fire ........................................................................................ 122

7.4.2 Intumescent Organic Polymeric Materials........................................................................... 123
7.4.3 Intumescent Textile .............................................................................................................. 127
7.4.4 Intumescent Inorganic Polymeric Materials ........................................................................ 129
7.4.5 Synergy in Intumescents ...................................................................................................... 129
7.5 Resistance to Fire of Intumescent Materials ..................................................................................... 131
7.5.1 Evaluation of the Resistance to Fire ..................................................................................... 131
7.5.2 Testing and Characterization of Intumescence at Reduced Scale ....................................... 133
7.5.3 Fire Protective Intumescent Materials ................................................................................. 136
7.6 Conclusion and Future Trends........................................................................................................... 141
References ....................................................................................................................................................141

Chapter 8 Silicon and Inorganic Flame Retardants...................................................................................................... 147

Walid H. Awad
8.1 Introduction ....................................................................................................................................... 147
8.2 Silicon-Based Flame Retardants ....................................................................................................... 147
8.2.1 Silicones ............................................................................................................................... 147
8.2.2 Silanes .................................................................................................................................. 149
8.2.3 Silsesquioxane ...................................................................................................................... 150
8.2.4 Silica ..................................................................................................................................... 155
8.2.5 Silicate .................................................................................................................................. 158
8.3 Inorganic Flame Retardants .............................................................................................................. 159
8.3.1 Tin Compounds .................................................................................................................... 159
8.3.2 Molybdenum Compounds .................................................................................................... 160
8.3.3 Iron Compounds ................................................................................................................... 160
8.3.4 Metal Oxides ........................................................................................................................ 160
8.3.5 Magnesium Carbonate-Based Materials .............................................................................. 160
8.4 Conclusion ......................................................................................................................................... 161
References .................................................................................................................................................... 161

Chapter 9 Boron-Based Flame Retardants ................................................................................................................... 164

Kelvin K. Shen
9.1 Introduction—Multifunctional Borates in Flame Retardancy.......................................................... 164
9.2 Properties of Boron-Based Products and Applications ..................................................................... 164
9.2.1 Boric Acid (H3BO3), Boric Oxide (B2O3), and Boric Acid Esters [B(OR)3] ........................ 164
9.2.2 Metallo-Borate ..................................................................................................................... 167
9.2.3 Boron-Nitrogen-Containing Compounds ............................................................................. 171
9.2.4 Boron-Phosphorus-Containing Compounds ........................................................................ 173
9.2.5 Boron-Silicon-Containing Compounds ............................................................................... 173
9.2.6 Boron-Carbon-Containing Compounds ............................................................................... 173
9.3 Conclusions........................................................................................................................................ 175
References ....................................................................................................................................................175

Chapter 10 Nitrogen-Based Flame Retardants ............................................................................................................... 178

Christopher Simpson, Qingliang He, and Michael Kuepfert
10.1 Introduction ....................................................................................................................................... 178
10.2 Main Types of Nitrogen-Based Flame Retardants ............................................................................ 178
10.3 Melamine-Based Flame Retardants .................................................................................................. 178
10.3.1 Melamine as Flame Retardant ............................................................................................. 179
10.3.2 Melamine Condensates as Flame Retardants ...................................................................... 179
10.3.3 Melamine Salts as Flame Retardants................................................................................... 180
10.4 Ammonia-Based Flame Retardants .................................................................................................. 183
10.4.1 Ammonium Polyphosphate .................................................................................................. 183
10.5 Cyanuric Acid–Based Flame Retardants .......................................................................................... 184
Contents ix

10.6 Nitrogen-Containing Radical Generators.......................................................................................... 185

10.7 Diethyl N,N-Bis(2-Hydroxyethyl)Aminomethylphosphonate ........................................................... 187
10.8 Phosphazenes..................................................................................................................................... 188
10.9 Polyphosphazenes .............................................................................................................................. 189
10.10 Oxyimides ......................................................................................................................................... 189
10.11 Triazoles ............................................................................................................................................ 189
10.12 Imidazole and Imidazolium Structures ............................................................................................. 190
10.13 Future Outlook and Concluding Remarks ......................................................................................... 190
References ....................................................................................................................................................190

Chapter 11 Non-Halogen Radical Generators for Enhanced Flame Retardancy of Plastics .......................................... 196
Carl-Eric Wilen and Rudolf Pfaendner
11.1 Introduction ....................................................................................................................................... 196
11.2 Radical Generators and Their Tentative Modes of Action in Flame Retardancy ............................. 196
11.3 Alkoxyamines .................................................................................................................................... 197
11.4 Sulfur-Containing Radical Generators.............................................................................................. 199
11.5 Oxyimides ......................................................................................................................................... 199
11.6 Sulfenamides, Sulfinamides, and Sulfonamides ............................................................................... 201
11.7 Radical Generators Based on Silylamine (N-Si) and Siloxyamine (N-O-Si) ...................................202
11.8 Carbon-Based Nanocomposites.........................................................................................................205
11.9 Summary ...........................................................................................................................................205
References .................................................................................................................................................... 205

Chapter 12 Polymer Nanocomposites .............................................................................................................................208

Daniel F. Schmidt and David D. Jiang
12.1 Introduction .......................................................................................................................................208
12.2 Structure and Properties of Nanoadditives........................................................................................208
12.2.1 Structure and Properties of Clay..........................................................................................208
12.2.2 Structure and Properties of Carbon Nanotubes and Other Nanoadditives .......................... 211
12.3 Surface Treatment of Nanoadditives ................................................................................................. 212
12.3.1 Surface Treatment of Clays .................................................................................................. 212
12.3.2 Surface Treatment of Carbon Nanotubes and Other Nanoadditives .................................... 217
12.4 Preparation of Polymer Nanocomposites .......................................................................................... 217
12.4.1 In Situ Polymerization .......................................................................................................... 218
12.4.2 Solvent Blending .................................................................................................................. 219
12.4.3 Melt Compounding............................................................................................................... 219
12.5 Structure of Polymer Nanocomposites .............................................................................................. 220
12.5.1 Structure of Polymer Nanocomposites ................................................................................. 220
12.5.2 Characterization ................................................................................................................... 221
12.6 Thermal and Fire Performance of Polymer Nanocomposites
and Associated Mechanisms ............................................................................................................. 223
12.6.1 Thermal and Fire Performance of Polymer Nanocomposites .............................................. 223
12.6.2 Mechanisms Underlying the Effects of Nanoadditives on
the Flammability of Polymers.............................................................................................. 230
12.7 Concluding Remarks and Future Directions ..................................................................................... 231
Further reading .............................................................................................................................................233
References ....................................................................................................................................................234

Chapter 13 Bio-Based Flame Retardants........................................................................................................................ 242

Xiu-Li Wang, Jing-Hong Liu, Yin-Long Wang, and Zheng-Ming Li
13.1 Introduction: Why We Need Bio-Based Flame Retardants .............................................................. 242
13.2 Biomacromolecules as FRs ............................................................................................................... 242
13.2.1 Chitosan................................................................................................................................ 242
13.2.2 Cellulose ...............................................................................................................................248
x Contents

13.2.3 Protein .................................................................................................................................. 250

13.2.4 Lignin ................................................................................................................................... 251
13.2.5 DNA ..................................................................................................................................... 253
13.2.6 Alginates .............................................................................................................................. 253
13.2.7 Other Biomacromolecules-Based FR................................................................................... 255
13.3 Bio-Based Small Molecule Compounds as FRs................................................................................ 256
13.3.1 Phytic Acid ........................................................................................................................... 256
13.3.2 Cyclodextrins........................................................................................................................ 259
13.3.3 Aromatic Compounds from Biomass ...................................................................................260
13.4 Summary and Outlook ...................................................................................................................... 277
References .................................................................................................................................................... 279

Chapter 14 Conformal Flame Retardant Coating Systems.............................................................................................284

Thomas J. Kolibaba, Federico Carosio, and Jaime C. Grunlan
14.1 Meeting the Flammability Challenge at the Interface ......................................................................284
14.1.1 Common Substrates for Flame-Retardant Surface Treatments ...........................................284
14.2 Layer-by-Layer Treatments................................................................................................................ 285
14.2.1 Practical Considerations of Layer-by-Layer Assembled
Flame-Retardant Treatments................................................................................................ 286
14.2.2 Use-Cases of Layer-by-Layer Assembled
Flame-Retardant Coatings ................................................................................................... 286
14.2.3 Outlook and Future Research Directions ............................................................................. 291
14.3 Polyelectrolyte Complex Coatings..................................................................................................... 291
14.3.1 Controlling Polyelectrolyte Complexation to Deposit Coatings .......................................... 291
14.3.2 Use-Cases of Polyelectrolyte Complex
Flame-Retardant Coatings ................................................................................................... 293
14.3.3 Outlook and Future Research Directions ............................................................................. 294
14.4 Sol-Gel Coatings ............................................................................................................................... 295
14.4.1 Sol-Gel Chemistry................................................................................................................ 295
14.4.2 Use-Cases of Sol-Gel Flame-Retardant Coatings................................................................ 296
14.4.3 Outlook and Future Research Directions ............................................................................. 298
14.5 Plasma and Vapor Based Treatments ................................................................................................ 298
14.6 Conclusions........................................................................................................................................ 299
References ....................................................................................................................................................300

Chapter 15 Flame Retardants without Conventional Flame-Retardant Elements..........................................................308

Bo-Wen Liu and Yu-Zhong Wang
15.1 Introduction .......................................................................................................................................308
15.2 Chemical Fundamentals ....................................................................................................................308
15.3 Establishment and Development .......................................................................................................309
15.3.1 Metal Ion Promoted Char Formation ...................................................................................309
15.3.2 Chemical Self-Cross-Linking .............................................................................................. 311
15.3.3 Thermal Rearrangement and Others.................................................................................... 316
15.4 The Combination of Conventional and Unconventional
Flame-Retardant Method .................................................................................................................. 322
15.5 Conclusion and Perspectives ............................................................................................................. 324
References ....................................................................................................................................................325

Chapter 16 Multi-Component Flame-Retardant Systems............................................................................................... 330

Bernhard Schartel
16.1 The Imperative for Multi-Component Solutions ............................................................................... 330
16.2 Concepts: Synergy, Tailored Systems, and Residue Design.............................................................. 333
16.3 Fibers, Fillers, Nanoparticles............................................................................................................. 335
Contents xi

16.4 Additives, Adjuvants, Synergists....................................................................................................... 337

16.5 Combining Distinct Flame Retardants..............................................................................................340
16.6 Flame Retardants with Different Flame-Retardant Groups .............................................................. 341
16.7 Summary ........................................................................................................................................... 342
References ....................................................................................................................................................342

Chapter 17 Uses of Fire Tests for Flame-Retardant Material Development ..................................................................360

Bernhard Schartel
17.1 Introduction .......................................................................................................................................360
17.2 Ignition: Reaction to a Small Ignition Source ................................................................................... 362
17.3 Developing Fire: Forced Flaming Combustion ................................................................................. 365
17.4 Fully Developed Fire ......................................................................................................................... 371
17.5 Other Fire Hazards ............................................................................................................................ 372
17.6 Understanding Fire Behavior and Fire-Retardant Modes of Action ................................................. 373
17.7 Conclusions........................................................................................................................................ 379
17.7.1 Acknowledgments ................................................................................................................ 379
References ....................................................................................................................................................380

Chapter 18 Material Flammability Measurements and Test Methods ........................................................................... 386

Marc Janssens
18.1 Fundamentals of Fire Testing ............................................................................................................ 386
18.1.1 Typical Development of a Compartment Fire ...................................................................... 386
18.1.2 The NFPA 550 Fire Concepts Tree ...................................................................................... 387
18.1.3 Reaction to Fire of Materials................................................................................................ 387
18.1.4 Types of Flammability Tests ................................................................................................ 389
18.2 Small Heat Source Ignition Tests ...................................................................................................... 389
18.2.1 General Concepts ................................................................................................................. 389
18.2.2 Examples of Small Heat Source Ignition Tests .................................................................... 390
18.2.3 Use and Limitations of Small Heat Source Ignition Tests ................................................... 391
18.3 Bench-Scale Reaction-to-Fire Tests .................................................................................................. 392
18.3.1 General Concepts ................................................................................................................. 392
18.3.2 Ignition ................................................................................................................................. 393
18.3.3 Heat Release Rate................................................................................................................. 396
18.3.4 Surface Flame Spread .......................................................................................................... 398
18.3.5 Smoke and Toxicity ..............................................................................................................400
18.4 Large-Scale Reaction-to-Fire Tests ...................................................................................................405
18.4.1 Furniture Calorimeter ..........................................................................................................405
18.4.2 Room/Corner Test ................................................................................................................406
18.4.3 Other Large-Scale Reaction-to-Fire Tests............................................................................407
18.5 Conclusions........................................................................................................................................407
Bibliography.................................................................................................................................................408
References ....................................................................................................................................................409

Chapter 19 Fire Emissions and Smoke Toxicity ............................................................................................................. 412

T Richard Hull and Anna A Stec
19.1 Introduction ....................................................................................................................................... 412
19.1.1 Fire Scenarios ....................................................................................................................... 412
19.1.2 Fire Hazards ......................................................................................................................... 415
19.2 Assessment of Fire Toxicity .............................................................................................................. 416
19.3 Composition of Fire Effluents ........................................................................................................... 417
19.3.1 Volatile Organic Compounds ............................................................................................... 418
19.3.2 Incapacitating Irritants ......................................................................................................... 418
19.3.3 Polycyclic Aromatic Hydrocarbons...................................................................................... 419
xii Contents

19.3.4 Isocyanates ........................................................................................................................... 421

19.3.5 Halogenated Dioxins ............................................................................................................ 421
19.3.6 Particulates ........................................................................................................................... 421
19.4 Toxicity Assessment from Small and Large-Scale Test Methods ..................................................... 422
19.4.1 The Steady State Tube Furnace (SSTF) ............................................................................... 423
19.4.2 Use of the Smoke Density Chamber for Assessment of Fire Toxicity ................................. 423
19.5 Effect of Fire Retardants on Smoke Toxicity .................................................................................... 424
19.5.1 Gas Phase Action ................................................................................................................. 424
19.5.2 Condensed Phase Action ...................................................................................................... 425
19.5.3 Assessment of Smoke Toxicity of Product Classes .............................................................. 425
19.5.4 Fire Retardancy and Performance in Large-Scale Fires ...................................................... 428
19.6 Conclusions........................................................................................................................................ 428
19.6.1 Future Prospects ................................................................................................................... 429
References ....................................................................................................................................................430

Chapter 20 Toward a Quantitative Relation between the Molecular Structure

and Fire Growth on Polymeric Solids .......................................................................................................... 434
Dushyant M. Chaudhari and Stanislav I. Stoliarov
20.1 Introduction ....................................................................................................................................... 434
20.1.1 Fire Growth Phenomenon .................................................................................................... 434
20.1.2 Fire Growth Modeling.......................................................................................................... 435
20.2 Overview of Pyrolysis and Pyrolysis Modeling ................................................................................ 436
20.2.1 Pyrolysis Phenomenon ......................................................................................................... 436
20.2.2 Comprehensive Pyrolysis Modeling ..................................................................................... 437
20.3 Overview of Modeling Tools ............................................................................................................. 439
20.3.1 ThermaKin ........................................................................................................................... 439
20.3.2 Fire Dynamics Simulator (FDS) .......................................................................................... 439
20.4 Quantifying Parameters to Develop Comprehensive Pyrolysis Models ........................................... 439
20.4.1 Materials...............................................................................................................................440
20.4.2 Milligram-Scale Experiments and Modeling ......................................................................440
20.4.3 Gram-Scale Experiments and Modeling.............................................................................. 442
20.4.4 State of the Art of Pyrolysis Modeling ................................................................................ 445
20.5 Relating Material Properties and Molecular Structure .....................................................................446
20.5.1 Group Contributions to Characterize Material Properties ...................................................446
20.5.2 State of the Art of Quantitative Structure-Property Relationships ...................................... 447
20.6 Fire Growth Modeling Case Study....................................................................................................448
20.6.1 Experiment Overview ..........................................................................................................448
20.6.2 Fire Growth Modeling Framework ...................................................................................... 450
20.6.3 Results and Discussion ......................................................................................................... 453
20.7 Sensitivity to Uncertainties in Property Values ................................................................................ 455
20.8 Conclusion ......................................................................................................................................... 457
20.8.1 Acknowledgments ................................................................................................................ 458
Bibliography.................................................................................................................................................458

Chapter 21 Full-Scale Fire Modeling and Simulation .................................................................................................... 462

