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<p>Preface xiii</p> <p><b>1 Regulations and Other Developments/Trends/Initiatives Driving Non-Halogenated Flame Retardant Use 1<br /></b><i>Alexander B. Morgan</i></p> <p>1.1 Regulatory History of Halogenated vs. Non-Halogenated Flame Retardants 1</p> <p>1.2 Regulations of Fire Safety and Flame Retardant Chemicals 6</p> <p>1.3 Current Regulations 8</p> <p>1.3.1 International – United Nations 8</p> <p>1.3.2 United States (Federal vs. State) 9</p> <p>1.3.3 Canada 10</p> <p>1.3.4 European Union 10</p> <p>1.3.5 Asia 11</p> <p>1.3.6 China 11</p> <p>1.3.7 Japan 12</p> <p>1.3.8 Korea 12</p> <p>1.3.9 Australia 13</p> <p>1.4 Fire Safety and Non-Fire Safety Issues Requiring Non-Halogenated Flame Retardants 13</p> <p>1.5 Regulatory Outlook and Future Market Drivers 16</p> <p>References 17</p> <p><b>2 Phosphorus-Based Flame Retardants 23<br /></b><i>Sergei Levchik</i></p> <p>2.1 Introduction 24</p> <p>2.2 Main Classes of Phosphorus-Based Flame Retardants 25</p> <p>2.3 Red Phosphorus 26</p> <p>2.4 Ammonium and Amine Phosphates 29</p> <p>2.5 Metal Hypophosphites, Phosphites and Dialkyl Phosphinates 36</p> <p>2.6 Aliphatic Phosphates and Phosphonates 40</p> <p>2.7 Aromatic Phosphates and Phosphonates 48</p> <p>2.8 Aromatic Phosphinates 58</p> <p>2.9 Phosphine Oxides 62</p> <p>2.10 Phosphazenes 64</p> <p>2.11 Environmental Fate and Exposure to Organophosphorus FRs 65</p> <p>2.12 Conclusions and Further Trends 67</p> <p>References 68</p> <p><b>3 Mineral Filler Flame Retardants 101<br /></b><i>Reiner Sauerwein</i></p> <p>3.1 Introduction 101</p> <p>3.2 Industrial Importance of Mineral Flame Retardants 102</p> <p>3.2.1 Market Share of Mineral FRs 103</p> <p>3.2.2 Synthetic Mineral FRs within the Industrial</p> <p>Chemical Process Chain 104</p> <p>3.2.3 Natural Mineral FRs 106</p> <p>3.3 Overview of Mineral Filler FRs 107</p> <p>3.3.1 Mineral Filler Flame Retardants by Chemistry 107</p> <p>3.3.2 Classification by Production Process 109</p> <p>3.3.2.1 Crushing and Grinding 109</p> <p>3.3.2.2 Air Classification 110</p> <p>3.3.2.3 Precipitation and Their Synthetic Processes 110</p> <p>3.3.2.4 Surface Treatment 113</p> <p>3.3.3 Physical Characterisation of Mineral FRs 114</p> <p>3.3.3.1 Particle Shape/Morphology/Aspect Ratio 115</p> <p>3.3.3.2 Particle Size Distribution 116</p> <p>3.3.3.3 Sieve Residue 117</p> <p>3.3.3.4 BET Surface Area 118</p> <p>3.3.3.5 Oil Absorption 118</p> <p>3.3.3.6 pH-Value/Specific Conductivity 119</p> <p>3.3.3.7 Bulk Density and Powder Flowability 120</p> <p>3.3.3.8 Thermal Stability/Loss on Ignition/Endothermic Heat 122</p> <p>3.3.4 General Impact of Mineral FRs on Polymer Material Properties 123</p> <p>3.3.4.1 Optical Properties 123</p> <p>3.3.4.2 Mechanical Properties 123</p> <p>3.3.4.3 Water Uptake and Chemical Resistance 124</p> <p>3.3.4.4 Thermal Properties 126</p> <p>3.3.4.5 Electrical Properties 127</p> <p>3.3.4.6 