Simo Hostikka
21.1 Introduction ....................................................................................................................................... 462
21.2 Gas Phase Physics Required for Fire Growth Predictions ................................................................ 463
21.2.1 Navier-Stokes Equations and Turbulence............................................................................. 463
21.2.2 Combustion...........................................................................................................................465
21.2.3 Radiative Heat Transfer ........................................................................................................469
21.2.4 Convective Heat Transfer ..................................................................................................... 474
21.3 Condensed Phase Pyrolysis ............................................................................................................... 475
21.3.1 Conjugate Heat Transfer ....................................................................................................... 475
Contents xiii

21.3.2 Empirical Models for Solid Fuels ........................................................................................ 477

21.3.3 Complex Pyrolysis Models for Solid Fuels .......................................................................... 478
21.3.4 Liquid Fuels .......................................................................................................................... 479
21.3.5 In-Depth Radiation ............................................................................................................... 479
21.3.6 Estimation of the Pyrolysis Model Parameters .................................................................... 481
21.3.7 Modeling Bench-Scale Experiments .................................................................................... 482
21.4 Simulation of Large-Scale Burning and Fire Growth.......................................................................484
21.4.1 Coupled Problem ..................................................................................................................484
21.4.2 Burning Rate Prediction for Stationary (Non-Spreading) Fires .......................................... 485
21.4.3 Flame Spread on Flat Surfaces ............................................................................................ 485
21.4.4 Predicting the Fire Growth on Electrical Cables ................................................................. 488
21.4.5 CFD Simulations Involving Fire-Retardant Polymers ......................................................... 490
References ....................................................................................................................................................491

Chapter 22 Regulations, Codes, and Standards Relevant to Fire Issues in the United States ........................................ 498
Marcelo M. Hirschler
22.1 Background: Regulations, Codes, and Standards ............................................................................. 498
22.2 Regulations ........................................................................................................................................ 499
22.2.1 How Does Regulation for Fire Safety Work in the United States ........................................ 499
22.2.2 Federal Regulations .............................................................................................................. 501
22.2.3 State Regulations .................................................................................................................. 501
22.2.4 Local Regulations................................................................................................................. 503
22.2.5 Regulations of Specific Items ...............................................................................................504
22.2.6 Comparison with International Regulations ........................................................................ 518
22.3 Codes ................................................................................................................................................. 523
22.3.1 International Code Council Codes ....................................................................................... 523
22.3.2 National Fire Protection Association Codes and Standards ................................................ 532
22.3.3 IAPMO Codes ...................................................................................................................... 541
22.4 Standards ........................................................................................................................................... 541
22.4.1 Organizations and Committees Issuing Fire Standards or Standards
with Fire Tests ...................................................................................................................... 541
22.4.2 Standard Test Methods ......................................................................................................... 542
22.4.3 Tests for Specific Products or Materials............................................................................... 554
22.5 Product Liability ................................................................................................................................ 554
22.6 Conclusions........................................................................................................................................ 555
22.7 Abbreviations..................................................................................................................................... 555
22.7.1 Regulations, Codes, Standards, and Organizations ............................................................. 555
22.8 Appendix: Fire Test Methods from ASTM, NFPA, and UL............................................................. 556
References ....................................................................................................................................................560

Chapter 23 Chemical Regulation of Flame Retardants .................................................................................................. 569

Adrian Beard
23.1 Introduction ....................................................................................................................................... 569
23.2 Regulatory Approach for Chemicals ................................................................................................. 569
23.3 International ...................................................................................................................................... 570
23.3.1 UN Stockholm Convention .................................................................................................. 570
23.3.2 UN Basel and Rotterdam Conventions ................................................................................ 571
23.3.3 Globally Harmonized System .............................................................................................. 572
23.4 Europe ............................................................................................................................................... 572
23.4.1 REACH ................................................................................................................................ 572
23.4.2 Restriction of Hazardous Substances in Electronics (RoHS and WEEE) ........................... 574
23.4.3 Swedish Chemical Tax ......................................................................................................... 575
23.5 North America ................................................................................................................................... 575
23.5.1 United States ........................................................................................................................ 575
xiv Contents

23.5.2 Canada.................................................................................................................................. 577

23.6 Asia, South America, and Africa ...................................................................................................... 577
23.6.1 China .................................................................................................................................... 577
23.6.2 Japan ..................................................................................................................................... 578
23.7 Nonregulatory Drivers....................................................................................................................... 578
23.7.1 Alternatives Assessments ..................................................................................................... 578
23.7.2 Eco-Labels and Green Procurement .................................................................................... 579
23.7.3 Safe and Sustainable-by-Design Concept in Europe............................................................ 580
23.8 Conclusions........................................................................................................................................ 580
References ....................................................................................................................................................581

Chapter 24 Recycling of Flame-Retardant Polymeric Materials: State of the Art

and Future Perspectives................................................................................................................................ 584
Aurelio Bifulco, Jiuke Chen, Arvindh Sekar, Wenyu Wu Klingler,
Ali Gooneie, Sabyasachi Gaan
24.1 Introduction: Background and Driving Forces.................................................................................. 584
24.2 Recycling of Thermoplastics Containing Halogenated Flame Retardants ....................................... 587
24.2.1 Mechanical Recycling of Thermoplastics Containing Halogenated
Flame Retardants ................................................................................................................. 588
24.2.2 Chemical Recycling of Thermoplastics Containing Halogenated
Flame Retardants ................................................................................................................. 588
24.3 Recycling of Thermoplastics Containing Halogen-Free Flame Retardants...................................... 589
24.3.1 Mechanical Recycling of Thermoplastics Containing Halogen-Free
Flame Retardants ................................................................................................................. 590
24.3.2 Chemical Recycling of Thermoplastics Containing Halogen-Free
Flame Retardants ................................................................................................................. 591
24.4 Recycling of Flame-Retarded Thermosets: From Conventional Disposal
Methods to Recent Approaches ......................................................................................................... 591
24.4.1 Waste Treatment of Conventional Flame-Retarded Thermosets ......................................... 592
24.4.2 Reprocessable Flame-Retardant Thermosets Based on CANs ............................................ 595
24.5 Conclusions and Future Outlooks...................................................................................................... 598
24.5.1 Author Statement .................................................................................................................. 599
24.5.2 Declaration of Competing Interest ....................................................................................... 599
References .........................................................................................................................................599

Chapter 25 Flame-Retardant Design and Protection for Fiber-Reinforced Composites ................................................607

Alexander B. Morgan and Baljinder K. Kandola
25.1 Introduction to Fiber-Reinforced Composites and Their Current Uses ............................................607
25.1.1 Aerospace .............................................................................................................................607
25.1.2 Mass Transit .........................................................................................................................608
25.1.3 Marine ..................................................................................................................................609
25.1.4 Offshore Platforms ...............................................................................................................609
25.1.5 Building Materials................................................................................................................609
25.2 Unique Fire Hazards with Composites .............................................................................................. 611
25.2.1 Mechanical Failure Prior to Ignition .................................................................................... 611
25.2.2 Emissions and Firefighting Measures .................................................................................. 611
25.3 Flame-Retardant Design of Composites ........................................................................................... 612
25.3.1 Choice of Constituents and Geometry ................................................................................. 612
25.3.2 Use of Flame Retardants ...................................................................................................... 616
25.3.3 Intumescent Fire Protection ................................................................................................. 617
25.3.4 Balance of Mechanical and Fire Properties ......................................................................... 618
25.4 Thermoplastic Composites for Structural Applications .................................................................... 620
25.5 Natural Fiber Composites: Unique Issues ......................................................................................... 621
25.6 Conclusions and Guidance Statements.............................................................................................. 622
References ....................................................................................................................................................623
Contents xv

Chapter 26 Flame-Retardant Design and Protection for Wood and Wood Products ..................................................... 627
Laura E. Hasburgh, Grant T. Kirker, and Katie M. Ohno
26.1 Introduction ....................................................................................................................................... 627
26.1.1 Wood Structure and Properties ............................................................................................ 627
26.1.2 Wood Pyrolysis, Combustion, and Products ........................................................................ 628
26.2 Wood Protection ................................................................................................................................ 630
26.2.1 Wood Protection Mechanisms ............................................................................................. 631
26.2.2 Wood Fire Retardant Treatment History.............................................................................. 631
26.2.3 Present-Day Fire-Retardant Chemicals, Treatments, and Systems...................................... 634
26.2.4 Modified Wood..................................................................................................................... 636
26.2.5 Wood-Plastic Composites..................................................................................................... 636
26.2.6 Effects of Fire-Retardant Treatments on Strength ............................................................... 637
26.3 Testing of Wood Protection ............................................................................................................... 637
26.3.1 Regulatory Fire Test Methods .............................................................................................. 638
26.3.2 Micro- and Bench-Scale Test Methods ................................................................................ 639
26.3.3 Durability/Impact to Wood Testing......................................................................................640
26.4 Technical Resources .......................................................................................................................... 642
26.5 Disposal ............................................................................................................................................. 643
References ....................................................................................................................................................643

Chapter 27 Flame-Retardant Design and Protection for Textiles ...................................................................................648

Baljinder K. Kandola
27.1 Introduction .......................................................................................................................................648
27.2 Measurement of Fabric Flammability and Testing Standards ..........................................................648
27.2.1 Simple Ignition Tests ............................................................................................................ 649
27.2.2 Flame Spread........................................................................................................................649
27.2.3 Heat Release Tests ................................................................................................................ 650
27.2.4 Mannequin Tests .................................................................................................................. 651
27.2.5 Full Product Tests ................................................................................................................. 651
27.3 Flammability of Different Fiber and Textile Types .......................................................................... 652
27.4 Application-Based Hazards and Performance Requirements ........................................................... 653
27.4.1 Apparel Fabrics .................................................................................................................... 653
27.4.2 Protective Clothing............................................................................................................... 654
27.4.3 Curtains and Drapes............................................................................................................. 655
27.4.4 Upholstery and Bedding Fabrics .......................................................................................... 655
27.4.5 Floor Coverings .................................................................................................................... 655
27.4.6 Tents and Marquees.............................................................................................................. 655
27.4.7 Transportation ...................................................................................................................... 655
27.4.8 Fiber-Reinforced Polymeric Composites ............................................................................. 656
27.5 Fire-Retardant Strategies (or Approaches) ........................................................................................ 657
27.5.1 Surface Treatments............................................................................................................... 658
27.5.2 Fire-Retardant Additives/Copolymers in Synthetic Fibers ..................................................664
27.5.3 Nanocomposite-Based Flame Retardants in Textiles .......................................................... 665
27.5.4 Heat Resistant and Inherently Fire-Retardant Fibers........................................................... 667
27.5.5 Fiber Blending ...................................................................................................................... 669
27.5.6 Composite Assemblies—Design Issues ............................................................................... 670
27.6 Future Trends..................................................................................................................................... 670
References ....................................................................................................................................................670

Chapter 28 Flame-Retardant Design and Protection for Electrical and Electronic Systems ......................................... 676
Sergei Levchik, Eyal Eden, and Lein Tange
28.1 Fire Hazards in Electrical and Electronic Equipment....................................................................... 676
28.2 Fire Tests ........................................................................................................................................... 676
28.3 Mechanical and Electrical Tests ........................................................................................................680
xvi Contents

28.4 Flame Retardants in Different Parts of E&E Equipment.................................................................. 682

28.4.1 Enclosures ............................................................................................................................ 682
28.4.2 Printed Wiring Boards ......................................................................................................... 686
28.4.3 Connectors............................................................................................................................ 689
28.4.4 Wires .................................................................................................................................... 692
28.5 Recycling of WEEE Polymers .......................................................................................................... 693
28.5.1 Volumes of WEEE Plastics .................................................................................................. 693
28.5.2 Collecting and Sorting ......................................................................................................... 694
28.5.3 Recycling Processes ............................................................................................................. 695
28.6 Conclusions and Future Trends ......................................................................................................... 696
References .................................................................................................................................................... 697

Chapter 29 Flame-Retardant Design and Protection for Wire and Cable ...................................................................... 701
Walid H. Awad
29.1 Introduction ....................................................................................................................................... 701
29.2 Product Development ........................................................................................................................ 701
29.3 Polymers Used in Wire and Cable..................................................................................................... 701
29.3.1 Polyethylene.......................................................................................................................... 701
29.3.2 Polypropylene ....................................................................................................................... 705
29.3.3 Ethylene Vinyl Acetate ......................................................................................................... 705
29.3.4 Ethylene Acrylate Copolymers (EAC) ................................................................................. 706
29.3.5 Polyolefin Elastomers ........................................................................................................... 706
29.3.6 Chlorinated Polyethylene (CPE)........................................................................................... 706
29.3.7 Chlorosulfonated Polyethylene (CSM) ................................................................................. 707
29.3.8 Polyvinyl Chloride ............................................................................................................... 707
29.3.9 Fluorinated Polymers ........................................................................................................... 707
29.3.10 Silicone Polymers................................................................................................................. 708
29.3.11 Polyamides ........................................................................................................................... 708
29.3.12 Thermoplastic Polyurethane (TPU) ..................................................................................... 709
29.4 Flame Retardancy of Wire and Cables.............................................................................................. 709
29.4.1 Principles of Flame Retardancy ........................................................................................... 709
29.4.2 Halogenated Flame Retardants ............................................................................................ 710
29.4.3 Non-Halogenated Flame Retardants .................................................................................... 711
29.5 Cable Manufacturing: Compounding and Coating Process .............................................................. 713
29.5.1 Extrusion Compounding ...................................................................................................... 713
29.5.2 Reactive Extrusion Compounding (Cross-linked HFFR) .................................................... 713
29.5.3 Wire and Cable Coating ....................................................................................................... 714
29.6 Flammability Testing for Wire and Cable ......................................................................................... 714
29.6.1 Small-Scale Fire Test ........................................................................................................... 716
29.6.2 Large-Scale Fire Test ........................................................................................................... 717
29.6.3 Correlation between Small- and Large-Scale Fire Testing .................................................. 718
29.7 Future Trends in Wire and Cable ...................................................................................................... 719
29.8 Conclusions........................................................................................................................................ 720
References ....................................................................................................................................................720

Chapter 30 Flame-Retardant Design and Protection for Building Materials ................................................................. 724
Alexander B. Morgan, Alessandra Lorenzetti
30.1 Introduction ....................................................................................................................................... 724
30.1.1 Building Components That Require Fire Protection ........................................................... 724
30.1.2 Fire Risk during and after Construction .............................................................................. 724
30.1.3 Building Codes—Local vs. International ............................................................................ 725
30.1.4 Fire Protection of Structures ................................................................................................ 727
30.2 Fire Protection of Roofing and Siding ............................................................................................... 727
30.3 Fire Protection of Insulation Systems ............................................................................................... 728
Contents xvii

30.4 Fire Protection of Structural Systems ............................................................................................... 732

30.5 Conclusions and Outlook ................................................................................................................... 733
References ....................................................................................................................................................733

Chapter 31 Flame-Retardant Design and Protection for Furniture and Furnishings ..................................................... 736
Mauro Zammarano, Alessandra Lorenzetti, Michele Modesti, Alexander B. Morgan
31.1 Introduction to the Fire/Furniture Problem....................................................................................... 736
31.2 Fire Codes and Regulations for Furniture and Furnishings .............................................................. 736
31.3 Fire Barrier Fabrics ........................................................................................................................... 738
31.4 Test Methods...................................................................................................................................... 738
31.5 Flexible Polyurethane Foam Fire Physics and Fire Growth.............................................................. 739
31.6 Flexible Polyurethane Foam Formulations and Chemistry............................................................... 744
31.6.1 Isocyanate and Polyol Chemistry Effects............................................................................. 745
31.6.2 Relevant Flame Retardant Chemistry .................................................................................. 746
31.7 Conclusions and Future Directions ................................................................................................... 749
References ....................................................................................................................................................750

Chapter 32 The Future of Material Fire Protection—Unmet Needs, New Fire Risk Scenarios,
and New Flame Retardant Approaches........................................................................................................ 753
Alexander B. Morgan
32.1 Introduction and Brief History of Reaction-to-Fire Events Driving Fire Protection Needs ............. 753
32.2 Current Unmet Needs for Polymeric Material Fire Protection ......................................................... 753
32.2.1 Reactive and Polymeric Additives........................................................................................ 753
32.2.2 Recyclable/End-of-Life Compatible Flame-Retardant Chemistries .................................... 754
32.2.3 Test Methods ........................................................................................................................ 755
32.2.4 Cost-Benefit Analysis—When Should We Use FR Additives?............................................ 756
32.3 New Fire Risk Scenarios ................................................................................................................... 756
32.3.1 Electric Transportation ......................................................................................................... 756
32.3.2 Aviation ................................................................................................................................ 758
32.3.3 Wildland Urban Interface (WUI)......................................................................................... 758
32.3.4 Additive Manufacturing ....................................................................................................... 759
32.3.5 Changing Power Systems ..................................................................................................... 760
32.4 Conclusions........................................................................................................................................ 761
References ....................................................................................................................................................761

Index .................................................................................................................................................................................. 765

Preface
Greetings, fellow fire safety scientist/engineer: disposal). It sounds like we’re underselling the book, but in
In your hands you hold the third edition of “Fire reality, we’re telling you that this book is a great place to
Retardancy of Polymeric Materials.” The first edition was start, and it’s got all the starting information in it, but expect
published in 2000, the second edition was published in to put in some work if you really want to get to solutions.
2010, and now we have the third edition. Each time an Once again, we would like to thank all those who have
edition has been published, the book has expanded, making helped make this book possible and helped build the foun­
it more comprehensive in scope. The book now covers every dation that has led to the 3rd edition. This includes all of
class of flame retardant chemistry, regulations, codes and our colleagues who contributed new chapters and those
standards, fire physics, emissions toxicity, aspects of fire who revised chapters from the second edition. Additionally,
safety engineering, testing, and how to apply fire protection we want to thank Taylor & Francis for agreeing to go with
to materials. Flame retardant material design was always a third edition and providing insight on changes to the book
multidisciplinary, and you’ll see this reflected in the book. market and e-books. Finally, we wish to thank our wives,
This book includes a wide range of authors and empha­ Julie Ann Morgan and Nancy Wilkie, for their tireless sup­
sizes the multidisciplinary aspect and teamwork required port, editing skills, and putting up with us talking “shop”
to generate successful fire safe materials. Successful fire well after work hours have ended.
protection of materials requires chemistry, physics, engi­
neering, and now more often, economics and environmen­ —Alexander B. Morgan, PhD
tal assessments to get it right. The field of fire protection, April, 2024. Dayton, Ohio USA
and indeed flame retardancy of polymeric materials, has
changed greatly since the second edition was published in —Charles A. Wilkie, Professor Emeritus
2010, and this book captures those changes, the additional April, 2024. Milwaukee, WI USA
needs, and proposes the way forward so that we can con­
tinue to practice this field. It’s important to realize that our
field of fire protection is driven by laws and regulations and Alexander B. Morgan received his BS
is a very old field of science. Fire protection of materials in chemistry from Virginia Military
has been in place since the dawn of recorded history, and Institute in 1994, his PhD in chemistry
as long as we have carbon-based materials and oxygen, fire from the University of South Carolina
can and will be something we must protect against. in 1998. Dr. Morgan has over 27 years
As with previous editions, this book is a mix of “how-to” of experience in the areas of materi­
guidance, distillates of technical knowledge, and reference als flammability, polymeric material
material to enable the fire safety scientist/engineer to protect flame retardancy, fire science, fire
polymeric materials. We’ve included bio-based materials in testing, thermal decomposition chem­
this edition as well, so fire protection of wood (which is a istry, and fire safety engineering with
polymeric material) is covered as well. We believe that this an emphasis on chemical structure property relationships and
book is an excellent place to start to “dive in” if you’re new fire safe material design. He has helped academic, govern­
to the field of fire safe materials, and for those of you with ment, and industrial customers solve their flame retardant and
experience or who are experts, we believe you’ll find some­ fire safety needs in a wide range of applications. Dr. Morgan
thing as well since THE experts in our field have contrib­ is on the editorial review board for Fire and Materials and is
uted to this book. It should be noted though (and this will the editor-in-chief for the Journal of Fire Science. He is also
be obvious to some) that you will not be able to learn every­ a member of ASTM, Sigma Xi, International Association of
thing just from reading the book as some experimentation Fire Safety Scientists, and the American Chemical Society.
and experience is required in this field. For those reading His current research areas include the following:
this book hoping to find a quick answer to solving a specific
material flame retardancy problem—you will find answers, • New Flame Retardant Technology with Reduced
but as you read the book, you will realize that there is no Environmental Impact for Electronics, Building
quick answer to material fire safety and material flammabil­ Materials, Bedding/Furniture, Wire and Cable,
ity. Flame retardancy of materials remains one of the most Transportation, Textiles
challenging materials science fields, as one must not only • Fire Testing Method Development
provide protection against fire for a polymeric material, but • Fire Safety/Survivability for Aircraft and Ground
one must provide that protection while considering all the Vehicles
other balance of property issues (cost, mechanical, and ther­ • Materials Development and Technology Assess­
mal performance) and ever increasing regulations (banned ment for Additive Manufacturing for Aerospace
chemistries, changing fire risks, recycling, end-of-life Applications

xix
xx Preface

Charles A. Wilkie received his read a paper on phosphorus-based flame retardants and
BS degree in chemistry from the decided to move into that area. He has worked in the field
University of Detroit in 1963 and of flame retardancy for more than 30 years. His initial
his PhD in Inorganic Chemistry work was to attempt to understand mechanistically how
from Wayne State University in a flame retardant interacts with a polymer. His research
1967. He subsequently joined group also did quite a bit of work on nanocomposite
Marquette University as an assis­ based flame retardancy. Wilkie has served, and continues
tant professor and rose through the to serve, on the editorial boards of several journals and
ranks until retiring in 2009; he now has been involved with organizing several meetings in
is a professor emeritus. In 1978, he this area.
Contributors
Walid H. Awad Ali Gooneie
SACO AEI Polymers, USA Circular Plastics, Department of Circular
Chemical Engineering, Faculty of Science
Adrian Beard and Engineering
Clariant Plastics and Coatings Deutschland GmbH Maastricht University
(Corporation) The Netherlands

Aurelio Bifulco Jaime C. Grunlan

Department of Chemical Materials and Industrial Department of Mechanical Engineering
Production Engineering (DICMaPI) Texas A&M University
University of Naples Federico II USA
Italy Department of Materials Science Engineering
Texas A&M University
Sergio Bocchini USA
DISMIC Politecnico di Torino sede di Alessandria Department of Chemistry
INSTM Research Unit Texas A&M University
Italy USA

Serge Bourbigot Laura E. Hasburgh

Univ. Lille, CNRS, INRAE, Centrale Lille, Institute for Materials Research and Innovation
UMR 8207—UMET—Unité Matériaux et University of Bolton
Transformations, F-59000 Lille UK
France
Institut Universitaire de France (IUF) Qingliang He
Giovanni Camino Lanxess AG
DISMIC Politecnico di Torino sede di Alessandria, Germany
INSTM Research Unit, V
Marcelo M. Hirschler
Italy
GBH International
Federico Carosio USA
Dipartimento di Scienza Applicata e Tecnologia,
Peter Hornsby
Politecnico di Torino, Italy
Queen’s University Belfast
Dushyant M. Chaudhari
A. Richard Horrocks
Fire Safety Research Institute (FSRI)
Fire Chemistry Laboratory
UL Research Institute
CMRI
USA
Simo Hostikka
Jiuke Chen
Aalto University
Laboratory for Advanced Fibers, Empa Swiss Federal
Espoo, Finland
Laboratories for Materials Science and Technology
Switzerland
T Richard Hull
Department of Materials
Centre for Fire and Hazards Science
ETH Zurich, Switzerland
University of Central Lancashire
Preston, UK
Eyal Eden
ICL-IP
Marc Janssens
USA
Southwest Research Institute
San Antonio, USA
Sabyasachi Gaan
Laboratory for Advanced Fibers, Empa Swiss Federal David D. Jiang
Laboratories for Materials Science and Technology Organic Technology/Corporate Research
Switzerland New York, USA

xxi
xxii Contributors

Paul Joseph Alessandra Lorenzetti

Institute of Sustainable Industries and Liveable Cities Department of Industrial Engineering
Victoria University University of Padova
Australia Italy

Baljinder K. Kandola Michele Modesti

Institute for Materials Research and Innovation Department of Industrial Engineering
University of Bolton University of Padova
UK Italy

Grant T. Kirker Alexander B. Morgan

Institute for Materials Research and Innovation University of Dayton Research Institute
University of Bolton Dayton, Ohio
UK
Katie M. Ohno
Wenyu Wu Klingler Institute for Materials Research and Innovation
Laboratory for Advanced Fibers, Empa Swiss University of Bolton
Federal Laboratories for Materials Science and UK
Technology
Switzerland Rudolf Pfaendner
Fraunhofer Institute for Structural Durability and System
Thomas J. Kolibaba Reliability LBF
Applied Chemicals and Materials Division Germany
National Institute of Standards and Technology
USA D. Price
Centre for Research and Innovation
Michael Kuepfert
University of Bolton
Lanxess AG
UK
Germany

Sergei Levchik Guillermo Rein

ICL-IP BRE Centre for Fire Safety Engineering
USA The University of Edinburgh
UK
Zheng-Ming Li
The Collaborative Innovation Center for Eco-Friendly and Bernhard Schartel
Fire-Safety Polymeric Materials (MoE) Bundesanstalt für Materialforschung und-prüfung (BAM)
National Engineering Laboratory of Eco-Friendly Germany
Polymeric Materials (Sichuan)
College of Chemistry Daniel F. Schmidt
Sichuan University Luxembourg Institute of Science and Technology (LIST)
China Luxembourg

Bo-Wen Liu Arvindh Sekar

The Collaborative Innovation Center for Eco-Friendly and Laboratory for Advanced Fibers
Fire-Safety Polymeric Materials (MoE) Empa Swiss Federal Laboratories for Materials Science
National Engineering Laboratory of Eco-Friendly and Technology
Polymeric Materials Switzerland
College of Chemistry
Sichuan University Kelvin K. Shen
China Rio Tinto/U.S. Borax, USA

Jing-Hong Liu Christopher Simpson

The Collaborative Innovation Center for Eco-Friendly and Lanxess AG
Fire-Safety Polymeric Materials (MoE) Germany
National Engineering Laboratory of Eco-Friendly
Polymeric Materials (Sichuan) Anna A Stec
College of Chemistry Centre for Fire and Hazards Science
Sichuan University University of Central Lancashire
China UK
Contributors xxiii

Stanislav I. Stoliarov Yu-Zhong Wang

Department of Fire Protection Engineering The Collaborative Innovation Center for Eco-Friendly and
University of Maryland Fire-Safety Polymeric Materials (MoE)
College Park National Engineering Laboratory of Eco-Friendly
Polymeric Materials (Sichuan)
Lein Tange College of Chemistry
ICL-IP Sichuan University
USA China

Jose L. Torero Carl-Eric Wilen

BRE Centre for Fire Safety Engineering Faculty of Science and Engineering
The University of Edinburgh Åbo Akademi University
UK Finland

Svetlana Tretsiakova-McNally Charles A. Wilkie

Belfast School of Architecture and the Built Environment Marquette University
Ulster University USA

Xiu-Li Wang Mauro Zammarano

The Collaborative Innovation Center for Eco-Friendly and Fire Research Division, Engineering Laboratory
Fire-Safety Polymeric Materials (MoE) National Institute of Standards and Technology
National Engineering Laboratory of Eco-Friendly USA
Polymeric Materials (Sichuan)
College of Chemistry
Sichuan University
China

Yin-Long Wang
The Collaborative Innovation Center for Eco-Friendly and
Fire-Safety Polymeric Materials (MoE)
National Engineering Laboratory of Eco-Friendly
Polymeric Materials (Sichuan)
College of Chemistry
Sichuan University
China
 1 An Introduction to Materials Flame
Retardancy and Fire Protection
Alexander B. Morgana and Charles A. Wilkieb
a University of Dayton Research Institute, Dayton, OH, 45469
b Marquette University, Milwaukee, WI, 53233

1.1 FIRE AND SOCIETY do work for us. It is not that modern society has lost its
fear of fire, but instead we have grown accustomed to con­
As per the US National Fire Prevention Association trolled, and controlling, fire, where we ignite the flame and
(NFPA) annual report on fire loss in the United States, for control its use. Uncontrolled fire activates our instinctual
the year 2021 there was 1.35 million reported fires result­ fear mechanism, but until we see it, we really do not think
ing in 3,800 deaths, 14,700 injuries, and property losses of about it. Only those who have encountered accidental fires
$15.9 billion.1 Fire losses vary by country outside the US, in their lifetime become acutely aware of fire dangers and
and some countries have larger fire losses than others, but hazards—the rest of us tend to not think about it until it
regardless, fire losses continue in just about every coun­ appears. So at first glance we might say that humanity
try on the planet.2 In the 14 years since the second edition has conquered fire except for the occasional outbreak, but
of this book was published, there has been an increase in when we return to the statistics, we see that this is not the
wildland-urban interface (WUI) fires, and some notable case. Fire can be prevented in most cases, yet we still have
fire losses that have made the news due to both natural catastrophic fire losses which result in loss of wealth, pos­
and manmade disasters. There is a lot to digest in all this sessions, livelihood, and life. It is for these reasons that
fire loss data, and detailed study does give insight into there are scientists and engineers who not only study fire
where more protection against fire is needed. Statistics, but seek to provide passive fire protection for daily life so
though, are just numbers and do not really tell the whole that we, as a society, will not have to worry about fire, and
story even though they attempt to. Most people are not should an accidental fire begin, it can be rapidly extin­
swayed by numbers that try to tell them something, but guished before it grows. If you are reading this book, a lot
humanity does react to stimuli, and one of those stimuli of this may be very obvious to you, but it is not obvious
is an innate fear of fire, and with good reason. Fire is a to everyone for many of the reasons described previously.
unique destructive force of nature; what it touches cannot Yes, we all know fire is there, but what many people do
easily be repaired, rebuilt, or restored to its normal form. not realize is the great potential for fire all around us. It is
Scientifically, fire is thermo-oxidative decomposition of a due to this potential that the discipline of flame retardancy
material, which means it converts carbon-based materi­ exists.
als and other combustible matter into CO2 and water. In
layman’s terms, fire consumes what it touches and leaves
1.2 DEFINITIONS OF FLAME RETARDANCY
behind nothing but ashes. Even non-carbon-based materi­
als will suffer fire damage, from melting to thermal shock Before one starts reading a book about flame retardancy,
damage, to oxidation of metal surfaces caused by fire. Even there are some terms which need to be defined for both
concrete suffers damage under fire as water trapped in the inexperienced and experienced reader, since one will
the concrete becomes superheated steam, which pushes out see many terms throughout the book that at first glance
of concrete with explosive force, leading to cracking and, look similar but have very different meaning when study­
in some severe cases, structural failure of the concrete. ing flame retardancy of materials. First of all, the terminol­
Fire is fatal to almost all life on the planet (except for a few ogy of “fire retardancy” and “flame retardancy” are used
plants which germinate after fire has destroyed forest and more or less interchangeably. There is some perception
underbrush) and is something that all of us know to avoid that flame retardancy involves a lower risk than fire retar­
since we know it will burn and maim us, and if we cannot dancy; in this volume these terms are both used and mean
escape, it will kill us. But in modern society, fire is some­ the same thing. However, it is important to understand fire
thing we use to make life easier. It is a universal energy protection terms as well, as the discipline of fire protec­
source for converting matter into heat energy, which is tion engineering drives the requirements that may require
either used directly or is used to drive other devices which a polymeric material to have flame retardant properties.