Rheological Properties 128</p> <p>3.4 Working Principle of Hydrated Mineral Flame Retardants 128</p> <p>3.4.1 Filler Loading, Flammability and Flame Propagation 130</p> <p>3.4.2 Smoke Suppression 132</p> <p>3.4.3 Heat Release 134</p> <p>3.5 Thermoplastic and Elastomeric Applications 136</p> <p>3.5.1 Compounding Technology 136</p> <p>3.5.2 Compound Formulation Principals 138</p> <p>3.5.3 Wire & Cable 140</p> <p>3.5.4 Other Construction Products 147</p> <p>3.5.5 Special Applications 150</p> <p>3.5.6 Engineering Plastics for E&E Applications 152</p> <p>3.6 Reactive Resins/Thermoset Applications 154</p> <p>3.6.1 Production Processes for Glass Fiber-Reinforced Polymer Composite 156</p> <p>3.6.1.1 Paste Production 156</p> <p>3.6.1.2 Hand Lamination/Hand-Lay-Up 157</p> <p>3.6.1.3 SMC and BMC 157</p> <p>3.6.1.4 Pultrusion 158</p> <p>3.6.1.5 RTM/RIM 158</p> <p>3.6.2 Formulation Principles 159</p> <p>3.6.3 Public Transport Applications of GFRP 160</p> <p>3.6.4 E&E Applications 161</p> <p>3.6.5 Construction and Industrial Applications 163</p> <p>3.7 Conclusion, Trends and Challenges 164</p> <p>References 165</p> <p><b>4 Intumescence-Based Flame Retardant 169<br /></b><i>Serge Bourbigot</i></p> <p>4.1 Introduction 169</p> <p>4.2 Fundamentals of Intumescence 172</p> <p>4.3 Intumescence on the Market 179</p> <p>4.4 Reaction to Fire of Intumescent Materials 180</p> <p>4.5 Resistance to Fire of Intumescent Materials 204</p> <p>4.6 Conclusion and Future Trends 224</p> <p>References 225</p> <p><b>5 Nitrogen-Based Flame Retardants 239<br /></b><i>Alexander B. Morgan and Martin Klatt</i></p> <p>5.1 Introduction 239</p> <p>5.2 Main Types of Nitrogen-Based Flame Retardants 240</p> <p>5.3 Ammonia-Based Flame Retardants 241</p> <p>5.3.1 Ammonium Polyphosphate 242</p> <p>5.3.2 Other Ammonia Salts 246</p> <p>5.4 Melamine-Based Flame Retardants 247</p> <p>5.4.1 Melamine as Flame Retardant 248</p> <p>5.4.2 Melamine Salts 250</p> <p>5.4.3 Melamine Cyanurate 251</p> <p>5.4.4 Melamine Polyphosphate 254</p> <p>5.4.5 Melamine Condensates and Its Salts 256</p> <p>5.5 Nitrogen-Based Radical Generators 257</p> <p>5.6 Phosphazenes, Phospham and Phosphoroxynitride 261</p> <p>5.7 Cyanuric-Acid Based Flame Retardants 263</p> <p>5.8 Summary and Conclusion 264</p> <p>References 265</p> <p><b>6 Silicon-Based Flame Retardants 271<br /></b><i>Alexander B. Morgan and Mert Kilinc</i></p> <p>6.1 Introduction 271</p> <p>6.2 Basics of Silicon Chemistry 272</p> <p>6.3 Industrial Applications of Silicones 274</p> <p>6.4 Silicon-Based Materials as Flame Retardant Materials 277</p> <p>6.4.1 Inorganic Silicon-Based Flame Retardants 278</p> <p>6.4.1.1 Silicon Dioxide (SiO2) (Silica) 278</p> <p>6.4.1.2 Wollastonite 280</p> <p>6.4.1.3 Magadiite 281</p> <p>6.4.1.4 Sepiolite 281</p> <p>6.4.1.5 Kaolin 282</p> <p>6.4.1.6 Mica 283</p> <p>6.4.1.7 Talc 283</p> <p>6.4.1.8 Halloysite 284</p> <p>6.4.1.9 Layered Silicate Nanocomposites 