DOI: 10.1201/9781003380689-1 1
2 Fire Retardancy of Polymeric Materials

By understanding fire protection principles it becomes not always straightforward. For more details on this, the
possible to know when to use flame retardants and when reader is encouraged to peruse Chapters 3, 17, 18, 21, and
other engineering methods of fire protection are more 22.
appropriate.
1.2.4 FLAME RETARDANT
1.2.1 FIRE PROTECTION
This term is used for any chemical that allows a material
This is the overarching concept driving the purpose behind to retard a flame, or for any polymer that shows the ability
this book. Because fire happens, and it leads to losses, there to slow fire growth when ignited. It does not mean non­
is a need to protect against it. Fire protection engineering combustible or ignition resistant—these are very different
uses a wide range of concepts and multiple fields of sci­ terms and should not be used to describe a flame retardant
ence to engineer solutions that protect materials against material.3 A material that is truly noncombustible or igni­
fire. Fire protection can take many forms, including active tion resistant either cannot be combusted (no thermo-oxi­
approaches such as someone on fire watch looking for fires dative decomposition can occur) or cannot be ignited with
that they then put out, to reactive approaches that activate a particular size flame/heat source. Here, things sometimes
once some sort of fire stimulus require them. A good exam­ get confusing: a material could be flame retarded so that
ple of reactive fire protection would be water sprinklers for under a test which measures aspects of ignition or combus­
buildings or temperature activated extinguishers for restau­ tibility, the material is measured/assessed to be noncombus­
rant exhaust hoods above cooking fryers. Then there are tible/ignition resistant, but under another set of conditions
passive fire protection methods which assume fire will hap­ it burns with ease (see Chapters 3, 7, 18, 21, and 22). It is
pen and the material needs to be there to slow fire growth/ important here to realize that the flame retardant effect of a
flame spread and allow time to escape. Flame retardants chemical is a function of its particular chemical structure in
typically fall into the passive category, but depending upon the presence of a particular polymer. Something that may
how they get used, they can be part of reactive approaches be a flame retardant for one polymeric material in one fire
as well. risk scenario may not provide any flame retardant effect for
another fire risk scenario. As this book will make it clear,
there is no generic class of “flame retardants.” The ability
1.2.2 FLAME RETARDANCY
of a chemical to have a flame retardant action is chemical
Flame retardancy means that something has been done structure dependent, and the chemical structures can be
to a material so that when exposed to a flame, either the highly varied. Of final note, the term “flame retardant” is
material will retard the growth and propagation of that often abbreviated as “FR,” such that flame retardant addi­
flame, or it will retard (slow) the growth and propaga­ tives are described as “FR additives” or sometimes just
tion of any flames that may come from the material once as “FRs.” A flame retardant plastic, though, may be listed
it has been ignited. Fire retardancy does not mean that as “FR plastic” or “FR resin,” or described simply as an
the material will not burn, but rather that it will be more “FR material.” When reading, look at how the author uses
difficult burn. In some cases the flame retardant mate­ the term since one may use an FR additive to make a FR
rial may self-extinguish after being ignited if the external polymer.
flame is removed, but in other cases, the flame retardant
approach assumes the material will stay lit once ignited
1.2.5 COMBUSTIBILITY
and will instead just burn slowly. What is required of a
flame retardant material (self-extinguishment or slow burn This is defined by a series of conditions, as is the ability to
rate) is dictated by the specific regulatory test under which resist ignition. It can be said that all carbon-based mate­
the material is rated/sold, which in turn is governed by fire rials can be combusted (converted to CO2 and H2O) with
risk scenarios. enough heat and oxygen, but it may be hard to do so under
some conditions, so a particular test may define certain
carbon-based materials as noncombustible. Only inorgan­
1.2.3 FIRE RISK SCENARIO
ics (glasses, ceramics) and metals in their highest oxida­
A fire risk scenario is considering how a material/structure/ tion state would be noncombustible using the definition of
assembly may be exposed to fire, and is it expected to thermo-oxidative decomposition. Again, Chapters 3, 17,
lead to loss and injury. More specifically, it considers the 18, 21, and 22 address aspects of these definitions, but the
probabilities of fires happening and the probability of that reader is encouraged to understand that fire retardant does
leading to loss, and how bad that loss could be. This is an not always mean noncombustible.
important concept to understand as, once identified, it helps
determine how a material will be fire retarded or made fire
1.2.6 THERMAL DEGRADATION/DECOMPOSITION
safe to resist that particular fire risk scenario, or at least not
contribute negatively to fire growth. Fire risk scenarios are Another set of definitions with which one should be aware
highly varied, and their relationship to regulatory tests is is the difference between thermal degradation and thermal
An Introduction to Materials Flame Retardancy and Fire Protection 3

decomposition, since they are not exactly the same thing.3 additional fire protection measures may be needed,
Thermal degradation means that under heat exposure, or guidance to customers not to use that product
some property of the material has degraded or become less outside the fire risk scenario it was designed for.
than what it was before exposure to heat. Fire Resistance: This is the ability of a material to
Thermal decomposition, on the other hand, means that withstand fire, or protect against it, for some period
the material has decomposed from its component parts of time. A flame retarded material may be able to
upon exposure to heat, and for polymeric materials, this generate fire resistance, but the time-based aspect
means that bonds have been broken, causing the polymer to of this is important to understand, as something
depolymerize and/or break up into potential fuel molecules. that may be flame retarded against a 60-second
It is important to remember that polymer decomposition is flame exposure could be very inappropriate for a
a free-radical process under fire conditions, and the chemi­ one-hour flame resistance tests.
cal reactions of bond cleavage and subsequent pyrolysis of Gasification: This is the process by which solid and
smaller molecular weight fragments from the polymer can liquid flammable materials are converted into a
be quite complex. A synopsis of these chemical pathways is gaseous state, which would enable ignition and
discussed in more detail throughout the book, with primary flame propagation. Simplistically, it’s the process
emphasis in Chapters 2, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, where something is heated up, and it goes from
15, 16, 19, and 20. Indeed, understanding how a polymer solid to liquid to gas, but the processes can be
decomposes is essential to understanding its flammability much more complex depending upon the chemi­
behavior and how to flame retard it. cal structures of the fuels involved and the heating
rates applied to the material.
Pyrolysis: This is a particular form of thermal
1.2.7 OTHER RELEVANT FIRE PROTECTION DEFINITIONS
decomposition that is very important to under­
Fire protection engineering uses other terms to determine stand. Specifically, it’s a gasification process that
if a flame retardant or other fire protection approach should occurs under anaerobic conditions (non-oxidizing).
be used, and while these terms are used mostly exclusively Effectively, post ignition, everything under the
in the fire safety engineering profession, it’s important to flame is pyrolysis meaning the polymeric material
understand them here as they do get used in test methods is decomposing and gasifying in the absence of
and fire safety standards. oxygen. This is why it’s so important to understand
thermal decomposition of materials measured
Fire Decision/Fire Safety Decision Tree: This is a under inert gases rather than oxidizing gases to
decisional “tree,” which provides guidance and really determine how it thermally decomposes.5,6
concept about what fire protection measures to use Thermal decomposition studies in oxidizing con­
and when to use them. The main guidance docu­ ditions (such as air) are best saved for studies on
ment for this work is NFPA 550: Guide to the Fire how materials smolder, or how they decompose
Safety Concepts Tree.4 This document helps fire pre-ignition.
protection engineers decide how to provide pro­
tection against a fire risk scenario and would pro­ 1.3 PROTECTION FROM FIRE—MODERN
vide guidance on when a flame retardant would be
VS. HISTORICAL VIEWPOINTS
best suited to use as either a source of primary or
secondary protection in a fire. The need to protect materials against fire has been a scien­
Fire Performance: This the how a material, product, tific undertaking for a very long time. The use of flame retar­
or structure/assembly responds to a particular fire dant additives for polymeric materials is, of course, a more
other than a controlled test fire. To better explain, recent thing, with modern synthetic polymeric materials
an analogy is useful. How a plastic behaves in a having been invented in the early 20th century. The earliest
small flame ignition test to simulate an electric fire retardants for synthetic polymers were halogen-based,
short circuit would be a “fire-test-response.” How based on the discovery of halogenated hydrocarbons and
that same plastic behaves in a room fire where waxes which effectively flame retarded Army tents.7 New
something else has caught fire and is radiating chemistries followed shortly thereafter, but each of these
heat onto it, and it ignites and starts to burn, would chemistries was created in response to a particular need to
be its fire performance. Sometimes, fire protection flame retard an object. It began with tents, but as more and
engineers do have to consider the fire performance more polymers moved into daily life, fire safety engineers
and the fire-test-response of a material in their and insurance companies found a need to push for addi­
protection decisions. For the material scientist try­ tional fire safety. It is worth mentioning again that this field
ing to design a fire safe product, it can be difficult of research is regulation-driven, and many of the fire safety
to protect against all fire scenarios, and therefore, regulations in effect today began in the early 20th century
one should consider if the product may encounter when insurance companies, tired of paying on losses due
fire outside of standard fire risk scenarios. If so, to fire, began to push for greater fire safety. Eventually fire
4 Fire Retardancy of Polymeric Materials

safety advocates took over pushing fire safety from the will damage structures, including parking garages.16 It
insurance companies, but this early start in the insurance will likely again take catastrophic fire losses for people
industry is why so many fire safety standards were created to react and demand a change in fire safety, but there is
by organizations like Underwriters Laboratories (UL) and hope that regulators will listen to history and be proac­
Factory Mutual (FM); commercial products today are certi­ tive, rather than reactive, to the problem. If a change in fire
fied by these organizations before they can be sold in the US. safety performance for automotive plastics is enacted, then
Later the US federal government added its own regulations there will be a huge demand for flame retardant products
for particular fire safety needs, as did US state governments in cars. It should be noted that with increased electrifica­
and other organizations worldwide. There is no one univer­ tion of cars and use of high energy intensity battery packs
sal fire standard worldwide, which is why fire risk scenarios (Lithium Ion) now being used in all-electric vehicles, the
set the fire test that a material must pass and, in turn, why fire risk scenario changes again from crash + fuel release
a particular flame retardant system is designed to pass that yielding fuel pool fires, to battery failures (in crash or dur­
test. This is important to understand because no one system ing charging/short circuit failure) yielding very fast fire
will pass all fire tests, and in general, today one designs a growth events and great difficulty in extinguishing lithium
system to meet a particular test, not to be flame retardant ion battery packs once they ignite.17–20 Despite the clear
against all fire situations. Since the intensity of a flame will and obvious issue behind Li Ion battery fires, it remains
vary from situation to situation, it is almost impossible to unclear when or if the fire safety standard for automotive
create a universal flame retardant system; instead, industry, plastics will change.
and others, design flame retardant polymeric materials to The flammability issues of polyurethane foam have been
pass the test which is related to a specific fire risk scenario. well understood for some time now, but the approaches to
This approach, though, runs into trouble with the “reactive” fire safety with this highly flammable material have been
approach of providing fire safety for a material. varied, including by country.21 In the US, the fire risk sce­
The way that new fire safety regulations have come into nario was identified as people smoking in bed, and the
being is from a reaction or response to a particular prob­ solution at the time was to educate the public about smoke
lem. There are many examples to choose from here, but we detectors, as well as to make sure the fabrics used could
will focus on three: plastics in cars, polyurethane foam, and resist a smoldering ember source, like that from a cigarette.
polymers for electronics. In the United Kingdom, though, the problem was tackled
For automobiles in the US in the 1970s, there was at the polyurethane level and required high levels of flame
strong concern over the high number of fires in automo­ retardancy to pass a very strict fire test, the Crib V test.22
bile crashes, but also over how the plastics in the interior This test, named for the class V wooden “crib” fire source, is
of the car would respond to small ignition sources (ciga­ still the strictest in the world for fire safety of polyurethane
rette ashes). A fire standard, Federal Motor Vehicle Safety foam used in furniture or bedding, and as such, the UK has
Standard 302 (FMVSS 302), was created to assess the practically no fire losses due to furniture or bedding igni­
potential for flame spread in an automobile. At the time, tion. The US, due to perceptions about the hazards of flame
the standard did its job, but as there is an ever increasing retardant chemicals vs. any potential benefit for fire protec­
demand for fuel efficiency in cars and a desire to use new tion,23 has instead now moved to smolder-only testing even
materials in automobile construction, the amount of plas­ though smoking in the US has decreased. This began with
tics in a car crept up from 10kg in a 1970s car to 90–100 a change to the California Technical Bulletin 117 (TB 117)
kg in a modern 1990s-2000s car.8 The FMVSS 302 test, in 2013, moving from open flame testing to cigarette test­
which is a very simple test to pass, really just assesses ing, and then this approach was codified into US law via 16
how well a flame will spread once a car interior mate­ CFR 1640 in 2021. This move to smolder-based testing has
rial is ignited, and almost any plastic today will pass the proven to be problematic, and fire loss statistics from 2013
test. This presents a problem in that a historical standard, to present are showing that when furniture is involved in
which worked for its time, has not kept up with modern fire events, it does lead to major losses and high probability
changes, so that now the primary fire risk in a collision is of injuries and death.24,25 Since polyurethane foam in furni­
not just from the fuel tank rupturing and leading to fire, but ture and bedding remains the number one source of flam­
the fact that there is about 90–100 kg of solid fuel inside mable fuel in the US home,26–28 it is clear that we need to
the automotive compartment where the passengers are fire protect this product either through flame retardants, use
located. Indeed, studies have shown that modern cars do of sprinklers in home, or the use of barrier fabrics. The cur­
much worse in fires than their older counterparts,9–15 but rent political and regulatory environment in the US seems to
the standard has remained unchanged since only recently indicate that the fire losses involving flexible polyurethane
has this concern begun to be voiced. Indeed, the high level foam are only going to increase in the near future, and it
of polymeric materials present on both the inside and the will likely take ever-increasing losses of life and property
outside of modern vehicles is leading not just to higher for this to change. Smolder-based testing does not provide
hazard for occupants but also increased fire hazard for any protection against open flames or high-intensity igni­
buildings that these vehicles are located in. Specifically, tion sources (such as failing lithium ion batteries from cell-
modern vehicles release high levels of heat release that phones or laptops), and so we have a situation here where
An Introduction to Materials Flame Retardancy and Fire Protection 5

fire safety is heading in the wrong direction, even though happen? The answer is very complex, and it depends upon
there are solutions available. the level of flame retardant in the plastic exposed to the
Since flame retardants are used in response to chang­ candle-like flame. If the plastic is UL-94 rated V-1 or bet­
ing fire scenarios, which develop as technology changes, it’s ter, nothing will happen, as the flame will go out, but if
noteworthy to speak about polymers for electronics and how the plastic has a lower flame retardant rating, the flame can
much the fire risk scenarios have changed due to techno­ spread rapidly, and in some cases can lead to very large
logical changes, even if the test methods to assess fire safety fires. Extensive studies done by many laboratories have
of electronics has changed very little. Electronics technol­ shown that a small candle-like flame can ignite a non-flame
ogy has changed a lot in the past 60+ years, and as it has retardant plastic casing for a TV set or printer which can
changed, so has plastic usage for this technology. Originally, easily lead to room flashover.34 The US National Institute
plastic components were a minor part of electronics, only of Standards and Technology (NIST) had a program called
used in some circuit boards and internal wiring and parts “Flammability Measures of Electronic Equipment,” which
of keyboards. Today, they are a part of almost every com­ studied several commercial plastics at both bench scale and
ponent on a computer (laptop or desktop) as well as most large scale, and they found that parts made from UL-94 V-1
modern electrical equipment and electronic appliances. or better plastics would not ignite with a small candle-like
Indeed, with many modern electronic appliances starting flame.35–37 However, if a non-flame retardant keyboard was
to have high levels of electronic control and, in some cases, put under a computer monitor case, and the keyboard was
wireless communication capability, there are far more elec­ ignited, the heat release from the burning keyboard would
tronic plastics in use today, and the amounts used continue overwhelm even the higher rated flame retardant plastics.
to increase. Since electrical short circuits (failures) can Therefore the fire risk scenario of electronics is continuing
be possible ignition sources, it is very important to flame to change as new technology enters the marketplace and the
retard the polymer if the plastic is anywhere near a power regulations are not keeping pace. Keeping materials with a
supply or electrical component that can give off heat when UL-94 V rating in place appears to be a reasonable place
it fails (capacitors, heat sinks, computer chips, wiring, etc.). to start, but many changes in how these items are mounted
The insurance industry helped create the early regulations on walls or used in homes may result again in regulators
and fire testing standards to protect electrical and electronic reacting to change rather than being proactive in fire safety
equipment, and the best example of this, still in use today, is performance.
the UL-94 test.29 This test exposes a small plastic specimen, None of these scenarios described in the previous section
in either a vertical or horizontal configuration, to a small are easy to address in a proactive manner. If regulators kept
calibrated Bunsen burner flame (25 to 125 mm in height) products from entering into use until they could determine
for short ten-second ignitions, and the time to extinguish­ all possible fire risk scenarios, many products might never
ment is recorded. The time to self-extinguishment deter­ come to the marketplace. Practically speaking, no regulator
mines the rating of the material, with higher ratings (V-0 can envision all possible fire risk scenarios for a material.
or 5-V) being typically used for electronic equipment. This Some things cannot be envisioned until they are used by
test originated in the early days of electronic equipment in the consumers, and therefore some regulation changes must
the US home, specifically the 1950s, where many US homes be reactive rather than proactive. Still, regulators and con­
had a television set in the living room. The UL-94 V test sumers need to be aware that fire risk never goes away, and
(V for vertical test) was designed to mimic the television so one should not be surprised when changes in technol­
(TV) set on wheels, which was often moved over the 1950s ogy lead to changes in consumer use which either defeats
style carpet for typical American family gatherings. If the the fire protection in place for that material or makes the
television set caught fire, flaming drips could fall from fire protection irrelevant for the ways the material is used.
the TV set and ignite the carpet underneath. Since then, Perhaps now more than at any other time in human history,
parts of the carpet have become flame retardant, and more the rapid changes in technology require all of us to be flex­
importantly, the design of the television set has changed. ible not just about how we use a material, but also how we
Flat screen TVs can be mounted on walls, ceilings, or many think about that material from a fire safety perspective and
other surfaces, and therefore if the power supply ignites and a total life cycle view.
the polymer drips—where would it go? The flame spread
may be much less if the plastic sticks to a painted wall (gyp­
sum wallboard, plaster), but could be much worse if the 1.4 CHANGING PERCEPTIONS,
wall is wooden. With other electronic equipment becom­ REGULATIONS, AND
ing so ubiquitous in the home, now the question arises
CUSTOMER DEMANDS
about not only internal ignition (electrical failure inside the
equipment) but also external ignition. There are increas­ Just as changes in technology result in new fire risk sce­
ing concerns about small flame sources igniting electrical narios, societal changes can affect flame retardancy and
equipment from the outside,30 especially in Europe.31–33 So fire safety as well. Some of the biggest changes in flame
when a candle flame touches a non-flame retardant plastic retardant materials have come from changes in waste dis­
on the outside of an electrical equipment item, what will posal and recycling of materials that have reached the end
6 Fire Retardancy of Polymeric Materials

of their usefulness. The best example of this is how the retardants, this directive affects how the plastic parts, cable
European Union (EU) disposes of its waste and the laws it jackets, and enclosures are flame retarded. If the plastic
enacted to deal with the waste. In the EU, landfills are not cannot be reground and recycled, it must go to incinera­
typically permitted since land in Europe is at a premium, tion, in which case it cannot form toxic by-products during
with almost all existing land either used for agriculture incineration. This has led to the rapid de-selection of bro­
or for living space and industry. So waste is incinerated minated FR additives in European plastics which are used
rather than sent to a landfill. Early on in this process, it in electronics, or the complete removal of FR additives from
was found, in some cases, that the brominated flame retar­ plastics used in electronics in Europe. This de-selection and
dants in flame retardant plastics would produce brominated removal led to increases in electrical fires in Europe, and
dioxin compounds. When this was discovered, some EU now customers and fire safety experts demand low envi­
states pushed to have these compounds removed from ronmental impact and fire safety. However, the existing
use in plastics, which led to a decade long legal struggle non-halogen flame retardant solutions brought in to replace
between EU governments, environmental non-government bromine have their own balance-of-property issues, and
organizations (NGOs), fire safety regulators, and the mak­ so research continues to develop materials that can meet
ers of brominated flame retardants. Much of this story and WEEE objectives. See Chapter 24 for more information on
the current state of these regulations are described later recycling of flame retardant polymers.
in Chapter 23, but to summarize, the change in a non-fire Of all the new regulations affecting flame retardant
related activity has led to changes in how flame retardants research, REACH is likely to have the greatest impact on
are used and which ones are perceived to be safe. More any new flame retardant solution created to address RoHS
importantly, it has led to a discussion about fire safety in and WEEE regulations. Since this regulation affects all
general and whether fire safety/flame retardancy is still an new and existing chemicals in the EU, all flame retardant
acceptable environmental policy. additives (each of which is a chemical compound) in use,
The environmental impact of waste disposal and of or proposed for future use, must go through extensive test­
chemical use in Europe has led to three legislative actions ing and certification before they can be used. If they do not
that, in today’s global economy, greatly affect flame pass this battery of tests, then they are banned from future
retardant use and research. These actions go by the acro­ use, which means there would be fewer solutions available
nyms of RoHS (Reduction of Hazardous Substances),38,39 for fire safety. Therefore, REACH affects not only current
WEEE (Waste Electrical and Electronic Equipment),40,41 flame retardant additive use, but also research to develop
and REACH (Registration, Evaluation, Authorisation, and new flame retardant additives. Why spend any time and
Restriction of Chemical substances).42 These actions are effort on the development of a new flame retardant solution
discussed in detail in Chapter 23 but need to be mentioned if it has no chance of passing REACH? This makes it more
here as they are clear examples of how changing regulations difficult for the flame retardant researcher to figure out
affect flame retardant use, selection, and new fire safety which chemical compounds to synthesize and test if they
developments. The first one, RoHS, refers to how new items do not pay attention to potential environmental impact and
are manufactured and specifically bans chemicals and toxicology first. Therefore, REACH may add yet another
elements of environmental and toxicological concern in scientific discipline to flame retardant research—toxicology
Europe. One fall-out item of RoHS is the move from lead- and environmental science. So one can ask—why did these
based solder on circuit boards to non-lead based solder. The regulations come into being in the EU and not everywhere
new solders (usually tin based) are higher melting and, as at once? To understand this, one must again look at the
such, require epoxy circuit boards of higher thermal sta­ “life-cycle” (creation, use, and disposal) of plastics.
bility. This has led to the some de-selection of brominated Plastics that contain flame retardant additives have
flame retardant epoxies simply because the C-Br bond on one of three fates at the end of their life cycle. One is to
tetrabromobisphenol A is not thermally stable enough to put the material into landfill; another is to incinerate it
survive exposure to the higher melting point solder. The to recover energy from the material; and the final is to
organobromine bonds break down upon exposure to this regrind, recycle, and reprocess the plastic for later use.
solder, which degrades circuit board performance. So the All three approaches have their advantages and disadvan­
selection of a material which at first glance has nothing to tages, but overall, incineration and recycling are preferred.
do with FR performance has led to a new paradigm in flame Within those two approaches though, the perception exists
retardant research: higher thermal stability of the polymer that flame retardants do not belong due to pollution they
itself to withstand high-temperature solder while maintain­ cause during incineration or pollution caused by recycling
ing flame retardant performance. the plastic which may cause the additive to leach out of the
WEEE has had a direct effect on flame retardant use, plastic. There is data both for and against these perceptions
since flame retardants are used in almost all electrical and of flame retardants in plastics, but the environmental NGO
electronic equipment to prevent fires from short circuits. groups have been winning public opinion that it is better
This directive lays down rules for disposal and recycling environmental policy to leave the flame retardants out com­
of all electrical and electronic equipment which goes back pletely. This argument, though, only holds true if that non-
to the previous incinerator discussion. In regards to flame flame retardant plastic does not catch fire. Several studies
An Introduction to Materials Flame Retardancy and Fire Protection 7

have shown that the amount of pollution which enters the particular component of the final article, the flame retar­
environment when a plastic catches fire is far greater than dant materials scientist will need to understand fire safety
the pollution used in creation and disposal of a flame retar­ engineering and these new models to better design their
dant plastic.43–51 This is because when a non-flame retar­ materials. It is likely that the change in performance-based
dant plastic catches fire, it tends to give off so much heat codes, along with changes in environmental standards, will
that it ignites other nearby objects, and those objects in turn yield all sorts of new flame retardant materials used in new
quickly cause the heat release in the room to escalate, lead­ and very creative ways. However, this change means that
ing to major fire losses, large amounts of toxic emissions, the burden of flame retarding the polymeric material may
and in some cases, loss of life (see Chapter 19 for more fall upon the final item/assembly producer and no longer on
information on fire emission toxicity). So one has to make a the resin companies which compound flame retardants into
decision—is it more acceptable to lose life and property to plastics before they sell it. All of this is uncharted territory,
fire for the potential long-term benefit of the environment, and the correct path for polymeric fire-retardant materials
or is it more acceptable to save lives and deal with potential remains to be seen. It is likely, though, that there are mul­
pollution issues when the plastics are not dealt with cor­ tiple paths forward where new engineering approaches and
rectly at the end of their lifetime? The answer to this ques­ flame retardant chemistry will coexist to produce new fire-
tion is complex, and both sides of the argument have made safe and environmentally friendly polymeric materials.
impassioned pleas for their side. It is possible to have both
fire safety and good environmental policy, but it requires an
1.5 FLAME RETARDANT CHEMISTRIES
understanding of the following:
With this background, one begins to see why this field is so
1) Passive fire protection (flame retardants in plas­ complex and that there is no simple answer to flame retar­
tics) is an important societal benefit. dancy of polymers. This complexity is also why there are
2) Passive fire protection can be developed in a way so many flame retardant chemistries to choose from since
that is environmentally friendly and is easily many flame retardant chemistries are tailored to a specific
recycled. polymer for a specific test (see Chapters 25–31). However,
3) The cost-benefit analysis of fire protection in rel­ there are some broad categories of flame retardants in use
evant fire risk scenarios. today, including the following:
4) Both sides will need to set aside their precon­
ceived notions about the other and be willing to • Halogenated compounds (Chapter 4)
work together. • Phosphorus-based compounds (Chapter 5)
• Mineral fillers (Chapter 6)
Humanity is, by nature, emotional, and emotions on both • Intumescent protective systems (Chapter 7)
sides of this issue make progress difficult for new fire safe • Silicon and inorganic oxides (Chapter 8)
materials, whether in response to new fire risk scenarios or • Boron chemistry (Chapter 9)
in response to non-fire related issues. This last point should • Nitrogen-based compounds (Chapter 10)
make it clear that flame retardancy of plastics is not a sim­ • Radical generators (Chapter 11)
ple scientific issue, but one that must take into consideration • Polymer nanocomposite systems (Chapters 12)
societal, emotional, and non-fire related issues to make an • Bio-based flame retardants (Chapter 13)
acceptable new flame retardant material in the 21st century. • Conformal coatings (Chapter 14)
Along with the changes in perceptions of flame retar­ • Inorganic/Unusual chemistries (Chapter 15)
dants, there are changes in fire safety requirements as • Multi-component systems (Chapter 16)
well. Many of the changes were discussed in the previ­
ous section, and they are covered in detail in Chapter 23, For many of the reasons described in the last section, haloge­
but one of the changes is a move from pass/fail testing to nated flame retardant chemistry is not as greatly researched
performance-based testing. Performance-based testing in academic circles as it once was, although it continues to
allows for more freedom in how an item is constructed be a robust field of flame retardant chemistry, especially
or assembled to meet fire safety needs. This tends to be amongst the industrial manufacturers who produce these
final article testing rather than testing of a specific flame compounds. Non-halogenated flame retardant systems have
retardant material, and therefore modeling becomes quite grown by leaps and bounds in the open literature as well as
important in performance-based methodology. These mod­ patent literature, again for the reasons previously described.
eling approaches are discussed in Chapters 20 and 21, and Within each of these chemical approaches to flame retar­
modeling allows regulators and fire safety engineers to see dancy, one will find a variety of chemical structures and
how a construction performs in a particular fire scenario. compounds that yield specific effects of flame retardancy
While this approach yields high flexibility for the fire safety under specific conditions. Some compounds are fairly uni­
engineer, it can make things difficult for the scientist try­ versal and reduce heat release under all conditions (halogen,
ing to flame retard a material for an application. With no phosphorus, mineral fillers), while others have unique acti­
guidance on what the flame retardant test should be for a vation conditions and protective schemes that can be very
8 Fire Retardancy of Polymeric Materials

robust but are limited to a small number of polymers with Listed in the next section are some of the pre-eminent
which they can be used (intumescent, inorganic compounds, fire safety and flame retardant research organizations
nanocomposites). Some materials by themselves enhance worldwide. The list is by no means comprehensive and
the flame retardancy of other compounds (boron, inorganic focuses on the organizations that are known to publish
oxides, nanocomposites), while others not only enhance a often in the fields of flame retardant research or fire safety
wide range of flame retardants, but also bring multifunc­ engineering. The list here includes links to the organiza­
tional performance to a material. Polymer nanocomposite tions to learn more about the range of services and research
technology fits this last category in that the nanocomposite they offer.
brings enhanced mechanical, thermal, and sometimes elec­
trical properties while also reducing the heat/fuel release • National Institute of Standards and Technology
of that specific polymer.52–58 Normally, flame retardant Fire Research Division (NIST): www.nist.gov/el/
chemistry has involved the addition of a particular material fire-research-division-73300
only for enhancement of flammability performance to the • Underwriters Laboratories Fire Safety Research
material, so the promise of bringing something in for flame Institute (UL-FSRI): www.ul.com/ and https://
retardancy and thermal and mechanical and other proper­ fsri.org/
ties has led to an explosion in new material science research • FM Global (Factory Mutual): www.fmglobal.com/
for nanocomposites in general, and it certainly has been a • Southwest Research Institute (SwRI) Fire Techno­
boon to flame retardant research as well. However, it should logy Division: www.swri.org/industries/fire
be noted that there has been no commercialization of flame • Federal Institute for Materials Research and Testing
retardant polymer nanocomposites besides one example in (Germany—BAM): www.bam.de/Navigation/EN/
wire and cable applications.* Therefore, it is not clear how Topics/Infrastructure/FireScience/fire-science.
well this technology will advance beyond its current use in html
coatings, as discussed in Chapter 14 of this book. • SP Technical Research Institute of Sweden: https://
It is important to remember, again, that this field of risefr.com/
research is driven by regulations, both fire and non-fire • Bolton Institute for Materials Research and
related, and with that the research sometimes is reactive Innovation www.bolton.ac.uk/explore-our-schools/
to the regulations rather than proactive. Flame retardant institute-for-materials-research-and-innovation/
chemistry is much more varied now than it has ever been, • State Key Laboratory of Fire Science, Hefei, China
and it will continue to grow as chemists look for new alter­ http://fire.ustc.edu.cn/
natives to existing flame retardant systems. • Commonwealth Scientific and Industrial Research
Organization (CSIRO) Fire Safety & Control
Division: www.csiro.au/en/work-with-us/services/
1.6 FLAME RETARDANT RESEARCH
testing-and-certification/fire-safety
Research into flame retardancy of polymeric materials, and
indeed fire safety of all materials in use today (wood, steel, 1.7 CONCLUSIONS AND KEY
glass, plastics, etc.), is truly a worldwide field of materials
ITEMS TO REMEMBER
science study. Research is done in academia, government,
and industry on every continent in the world today, and As you proceed through this book, remember the impor­
each group has its own areas of emphasis and expertise. tance of knowing the definitions of flame retardancy and
Industrial work focuses largely on the development of new fire protection, and then see how the book is organized.
materials for sale that meet the regulations and, as such, is Flame retardant chemistries come first, followed by the
not broadly shown in the scientific literature and is almost fundamentals of how to assess material flammability (test
completely limited to the patent literature. Therefore, it methods, emissions, modeling), and then the regulations.
is hard to determine which companies are leading the The final chapters of the book explain how flame retardants
way in new flame retardant material research other than are used in specific applications, and then the book ends
by looking at their offerings of flame retardant products. with a potential view of the future and expected research/
Obviously, the main flame retardant additive manufactur­ regulatory trends.
ers (ICL, Albemarle, Clariant, Lanxess) conduct the great­ The field of polymeric flame retardancy is undergoing
est amount of new flame retardant chemical research, but a great deal of change, reacting to new requirements, fire
it is not unheard of for the end-users of these additives to risk scenarios, and other requirements for polymeric mate­
conduct their own flame retardant chemical research. So in rials. Those who pay attention to these coming changes, as
published research of access to everyone, most of the con­ well as being aware of the current technology available to
ducted research focuses on fire safety engineering more flame retardancy, should be able to develop new materials
than new flame retardant chemistry, but still, the work is in response to these changes, as well as come up with new
related as the new fire safety engineering research leads to innovations in flame retardancy. Fire will not just go away
new regulations which the flame retardant chemistry has as our society advances, and it is very likely that we will
to meet. see more, not fewer, polymers in use throughout society
An Introduction to Materials Flame Retardancy and Fire Protection 9

worldwide. With this increase it seems that there will be files (1978–2001). Society of Automotive Engineers
more need, not less, for those of us who practice this field of World Congress, Detroit, MI, 11–14 April 2005. Paper
science. At the moment in some countries the level of flame 200501–1421.
12. “Guide on Methods for Evaluating Fire Hazard to Occupants
retardant research funding is quite low (US), while in other
of Passenger Road Vehicles—NFPA 556” National Fire
countries the funding is higher (EU, Asia), but perhaps still Prevention Association (NFPA). www.nfpa.org/codes-and-
not high enough to keep up with the changes. Since poly­ standards/all-codes-and-standards/list-of-codes-and­
meric materials will only be used more in modern society, standards/detail?code=556 (accessed 10/22/22).
it falls upon fire scientists and fire safety engineers to edu­ 13. “Investigation of Smoke Gases and Temperatures During
cate the public that these materials are inherently flam­ Car Fire—Large-Scale and Small-Scale Tests and
mable unless they are made flame retardant. Ideally, we Numerical Investigations” Krüger, S.; Hofmann, A.; Berger,
A.; Gude, N. Fire Mater. 2016, 40, 785–799.
would like to have the fire protection in place before cata­
14. “Post-Collision Fires in Road Vehicles between 2002 and
strophic fires occur, but we have to keep in mind that there 2015” Otxoterena, P.; Bjornstig, U.; Lindkvist, M. Fire
are many demands on the few resources that society has at Mater. 2020, 44, 767–775.
the moment, and if we want those resources, we will have to 15. “Human Survivability in Motor Vehicle Fires” Digges, K.
voice the need for it. Until then, it is up to those of us who H.; Gann, R. G.; Grayson, S. J.; Hirschler, M. M.; Lyon,
practice in this field to keep guard over the potential for fire R. E.; Purser, D. A.; Quintiere, J. G.; Stephenson, R. R.;
in plastics and be willing to lend a hand when society asks Tewarson, A. Fire Mater. 2008, 32, 249–258.
16. “Fire Hazard Analysis of Modern Vehicles in Parking
for our help.
Facilities” Boehmer, H. R.; Klassen, M. S.; Olenick, S. M.
Fire Technol. 2021, 57, 2097–2127.
NOTE 17. “Heat Release During Thermally-Induced Failure of a
Lithium Ion Battery: Impact of Cathode Composition”
* Products reported by Dr. Günter Beyer of Kabelwerk Eupen Liu, X.; Wu, Z.; Stoliarov, S. I.; Denlinger, Ml; Masias, A.;
at many conferences up to 2016, but unclear if this product Snyder, K. Fire Saf J. 2016, 85, 10–22.
is still being sold. Cannot find product ID or number on 18. “Analysis of Effectiveness of Suppression of Lithium Ion
Kabelwerk Eupen website. Information based upon per­ Battery Fires With a Clean Agent” Said, A. O.; Stoliarov, S.
sonal communications between authors and Dr. Günter I. Fire Saf J. 2021, 121, 103296.
Beyer. 19. “Experimental Investigation of Suppression of 18650
Lithium Ion Cell Array Fires with Water Mist” Said, A. O.;
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Material Flammability Measurements and Test Methods

‘ABD 0031: Airbus Directives (ABD) and Procedures for Fire— Smoke—Toxicity (FST).’ Airbus Industries.
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(Withdrawn 1976).’ ASTM International, West Conshohocken, PA.
‘ASTM D1929: Test Method for Determining Ignition Temperature of Plastics.’ ASTM International, West Conshohocken, PA.
‘ASTM D2863: Test Method for Measuring the Minimum Oxygen Concentration to Support Candle-Like Combustion of Plastics
(Oxygen Index).’ ASTM International, West Conshohocken, PA.
‘ASTM D3801: Test Method for Measuring the Comparative Burning Characteristics of Solid Plastics in a Vertical Position.’ ASTM
International, West Conshohocken, PA.
‘ ASTM D5485: Standard Test Method for Determining the Corrosive Effect of Combustion Products Using the Cone Corrosimeter .’
Annual Book of Standards , Vol. 04 .07, ASTM International, West Conshohocken, PA.
‘ ASTM D7295: Standard Practice for Sampling and Determination of Hydrogen Cyanide (HCN) in Combustion Effluents and Other
Stationary Sources .’ Annual Book of Standards , Vol. 11 .07, ASTM International, West Conshohocken, PA.
‘ASTM D7309: Standard Test Method for Determining Flammability Characteristics of Plastics and Other Solid Materials Using
Microscale Combustion.’ Annual Book of Standards, Vol. 08.03, ASTM International, West Conshohocken, PA.
‘ASTM E84: Standard Test Method for Surface Burning Characteristics of Building Materials.’ Annual Book of Standards , Vol. 04 .07,
ASTM International, West Conshohocken, PA.
‘ASTM E162: Standard Test Method for Surface Flammability of Materials Using a Radiant Heat Energy Source.’ Annual Book of
Standards, Vol. 04.07, ASTM International, West Conshohocken, PA.
‘ASTM E648: Standard Test Method for Critical Radiant Flux of Floor Covering Systems Using a Radiant Heat Energy Source.’ Annual
Book of Standards, Vol. 04.07, ASTM International, West Conshohocken, PA.
‘ASTM E662: Standard Test Method for Specific Optical Density of Smoke Generated by Solid Materials.’ ASTM International, West
Conshohocken, PA.
‘ASTM E800: Standard Guide for Measurement of Gases Present or Generated During Fires.’ Annual Book of Standards , Vol. 04 .07,
ASTM International, West Conshohocken, PA.
‘ASTM E906: Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products.’ Annual Book of
Standards, Vol. 04.07, ASTM International, West Conshohocken, PA.
‘ASTM E1317: Standard Test Method for Flammability of Marine Surface Finishes.’ Annual Book of Standards, Vol. 04.07, ASTM
International, West Conshohocken, PA.
‘ASTM E1321: Test Method for Determining Material Ignition and Flame Spread Properties.’ ASTM International, West Conshohocken,
PA.
‘ASTM E1354: Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen
Consumption Calorimeter.’ Annual Book of Standards , Vol. 04 .07, ASTM International, West Conshohocken, PA.
‘ASTM E1537: Standard Test Method for Fire Testing of Upholstered Furniture.’ Annual Book of Standards , Vol. 04 .07, ASTM
International, West Conshohocken, PA.
‘ASTM E1623: Test Method for Determination of Fire and Thermal Parameters of Materials, Products, and Systems Using an
Intermediate Scale Calorimeter (ICAL).’ ASTM International, West Conshohocken, PA.
‘ASTM E1590: Standard Test Method for Fire Testing of Mattresses.’ Annual Book of Standards , Vol. 04 .07, ASTM International,
West Conshohocken, PA.
‘ASTM E1678: Standard Test Method for Measuring Smoke Toxicity for Use in Fire Hazard Analysis.’ ASTM International, West
Conshohocken, PA.
‘ASTM E1822: Standard Test Method for Fire Testing of Stacked Chairs.’ Annual Book of Standards , Vol. 04 .07, ASTM International,
West Conshohocken, PA.
‘ASTM E1995: Standard Test Method for Measurement of Smoke Obscuration Using a Conical Radiant Source in a Single Closed
Chamber, With the Test Specimen Oriented Horizontally.’ ASTM International, West Conshohocken, PA.
‘ASTM E2058: Standard Test Methods for Measurement of Synthetic Polymer Material Flammability Using a Fire Propagation
Apparatus.’ Annual Book of Standards , Vol. 04 .07, ASTM International, West Conshohocken, PA.
‘ASTM E2257: Standard Test Method for Room Fire Test of Wall and Ceiling Materials and Assemblies.’ Annual Book of Standards ,
Vol. 04 .07, ASTM International, West Conshohocken, PA.
‘CAL TB 117: Requirements, Test Procedures and Apparatus for Testing the Flame Retardance of Resilient Filling Materials Used in
Upholstered Furniture,’ Bureau of Home Furnishings and Thermal Insulation, Sacramento, CA.
‘EN 13501: Fire classification of construction products and building elements—Part 1—Classification using test data from reaction-to-
fire tests.’ European Committee for Standardization, Brussels.
‘EN 13823: Reaction to fire tests for building products—Building Products Excluding Flooring Exposed to the Thermal Attack of a
single burning item.” European Committee for Standardization, Brussels.
‘FMVSS 302: Motor Vehicle Interior Materials Fire Test.’ National Highway Traffic Safety Administration, Washington, DC.
‘IEC 60695–2–13: Fire hazard testing—Part 2–13: Glowing/ hot-wire based test methods—Glow-wire ignitability test method for
materials.’ International Electrotechnical Commission, Geneva.
‘IMO FTP Code: International Code for Application of Fire Test Procedures, Annex 1. Part 2.’ International Maritime Organization,
London.
‘IMO FTP Code: International Code for Application of Fire Test Procedures, Annex 1. Part 5.’ International Maritime Organization,
London.
‘ISO 4589–2: Plastics—Determination of burning behavior by Oxygen Index—Part 2: Ambient-temperature test.’ International
Organization for Standardization, Geneva.
‘ISO 5657: Fire tests—Reaction to fire—Ignitability of building products.’ International Organization for Standardization, Geneva.
‘ISO 5659–2: Plastics—Smoke generation –Part 2: Determination of optical density by a single-chamber test.’ International
Organization for Standardization, Geneva.
‘ISO 5660–1: Reaction-to-fire tests—Heat release, smoke production and mass loss rate—Part 1: Heat Release Rate (Cone
Calorimeter Method).’ International Organization for Standardization, Geneva.
‘ISO 9239–1: Reaction to fire tests for floorings—Part 1: Determination of the Burning Behaviour Using a Radiant Heat Source.’
International Organization for Standardization, Geneva.
‘ISO 9705: Fire tests—Reaction-to-fire—Room fire test.’ International Organization for Standardization, Geneva.
‘ISO TS 19700: Fire tests—Controlled equivalence ratio method for the determination of hazardous components of fire effluents.’
International Organization for Standardization, Geneva.
‘ISO 19701—Methods for analysis and sampling of fire effluents.’ International Organization for Standardisation, Geneva.
‘MIL-STD-2031: Fire and Toxicity Test Methods and Qualification Procedure for Composite Material Systems Used in Hull, Machinery
and Structural Applications Inside Naval Submarines.’
‘NFPA 265: Standard Method of Tests for Evaluating Room Fire Growth Contribution of Textile Wall Coverings.’ National Fire
Protection Association, Quincy, MA.
‘NFPA 269: Standard Test Method for Developing Toxic Potency Data for Use in Fire Hazard Modeling.’ National Fire Protection
Association, Quincy, MA.
‘NFPA 271: Standard Method of Test for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen
Consumption Calorimeter.’ National Fire Protection Association, Quincy, MA.
‘NFPA 286: Standard Method of Tests for Evaluating Contribution of Wall and Ceiling Interior Finish to Room Fire Growth.’ National
Fire Protection Association, Quincy, MA.
‘NFPA 550: Guide to the Fire Safety Concepts Tree.’ National Fire Protection Association, Quincy, MA.
‘SMP 800-C: Bombardier Material and Process Specification, Toxic Gas Generation.’ Bombardier, Montréal.
‘SOLAS: Consolidated Edition, 2001, Chapter II-2–Construction: Fire protection, fire detection and fire extinction.’ International
Maritime Organization, London.
‘UL 94: Test for Flammability of Plastic Materials for Parts in Devices and Appliances.’ Underwriters Laboratories, Northbrook, IL.
Quintiere, J. , Principles of Fire Behavior, 2nd Edition. CRC Press, Taylor & Francis Group: Boca Raton, FL, 2016.
Gann, R. ; Babrauskas, V. ; Peacock, R. ; Hall, J. , Fire Conditions for Smoke Toxicity Measurement. Fire and Materials 1994, 18,
193–199.
Tu, K. ; Quintiere, J. , Wall Flame Heights With External Radiation. Fire Technology 1991, 27, 195–203.
Evans, D. ; Stroup, D. , Methods to Calculate the Response Time of Heat and Smoke Detectors Installed Below Large Unobstructed
Ceilings. Fire Technology 1986, 22, 54–65.
Evans, D. , Calculating Sprinkler Actuation Time in Compartments. Fire Safety Journal 1985, 9, 147–155.
Deal, S. ; Beyler, C. , Correlating Preflashover Room Fire Temperatures. Journal of Fire Protection Engineering 1990, 2, 33–48.
Foote, K. ; Pagni, P. ; Alvarez, N. Temperature Correlations for Forced Ventilation Compartment Fires, First International Symposium
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McCaffrey, B. ; Quintiere, J. ; Harkleroad, M. , Estimating Room Fire Temperatures and the Likelihood of Flashover Using Fire Test
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Cooper, L. , A Mathematical Model for Estimating Available Safe Egress Time in Fires. Fire and Materials 1982, 6, 135–144.
Jones, W. ; Peacock, R. ; Forney, G. ; Reneke, P. CFAST: Consolidated Model of Fire Growth and Smoke Transport (Version 5).
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McGrattan, K. B. H. S. ; Floyd, J. E. ; Baum, H. R. ; Rehm, R. G. Fire Dynamics Simulator (Version 5): Technical Reference Guide.
NIST Special Publication 1018–5; National Institute of Standards and Technology: Gaithersburg, MD, 2007; p 100.
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Thomas, P. , Testing Products and Materials for Their Contribution to Flashover in Rooms. Fire and Materials 1980, 5, 103–111.
Babrauskas, V. , Estimating Room Flashover Potential. Fire Technology 1980, 16, 94–104.
Babrauskas, V. , A Closed Form Approximation for Post-Flashover Compartment Fire Temperatures. Fire Safety Journal 1981, 4,
63–73.
Thomas, P. , SFPE Classic Paper Review: Fire Behavior In Rooms by Kunio Kawagoe. Journal of Fire Protection Engineering 2004,
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Jin, T. , Visibility Through Smoke. Journal of Fire and Flammability 1978, 9, 135–155.
Babrauskas, V. , Ignition Handbook. Fire Science Publishers: Issaquah, WA, 2003.
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Conference on Flame Retardancy, Stamford, CT, May 21–23, 2007; Business Communications Co.: Stamford, CT, 2007.
Morgan, A. ; Bundy, M. , Cone Calorimeter Analysis of UL 94 V-Rated Plastics. Fire and Materials 2007, 31, 257–283.
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ASTM Fire Standards and Related Technical Material, 7th Edition. ASTM International: West Conshohocken, PA, 2007.
Roed, J. Low Voltage Directive, FIRESEL 2003, Borås, Sweden, May 27–28, 2003; SP, Borås, Sweden, 2003.
Hallman, J. Ignition of Polymers by Radiant Energy. Ph.D. Thesis, University of Oklahoma, Norman, OK, 1971.
Koohyar, A. Ignition of Wood by Flame Radiation. Ph.D. Thesis, University of Oklahoma, Norman, OK, 1967.
Rasbash, D. ; Drysdale, D. ; Deepak, D. , Critical Heat and Mass Transfer at Pilot Ignition and Extinction of a Material. Fire Safety
Journal 1986, 10, 1–10.
Thomson, H. ; Drysdale, D. , Flammability of Plastics, I: Ignition Temperatures. Fire and Materials 1987, 11, 163–172.
Thomson, H. ; Drysdale, D. ; Beyler, C. , An Experimental Evaluation of Critical Surface Temperature as a Criterion for Piloted Ignition
of Solid Fuels. Fire Safety Journal 1988, 13, 185–196.
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1983.
Atreya, A. ; Carpentier, C. ; Harkleroad, M. Effect of Sample Orientation on Piloted Ignition and Flame Spread, First International
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Abu-Zaid, M. Effect of Water on Ignition of Cellulosic Materials. Ph.D. Thesis, Michigan State University, East Lansing, MI, 1988.
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27, 249–259.
Janssens, M. Thermal Model for Piloted Ignition of Wood Including Variable Thermophysical Properties, Third International
Symposium on Fire Safety Science, Edinburgh, Scotland , Cox, G.; Langford, B. , Eds. Elsevier Applied Science, New York, NY, 1991;
pp 167–176.
Moghtaderi, B. ; Novozhilov, V. ; Fletcher, D. ; Kent, J. , A New Correlation for Bench-Scale Piloted Ignition Data of Wood. Fire Safety
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Orientation. Fire and Materials 1993, 17, 205–208.
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Khan, M. ; deRis, J. Operator Independent Ignition Measurements, Eighth International Symposium on Fire Safety Science, Beijing,
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Khan, M. ; deRis, J. Device and Method for Measuring Absorbed Heat Flux, 10th Fire and Materials Conference, San Francisco, CA,
Interscience Communications, London, 2007; pp 25–26 (abstract, full paper on CD).
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Gaithersburg, MD, 1984.
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Parker, W. , Calculations of the Heat Release Rate by Oxygen Consumption for Various Applications. Journal of Fire Sciences 1984,
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Analysis; Special Publication 827; National Institute of Standards and Technology: Gaithersburg, MD, 1991.
Babrauskas, V. ; Gann, R. ; Levin, B. ; Paabo, M. ; Harris, R. ; Peacock, R. ; Yusa, S. , A Methodology for Obtaining and Using Toxic
Potency Data for Fire Hazard Analysis. Fire Safety Journal 1998, 31, 345–358.
Babrauskas, V. , The Generation of CO in Bench-Scale Fire Tests and the Prediction for Real-Scale Fires. Fire and Materials 1995,
19, 205–213.
Gann, R. ; Babrauskas, V. ; Peacock, R. , Fire Conditions for Smoke Toxicity Measurement. Fire and Materials 1994, 18, 193–199.
Gross, D. ; Loftus, J. ; Robertson, A. Method for Measuring Smoke From Burning Materials, Fire Test Methods: Restraint and Smoke,
ASTM STP 422, June 26–July 1, 1966, Atlantic City, NJ, American Society for Testing and Materials, Philadelphia, PA: 1967; pp
166–204.
Ames, S. ; Rogers, S. Large and Small Scale Fire Calorimetry Assessment of Upholstered Furniture, 5th Interflam Conference,
Canterbury, September 17–19, 2001; Interscience Communications, London, England: Canterbury, England, 1990; pp 221–232.
Babrauskas, V. ; Lawson, J. ; Walton, W. ; Twilley, W. Upholstered Furniture Heat Release Rates Measured with a Furniture
Calorimeter; NBSIR 82–2604; National Bureau of Standards: Gaithersburg, MD, 1982.
Smith, D. ; Marshall, N. ; Shaw, K. ; Colwell, S. Correlating Large-Scale Fire Performance with the Single Burning Item Test, 9th
Interflam Conference, Edinburgh, Interscience Communications, London: Edinburgh, 2001; pp 531–542.
Comprehensive compilations and an extensive discussion of various uses of flammability test methods can be found in the following
two books:
Apte, V. Flammability Testing of Materials Used in Construction, Transport and Mining, 2nd Edition, Woodhead Publishing (an imprint
of Elsevier), Cambridge, England, 2022.
Troitzsch, J. , ed. Plastics Flammability Handbook—Principles, Regulations, Testing, and Approval, 4th Edition, Hanser Publisher,
Munich, 2021.
All standards developed and maintained by ASTM Committee E05 on fire standards are in Volume 04.07 of the Annual Book of ASTM
Standards. Members of ASTM have access free of charge to one volume of their choosing (see www.astm.org/astm-bos-
04.07.htmlfordetails).
ASTM Fire Standards and Related Technical Material, 7th Edition, ASTM International, West Conshohocken, PA, 2007.
An extensive discussion of the principles of fire physics and chemistry and the behavior of materials in fire can be found in:
Fire Protection Handbook, 21st Edition, National Fire Protection Association, Quincy, MA, 2023 (https://catalog.nfpa.org/).
SFPE Handbook of Fire Protection Engineering. Springer, 5th Edition, Springer (https://link.springer.com/book/10.1007/978-1-4939-
2565-0).
Finally, a tremendous amount of useful information can be found on the Internet. Instead of providing a list of web sites in this chapter,
the reader is referred to the site of Dr. Vyto Babrauskas’ company, Fire Science and Technology (URL: http://doctorfire.com). Not only
is there a lot of useful information on this site, but you will also find what is, to the author of this chapter's knowledge, the longest list of
fire-related links on the web (URL: http://doctorfire.com/links.html).

Fire Emissions and Smoke Toxicity

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Shi, J. ; Boyer, G. ; Mourzenko, V. ; Thovert, J.-F. A Comprehensive Numerical Model for the Pyrolysis of Intumescent Polymers:
Application to EVA-ATH Compounds. Chem. Eng. Sci. 2023, 268, 118385. https://doi.org/10.1016/j.ces.2022.118385
De Cachinho Cordeiro, I. M. ; Chen, T. B. Y. ; Yuen, A. C. Y. ; Wang, C. ; Chan, Q. N. ; Zhang, J. ; Heng Yeoh, G. Pyrolysis and
Combustion Characterisation of HDPE/APP Composites via Molecular Dynamics and CFD Simulations. J. Anal. Appl. Pyrolysis. 2022,
163, 105499. https://doi.org/10.1016/j.jaap.2022.105499
De Cachinho Cordeiro, I.M. , Chen, T.B.Y. , Yuen, A.C.Y. , Wang, C. , Chan, Q.N. , Zhang, J. , Heng Yeoh, G. Pyrolysis and
combustion characterisation of HDPE/APP composites via molecular dynamics and CFD simulations. Journal of Analytical and
Applied Pyrolysis, 163, 2022, 105499. https://doi.org/10.1016/j.jaap.2022.105499

Regulations, Codes, and Standards Relevant to Fire Issues in the United States
The Construction Products Directive (CPD) as Regards the Classification of the Reaction-to-Fire Performance of Construction
Products, Council Directive 89/106/EEC, 21 December 1988, Brussels, Belgium, 1988, European Commission, Enterprise and
Industry Directorate-General, Construction.
Construction Products Regulation (CPR), European Commission, 2022. https://single-market-
economy.ec.europa.eu/sectors/construction/construction-productsregulation-cpr_en
International Building Code (IBC), International Code Council, Washington, DC.
International Fire Code (IFC), International Code Council, Washington, DC.
International Mechanical Code (IMC), International Code Council, Washington, DC.
International Wildland Urban Interface Code (IWUIC), International Code Council, Washington, DC.
International Residential Code for One- and Two-Family Dwellings (IRC), International Code Council, Washington, DC.
International Existing Building Code (IEBC), International Code Council, Washington, DC.
NFPA 70, National Electrical Code (NEC), National Fire Protection Association, Quincy, MA.
NFPA 101, National Life Safety Code, National Fire Protection Association, Quincy, MA.
NFPA 90A, Standard for the Installation of Air-Conditioning and Ventilating Systems, National Fire Protection Association, Quincy, MA.
NFPA 13, Standard for the Installation of Sprinkler Systems, National Fire Protection Association, Quincy, MA.
NFPA 130, Standard for Fixed Guideway Transit and Passenger Rail Systems, National Fire Protection Association, Quincy, MA.
16 CFR 1610, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1610, “Standard for the
Flammability of Clothing Textiles”, Flammable Fabrics Act Regulations, US Federal Government.
ASTM D1230, “Standard Test Method for Flammability of Apparel Textiles”, American Society for Testing and Materials, West
Conshohocken, PA.
16 CFR Part 1630, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1630, “Standard for the
Surface Flammability of Carpets and Rugs (FF 1–70)”, Flammable Fabrics Act Regulations, US Federal Government.
16 CFR Part 1631, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1631, “Standard for the
Surface Flammability of Small Carpets and Rugs (FF 2–70)”, Flammable Fabrics Act Regulations, US Federal Government.
ASTM D2859, “Standard Test Method for Flammability of Finished Textile Floor Covering Materials”, American Society for Testing and
Materials, West Conshohocken, PA.
16 CFR 1615, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1615, “Standard for the
Flammability of Children's Sleepwear: Sizes 0 Through 6X (FF 3–71)”, Flammable Fabrics Act Regulations, US Federal Government.
16 CFR 1616, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1616, “Standard for the
Flammability of Children's Sleepwear: Sizes 7 Through 14 (FF 5–74)”, Flammable Fabrics Act Regulations, US Federal Government.
ASTM D6545, “Standard Test Method for Flammability of Textiles Used in Children's Sleepwear”, American Society for Testing and
Materials, West Conshohocken, PA.
16 CFR 1632, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1632, “Standard for the
Flammability of Mattresses (FF 4–72)”, Flammable Fabrics Act Regulations, US Federal Government.
16 CFR 1500.44, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1500, “Hazardous
Substances and Articles; Administration and Enforcement Regulations: Method for Determining Extremely Flammable and Flammable
Solids”, US Federal Government.
16 CFR 1633, Title 16, Commercial Practices, Chapter II, Consumer Product Safety Commission, Part 1633, “Standard for the
Flammability (Open Flame) of Mattress Sets”, Flammable Fabrics Act Regulations, US Federal Government.
ASTM F963, “Standard Consumer Safety Specification for Toy Safety”, American Society for Testing and Materials, West
Conshohocken, PA.
Proposed 16 CFR Part 1634, “Standard for the Flammability of Residential Upholstered Furniture”,
www.cpsc.gov/businfo/frnotices/fr08/cpscfr08.html, March 4, 2008.
16 CFR 1640, “Standard for the Flammability of Upholstered Furniture”, www.ecfr.gov/current/title-16/chapter-II/subchapter-D/part-
1640.
ASTM E2187, “Standard Test Method for Measuring the Ignition Strength of Cigarettes”, American Society for Testing and Materials,
West Conshohocken, PA.
New York State Combustion Toxicity Regulations: “Combustion Toxicity Testing”, Article 15, Part 1120 (9 NYCRR 1120)—Effective
December 16, 1986.
Alarie, Y. C. ; Anderson, R. C. Toxicologic and Acute Lethal Hazard Evaluation of Thermal Decomposition Products of Synthetic and
Natural Polymers. Toxicol. Appl. Pharmacol. 1979, 51, 341.
Norris, J.C. , 1990, “Investigation of the Dual LC50 Values in Woods Using the University of Pittsburgh Combustion Toxicity
Apparatus”, in “Characterization and Toxicity of Smoke”, ASTM STP 1082, Amer. Soc. Testing and Materials, Philadelphia, PA, Ed.
H.J. Hasegawa , pp. 57–71.
Hirschler, M.M. , 1990, “General Principles of Fire Hazard and the Role of Smoke Toxicity”, in “Fire and Polymers: Hazards
Identification and Prevention” (Ed. G.L. Nelson ), ACS Symposium Series 425, Amer. Chem. Soc., Washington, DC, Chapter 28, pp.
462–478.
Hirschler, M. M. Smoke Toxicity Measurements Made So That the Results Can Be Used for Improved Fire Safety. J. Fire Sci. 1991, 9,
330–347.
Hirschler, M. M. ; Toxicity of the Smoke From PVC Materials: New Concepts. Prog. Rubber Plast. Technol. 1994, 10–12, 154–169.
Ahrens, M. , U.S. Vehicle Fire Trends and Patterns, NFPA, Quincy, MA, August 2001.
Ahrens, M. , The U.S. Fire Problem Overview Report: Leading Causes and Other Patterns and Trends, NFPA, Quincy, MA, June
2001.
Ahrens, M. , Vehicle Fires, NFPA, Quincy, MA , March 2020.
Janssens, M.L. , “Database on Full-Scale Calorimeter Tests on Motor Vehicles”, HAR-AAA TC Meeting, Detroit, MI, October 23–24,
2006.
FMVSS 302, “Motor Vehicle Safety Standard No. 302, Flammability of Materials—Passenger Cars, Multipurpose Passenger Vehicles,
Trucks and Buses”, National Highway Traffic Safety Administration, Washington, DC. [Code of Federal Regulations § 571.302,
Originally Federal Register 34, No. 229, pp. 20434–20436 (December 31, 1969)].
ISO 3795, “Road Vehicles, and Tractors and Machinery for Agriculture and Forestry—Determination of Burning Behaviour of Interior
Materials”, International Organization for Standardization (ISO), Geneva.
“Fire and Transportation Vehicles—State of the Art: Regulatory Requirements and Guidelines—A White Paper”, M.M. Hirschler
(Technical Coordinator) et al., Fire Protection Research Foundation Research Advisory Council on Transportation Vehicles, October
2004.
NFPA 556, Guide on Methods for Evaluating Fire Hazard to Occupants of Passenger Road Vehicles, National Fire Protection
Association, Quincy, MA.
Federal Transit Administration, “Recommended Fire Safety Practices for Transit Bus and Van Materials Selection”, Federal Register,
pp. 54249–54254, October 20, 1993.
“Aircraft Materials Fire Test Handbook”, www.fire.tc.faa.gov/, US Department of Transportation, Federal Aviation Administration,
Washington, DC.
Federal Register, Vol. 66, No. 36/Thursday, February 22, 2001, FAA Policy on Use of the “Aircraft Materials Fire Test Handbook”, pp.
11197–11199, 2001.
Smith, E.E. , “Ignition, Heat Release and Noncombustibility of Materials, ASTM STP 502”, (Ed. A.F. Robertson ), Am. Soc. Test. Mats,
Philadelphia, PA, 1972, p. 119.
ASTM E906, “Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products”, American Society for
Testing and Materials, West Conshohocken, PA.
ASTM E662, “Standard Test Method for Specific Optical Density of Smoke Generated by Solid Materials”, American Society for
Testing and Materials, West Conshohocken, PA.
ASTM E648, “Standard Test Method for Critical Radiant Flux of Floor-Covering Systems Using a Radiant Heat Energy Source”,
American Society for Testing and Materials, West Conshohocken, PA.
International Convention for the Safety of Life at Sea (SOLAS), 1974, with Periodic Amendments, Consolidated Edition, International
Maritime Organization, London.
International Maritime Organization (IMO), London.
International Code for Application of Fire Test Procedures (FTP Code), International Maritime Organization, London.
International Code of Safety for High-Speed Craft (HSC Code), International Maritime Organization, London.
Code of Federal Regulations, US Federal Government— Coast Guard: Title 46, Shipping, CFR, Parts 1–199, Subchapter J: Electrical
Engineering (Parts 110–113).
US Coast Guard, NVIC (Navigation and Vessel Inspection Circular), US Coast Guard Guide to Structural Fire Protection.
NFPA 301, Code for Safety to Life from Fire on Merchant Vessels, National Fire Protection Association, Quincy, MA.
ISO 834–1, “Fire-Resistance Tests—Elements of Building Construction—Part 1: General Requirements”, International Organization for
Standardization (ISO), Geneva.
ASTM E119, “Standard Test Methods for Fire Tests of Building Construction and Materials”, American Society for Testing and
Materials, West Conshohocken, PA.
ISO 9705–1, “Reaction to Fire Tests—Room Corner Test for Wall and Ceiling Lining Products—Part 1: Test Method for a Small Room
Configuration”, International Organization for Standardization (ISO), Geneva.
NFPA 302, “Fire Protection Standard for Pleasure and Commercial Motor Craft”, National Fire Protection Association, Quincy, MA.
Sorathia, U. , “Materials in Military Applications”, in Business Communications Company Fourteenth Ann. Conference on Recent
Advances in Flame Retardancy of Polymeric Materials, June 2–4, Stamford, CT, Ed. M. Lewin, Norwalk, CT , 2003.
Federal Register, Vol. 64, No. 91/Wednesday May 12, 1999, “Department of Transportation, Federal Railroad Administration, 49 CFR
Part 216 et al., Passenger Equipment Safety Standards; Final Rule”, pp. 25539– 25705, 1999.
Federal Register, Vol. 67, No. 122/Tuesday, June 25, 2002, “Department of Transportation, Federal Railroad Administration, 49 CFR
Part 238, [FRA Docket No. PCSS– 1, Notice No. 8] RIN 2130–AB48, Passenger Equipment Safety Standards”, pp. 42892–42912,
2002.
ASTM E162, “Standard Test Method for Surface Flammability of Materials Using a Radiant Heat Energy Source”, American Society for
Testing and Materials, West Conshohocken, PA.
Peacock, R.D. , Bukowski, R.W. , Jones, W.J. , Reneke, P.A. , Babrauskas, V. , and Brown, J.E. , “Fire Safety of Passenger Trains: A
Review of U.S. and Foreign Approaches”, National Institute of Standards and Technology (Under Contract to US Dept. of
Transportation, John A. Volpe National Transportation Systems Center, Cambridge, MA), Gaithersburg, MD (NIST Technical Note
1406), 1994.
ASTM E2061, “Guide for Fire Hazard Assessment of Rail Transportation Vehicles”, American Society for Testing and Materials, West
Conshohocken, PA.
Hirschler, M.M. , “Fire Safety in Rail Transportation Vehicles: Special Focus on Recent Activities at the Federal Railroad
Administration, NFPA 130 and ASTM E2061”, Fire Protection Research Foundation Fire Risk and Hazard Assessment Research
Application Symposium, July 9–11, 2003, Baltimore, MD.
UL 2556, “Wire and Cable Test Methods”, Vertical Tray Flame Test Method 2 and ST1 Limited Smoke,” Underwriters Laboratories,
Northbrook, IL.
CSA FT4, “Vertical Cable Tray Test in CSA 22.2, Test Methods for Electrical Wires and Cables (C22.2 No. 0.3)”, Canadian Standards
Association, Rexdale, ON.
NFPA 262, “Standard Method of Test for Fire and Smoke Characteristics of Wires and Cables,” National Fire Protection Assn., NFPA,
Quincy, MA.
Grayson, S.J. , and Hirschler, M.M. , “Fire Performance of Plastics in Car Interiors”, Flame Retardants 2002, February 5–6, London,
pp. 197–207, Interscience Communications, London, 2002.
Hirschler, M.M. , Hoffmann, D.J. , Hoffmann, J.M. , and Kroll, E.C. , “Fire Hazard Associated with Passenger Cars and Vans”, Fire and
Materials Conf., San Francisco, CA, Jan. 27–28, 2003, Interscience Communications, London, pp. 307–319.
Janssens, M.L. , and Huczek, J.P. , “Comparison of Fire Properties of Automotive Materials”, in Business Communications Company
Fourteenth Ann. Conference on Recent Advances in Flame Retardancy of Polymeric Materials, June 2–4, Stamford, CT, Ed. M. Lewin
, Norwalk, CT, 2003.
Hirschler, M.M. , “Improving the Fire Safety of Road Vehicles”, Chapter 17 in “Advances in Fire Retardant Materials”, Ed. R. Horrocks
and D. Price, Woodhead Publishing Ltd., London, 2008.
National Highway Traffic Safety Administration (NHTSA), “Car and Van Fire Research Work Conducted under the General Motors
Corporation—Settlement Agreement— Section B. Fire Safety Research” at the web site: http://dms.dot.gov/, Docket # 3588.
ASTM E1354, “Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen
Consumption Calorimeter (Cone Calorimeter)”, American Society for Testing and Materials, West Conshohocken, PA.
Battipaglia, K. , Huczek, J. , Janssens, M. , and Miller, M. , ‘Development of a Method to Assess the Fire Hazard of Automotive
Materials’, in Proc. Interflam ’04, 10th Int. Fire Safety Conference, July 5–7, 2004, Interscience Communications, Edinburgh, pp.
1587–1596.
Huczek, J.P. , and Blais, M.S. , “Motorcoach Fire Safety” (Final Report. Report No. DOT HS 812 213). National Highway Traffic Safety
Administration, Washington, DC, November 2015.
ASTM D5132, “Standard Test Method for Horizontal Burning Rate of Polymeric Materials Used in Occupant Compartments of Motor
Vehicles”, American Society for Testing and Materials, West Conshohocken, PA.
Code of Federal Regulations, Title 49, Transportation, Chapter V, National Highway Traffic Safety Administration, Department of
Transportation, Part 571, Federal Motor Vehicle Safety Standards, 571.301 Standard No. 301; Fuel System Integrity.
Braun, E. , Davis, S. , Klote, J. , Levin, B. , and Paabo, M. , “Assessment of the Fire Performance of School Bus Interior Components”,
NISTIR 4347, Nat Inst. Stand. Tech., Gaithersburg, MD, 1990.
“School Bus Seat Upholstery Fire Block Test”, Approved by the National Conference on School Transportation as Part of the National
Standards for School Buses and National Standards for School Bus Operations (Available from National Safety Council, 444 North
Michigan Avenue, Chicago, IL).
ASTM E2574/E2574M, “Standard Test Method for Fire Testing of School Bus Seat Assemblies”, American Society for Testing and
Materials, West Conshohocken, PA.
Hirschler, M. M. ; Piansay, T. Survey of Small Scale Flame Spread Test Results of Modern Fabrics. Fire Mater. 2007, 31, 373–386.
Hirschler, M.M. , Zicherman, J.B. , and Umino, P.Y. , “Forensic Evaluation of Clothing Flammability”, Fire and Materials (2008).
CA TB 129, California Technical Bulletin 129, “Flammability Test Procedure for Mattresses for Use in Public Buildings”, California
Bureau of Home Furnishings and Thermal Insulation, North Highlands, CA, 1992.
BS 5852, “Methods of Test for Assessment of the Ignitability of Upholstered Seating by Smoldering and Flaming Ignition Sources”,
British Standards Institution, London.
CA TB 117, California Technical Bulletin 117, “Requirements, Test Procedures and Apparatus for Testing the Flame Retardance of
Resilient Filling Materials Used in Upholstered Furniture”, California Bureau of Home Furnishings and Thermal Insulation, North
Highlands, CA, 2000.
CA TB 121, California Technical Bulletin 121, “Flamm-ability Test Procedure for Mattresses for Use in High Risk Occupancies”,
California Bureau of Home Furnishings and Thermal Insulation, North Highlands, CA, 1980.
ASTM E1590, “Standard Method for Fire Testing of Mattresses”, American Society for Testing and Materials, West Conshohocken,
PA.
Ohlemiller, T. , Shields, J. , McLane, R. , and Gann, R. , “Flammability Assessment Methodology for Mattresses,” National Institute of
Standards and Technology NISTIR 6497, Gaithersburg, MD, June, 2000.
Ohlemiller, T. , and Gann, R. , “Estimating Reduced Fire Risk Resulting From an Improved Mattress Flammability Standard,” National
Institute of Standards and Technology Technical Note 1446, Gaithersburg, MD, August, 2002.
CA TB 603, California Technical Bulletin 603, “Requirements and Test Procedure for Resistance of a Mattress/Box Spring Set to a
Large Open Flame”, California Bureau of Home Furnishings and Thermal Insulation”, North Highlands, CA, 2003.
ASTM E1353, “Standard Test Methods for Cigarette Ignition Resistance of Components of Upholstered Furniture”, American Society
for Testing and Materials, West Conshohocken, PA (withdrawn).
ASTM E1352, “Standard Method of Test for Cigarette Ignition Resistance of Mock-Up Upholstered Furniture Assemblies”, American
Society for Testing and Materials, West Conshohocken, PA (withdrawn).
NFPA 260, Standard Methods of Tests and Classification System for Cigarette Ignition Resistance of Components of Upholstered
Furniture, National Fire Protection Association, Quincy, MA.
NFPA 261 , Standard Method of Test for Determining Resistance of Mock-Up Upholstered Furniture Material Assemblies to Ignition by
Smoldering Cigarettes, National Fire Protection Association, Quincy, MA.
CA TB 117-2013, California Technical Bulletin 117-2013, Requirements, Test Procedure and Apparatus for Testing the Smolder
Resistance of Materials Used in Upholstered Furniture, California Bureau of Electronic & Appliance Repair, Home Furnishings and
Thermal Insulation, Sacramento, CA, 2013.
CATB 133, California Technical Bulletin 133, Flammability Test Procedure for Seating Furniture for Use in Public Occupancies,
California Bureau of Home Furnishings and Thermal Insulation, North Highlands, CA, 1991.
ASTM E1537, “Standard Method for Fire Testing of Upholstered Furniture”, American Society for Testing and Materials, West
Conshohocken, PA.
Verakis, H. , “Conveyor Belt Flammability”, Mine Safety & Health Administration, www.msha.gov/beltair/msha/january/verakis 2007
presentation.ppt
ASTM D635, “Standard Test Method for Rate of Burning and/or Extent and Time of Burning of Self-Supporting Plastics in a Horizontal
Position”, American Society for Testing and Materials, West Conshohocken, PA.
“The Final Report of the Technical Study Panel on the Utilization of Belt Air and the Composition and Fire Retardant Properties of Belt
Materials in Underground Coal Mining”, by J.M. Mutmansky , J.F. Brune , F. Calizaya , T.P. Mucho , J.C. Tien , and J.L. Weeks (2007),
www.cdc.gov/niosh/mining/mineract/pdfs/BeltAirFinalReportl22007.pdf.
www.federalregister.gov/documents/2008/12/31/E8-30639/flame-resistant-conveyor-belt-fire-preventionand-detection-and-use-of-air-
from-the-belt-entry.
Hirschler, M.M. , and Earl, T. , “Is Upholstered Furniture a Flammable Solid?”, Business Communications Company Seventeenth Ann.
Conference on Recent Advances in Flame Retardancy of Polymeric Materials, June 9-11, Stamford, CT, Ed. M, Lewin, Norwalk, CT,
2008.
“Regulation (EU) No 305/2011 of the European Parliament and of the Council of 9 March 2011 Laying Down Harmonised Conditions
for the Marketing of Construction Products and Repealing Council Directive 89/106/EEC”, https://eur-lex.europa.eu/legal-
content/EN/TXT/?uri=CELEX: 32011R0305—European Union Website, 2011.
“Roadmap for the Implementation of the Construction ProductsRegulation(CPR)—DocumentDate:29/02/2020— Created by
GROW.I.2—Last Update: 29/03/2021”, https://ec.europa.eu/docsroom/documents/45224—European Union Website, 2020.
EN 13501-1, “Fire Classification of Construction Products and Building Elements—Part 1: Classification Using Test Data from
Reaction to Fire Tests”, CEN (European Committee for Standardization), Brussels.
EN ISO 1182, “Reaction to Fire Tests, for Building Products—Non-Combustibility Test”, CEN (European Committee for
Standardization), Brussels.
EN ISO 1716, “Reaction to Fire Tests for Building Products—Determination of the Heat of Combustion”, CEN (European Committee
for Standardization), Brussels.
EN 13823, “Reaction to Fire Tests for Building Products. Building Products Excluding Floorings Exposed to the Thermal Attack by a
Single Burning Item”, CEN (European Committee for Standardization), Brussels.
EN ISO 11925-2, “Reaction to Fire Tests—Ignitability of Building Products Subjected to Direct Impingement of Flame—Part 2: Single-
Flame Source Test”, CEN (European Committee for Standardization), Brussels.
EN 9239–1, “Reaction to Fire Tests for Floorings— Part 1: Determination of the Burning Behaviour Using a Radiant Heat Source”,
CEN (European Committee for Standardization), Brussels.
Pipe Insulation: Commission Decision of 26 August 2003 Amending Decision 2000/147/EC Implementing Council Directive
89/106/EEC as Regards the Classification of the Reaction-to-Fire Performance of Construction Products (2003/632/EC).
Cables: Commission Decision of 27 October 2006 Amending Decision 2000/147/EC Implementing Council Directive 89/106/EEC as
Regards the Classification of the Reaction-to-Fire Performance of Construction Products (2006/751/EC).
Grayson, S. , Van Hees, P. , Vercellotti, U. , Breulet, H. , and Green, A. , “Fire Performance of Electrical Cables—New Test Methods
and Measurement Techniques. Final Report of EU SMT Project SMT4-CT96–2059,” Interscience Communications, London, 2000.
EN 50399, “Common Test Methods for Cables Under Fire Conditions—Heat Release and Smoke Production Measurement on Cables
During Flame Spread Test—Test Apparatus, Procedures, Results.” European Committee for Electrotechnical Standardization
(CENELEC), Brussels.
United Kingdom Furniture Regulations, “The Furniture and Furnishings (Fire) (Safety) Regulations 1988”, Statutory Instrument 1988
No. 1324—Amended 1993 by Statutory Instrument 1993 No. 207.
United Kingdom Mattress Regulations, “The Furniture and Furnishings (Fire) (Safety) Regulations 1988”, Statutory Instrument 1988
No. 1324—Amended 1989 by Statutory Instrument 1989 No. 2358.
UK Government Consumer Safety Research, “Effectiveness of the Furniture and Furnishings (Fire) (Safety) Regulations 1988”,
Consumer Affairs Directorate, Dept. Trade and Industry, London, June 2000 [Research Conducted by Professor Gary Stevens, Univ.
of Surrey, Guildford].
CBUF Report, “Fire Safety of Upholstered Furniture—the Final Report on the CBUF Research Programme”, Ed. B. Sundstrom , EUR
16477 EN, European Commission, Measurements and Testing Report, Contract No. 3478/1/ 0/196/11-BCR-DK(30), 1995,
Interscience Communi- cations, London.
ISO 5660 –1, “Reaction-to-Fire Tests—Heat Release, Smoke Production and Mass Loss Rate—Part 1: Heat Release Rate (Cone
Calorimeter Method) and Smoke Production Rate (Dynamic Measurement)”, International Organization for Standardization (ISO),
Geneva.
ICBO (International Conference of Building Officials), Whittier, CA.
BOCA (Building Officials and Code Administrators), Country Club Hills, IL.
SBCCI (Southern Building Code Conference International), Birmingham, AL.
Hirschler, M. M. Procedures for Development and Revision of Codes and Standards Associated with Fire Safety in the USA and Its
Fire Properties. Fire Mater. J. 2017, 41(8), 1058–1071.
NFPA 286, Standard Methods of Fire Tests for Evaluating Contribution of Wall and Ceiling Interior Finish to Room Fire Growth,
National Fire Protection Association, Quincy, MA.
ASTM E84, “Standard Test Method for Surface Burning Characteristics of Building Materials”, American Society for Testing and
Materials, West Conshohocken, PA.
NFPA 265, Standard Methods of Fire Tests for Evaluating Room Fire Growth Contribution of Textile Coverings on Full Height Panels
and Walls, National Fire Protection Association, Quincy, MA.
NFPA 275, Standard Method of Fire Tests for the Evaluation of Thermal Barriers, National Fire Protection Association, Quincy, MA.
NFPA 285, Standard Fire Test Method for Evaluation of Fire Propagation Characteristics of Exterior Wall Assemblies Containing
Combustible Components, National Fire Protection Association, Quincy, MA.
ASTM E108, “Standard Test Methods for Fire Tests of Roof Coverings”, American Society for Testing and Materials, West
Conshohocken, PA.
Evans, D.H. , and Hirschler, M.M. , “Foam Plastics in Building Construction”, Session T44 at NFPA Conference and Expo, June 9–12,
2014, Las Vegas, NV.
ASTM D1929, “Standard Test Method for Determining Ignition Temperature of Plastics”, American Society for Testing and Materials,
West Conshohocken, PA.
ASTM D2843, “Standard Test Method for Density of Smoke from the Burning or Decomposition of Plastics”, American Society for
Testing and Materials, West Conshohocken, PA.
ASTM D8484, “Standard Specification for Plastic Lumber Materials and Wood-Plastic Composite Materials Used as Exterior Wall
Coverings”, American Society for Testing and Materials, West Conshohocken, PA.
UL 1975, Standard for Fire Tests for Foamed Plastics Used for Decorative Purposes”, Underwriters Laboratories, Northbrook, IL.
NFPA 289, “Standard Method of Fire Test for Individual Fuel Packages”, National Fire Protection Association, Quincy, MA.
CPSC 16 CFR Parts 1209, “Interim Safety Standard for Cellulose Insulation”, www.ecfr.gov/current/title-16/chapter-II/subchapter-
B/part-1209?toc=1.
CPSC 16 CFR Parts 1404, “Cellulose Insulation”, www.ecfr.gov/current/title-16/chapter-II/subchapter-B/part-1404.
CAN/ULC-S102.2, “Standard Method of Test for Surface Burning Characteristics of Flooring, Floor Covering, and Miscellaneous
Materials and Assemblies”, Underwriters Laboratories of Canada, Richmond, BC.
ASTM E970, “Standard Test Method for Critical Radiant Flux of Exposed Attic Floor Insulation Using a Radiant Heat Energy Source”,
American Society for Testing and Materials, West Conshohocken, PA.
ASTM F1085, “Standard Specification for Mattress and Box Springs for Use in Berths in Marine Vessels (Annexes A1 and A3)”,
American Society for Testing and Materials, West Conshohocken, PA.
NFPA 701, “Standard Methods of Fire Tests for Flame-Propagation of Textiles and Films”, National Fire Protection Association,
Quincy, MA.
ASTM E3082, “Standard Methods for Determining the Effectiveness of Fire Retardant Treatments for Natural Christmas Trees”,
American Society for Testing and Materials, West Conshohocken, PA.
UL 1820, “Standard for Safety Fire Test of Pneumatic Tubing for Flame and Smoke Characteristics”, Underwriters Laboratories,
Northbrook, IL.
UL 1887, “Standard for Safety Fire Test of Plastic Sprinkler Pipe for Visible Flame and Smoke Characteristics”, Underwriters
Laboratories, Northbrook, IL.
UL 2024, “Standard for Cable Routing Assemblies and Communications Raceways”, Underwriters Laboratories, Northbrook, IL.
UL 2043, “Standard for Safety Fire Test for Heat and Visible Smoke Release for Discrete Products and Their Accessories Installed in
Air-Handling Spaces”, Underwriters Laboratories, Northbrook, IL.
ASTM E2768, “Standard Test Method for Extended Duration Surface Burning Characteristics of Building Materials (30 min Tunnel
Test)”, American Society for Testing and Materials, West Conshohocken, PA.
NFPA 703, “Standard for Fire Retardant Impregnated Wood and Fire Retardant Coatings for Building Materials”, National Fire
Protection Association, Quincy, MA.
Hirschler, M.M. , “Wildland Urban Interface Code Comparisons: IWUIC (ICC) and Chapter 7A (California)”, Wildfire Resilient Structures
(WiReS) Conference and Tradeshow, February 7–10, 2023, San Diego, CA.
International Code Council Performance Code for Buildings and Facilities (ICCPC), International Code Council, Washington, DC.
NFPA 501, “Standard on Manufactured Housing”, National Fire Protection Association, Quincy, MA (withdrawn).
UL 1666, “Standard Test for Flame Propagation Height of Electrical and Optical-Fiber Cables Installed Vertically in Shafts”,
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IEEE 1202, “IEEE Standard for Flame-Propagation Testing of Wire & Cable”, Institute of Electrical and Electronics Engineers, New
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UL 1685, “Standard Vertical-Tray Fire-Propagation and Smoke-Release Test for Electrical and Optical-Fiber Cables”, Underwriters
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NFPA 5000, “Building Construction and Safety Code”, National Fire Protection Association, Quincy, MA.
NFPA 75, “Standard for the Fire Protection of Information Technology Equipment”, National Fire Protection Association, Quincy, MA.
NFPA 909, “Code for the Protection of Cultural Resource Properties—Museums, Libraries, and Places of Worship”, National Fire
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NFPA 914, “Code for Fire Protection of Historic Structures”, National Fire Protection Association, Quincy, MA.
ASTM E1995, “Standard Test Method for Measurement of Smoke Obscuration Using a Conical Radiant Source in a Single Closed
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NFPA 270, “Standard Test Method for Measurement of Smoke Obscuration Using a Conical Radiant Source in a Single Closed
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NFPA 259, “Standard Test Method for Potential Heat of Building Materials”, National Fire Protection Association, Quincy, MA.
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