285</p> <p>6.4.1.10 Sodium Silicate 289</p> <p>6.4.1.11 Silsesquioxane 289</p> <p>6.4.2 Organic Silicone-Based Flame Retardants 290</p> <p>6.4.2.1 Polyorganosiloxanes 290</p> <p>6.4.2.2 Silanes 292</p> <p>6.4.3 Other Silicone-Based Flame Retardants 293</p> <p>6.4.4 Silicone/Silica Protective Coatings 294</p> <p>6.5 Mode of Actions of Silicone-Based Flame Retardants and Practical Use Considerations 294</p> <p>6.5.1 Silicon Dioxide 294</p> <p>6.5.2 Silicate-Based Minerals 295</p> <p>6.5.3 Silicones 296</p> <p>6.6 Future Trends in Silicon-Based Flame Retardants 296</p> <p>6.7 Summary and Conclusions 298</p> <p>References 299</p> <p><b>7 Boron-Based Flame Retardants in Non-Halogen Based Polymers 309<br /></b><i>Kelvin K. Shen</i></p> <p>7.1 Introduction 309</p> <p>7.2 Major Functions of Borates in Flame Retardancy 310</p> <p>7.3 Major Commercial Boron-Based Flame Retardants and Their Applications 311</p> <p>7.4 Properties and Applications of Boron-Base Flame Retardants 311</p> <p>7.4.1 Boric Acid [B2O3·3H2O/B(OH)3], Boric Oxide (B2O3) 311</p> <p>7.4.2 Alkaline Metal Borate 314</p> <p>7.4.2.1 Borax Pentahydrate (Na2O·2B2O3·5H2O), Borax Decahydrate (Na2O·2B2O3·10H2O) 314</p> <p>7.4.2.2 Disodium Octaborate Tetrahydrate (Na2O·4B2O3·4H2O) 315</p> <p>7.4.3 Alkaline-Earth Metal Borate 317</p> <p>7.4.3.1 Calcium Borates (xCaO·yB2O3·zH2O) 317</p> <p>7.4.3.2 Magnesium Borate (xMgO·yB2O3·zH2O) 317</p> <p>7.4.4 Transition Metal Borates 317</p> <p>7.4.4.1 Zinc Borates (xZnO·yB2O3·zH2O) 317</p> <p>7.4.5 Nitrogen-Containing Borates 324</p> <p>7.4.5.1 Melamine Diborate [(C3H8N6)O·B2O3·2H2O)]/(C3H6N6·2H3BO3 ) 324</p> <p>7.4.5.2 Ammonium Pentaborate [(NH4)2O·5B2O3·8H2O)] 325</p> <p>7.4.5.3 Boron Nitride (h-BN) 325</p> <p>7.4.5.4 Ammonium Borophosphate 327</p> <p>7.4.6 Phosphorus-Containing Borates 327</p> <p>7.4.6.1 Boron Phosphate (BPO4) 327</p> <p>7.4.6.2 Metal Borophosphate 328</p> <p>7.4.7 Silicon-Containing Borates 328</p> <p>7.4.7.1 Borosilicate Glass and Frits 328</p> <p>7.4.8 Carbon-Containing Boron or Borates 329</p> <p>7.4.8.1 Graphene (Boron-Doped) 329</p> <p>7.4.8.2 Boric Acid Esters [B(OR)3] 329</p> <p>7.4.8.3 Boronic Acid [ArB(OH)2] 330</p> <p>7.4.8.4 Boron Carbide (B4C) 331</p> <p>7.5 Mode of Actions of Boron-Based Flame Retardants 331</p> <p>7.6 Conclusions 332</p> <p>References 333</p> <p><b>8 Non-Halogenated Conformal Flame Retardant Coatings 337<br /></b><i>Federico Carosio</i></p> <p>List of Acronyms 337</p> <p>8.1 Introduction to Conformal Coatings: The Role of Surface During Combustion 339</p> <p>8.2 Fabrics 346</p> <p>8.2.1 Natural Fabrics 347</p> <p>8.2.2 Synthetic Fabrics and Blends 358</p> <p>8.2.3 Process Equipment and Related Patents 371</p> <p>8.3 Porous Materials 373</p> <p>8.3.1 Open Cell PU Foams 374</p> <p>8.3.2 Other Porous Substrates 386</p> <p>8.3.3 Process Equipment and Related Patents 391</p> <p>8.4 Other Substrates 393</p> <p>8.5 Future Trends and Needs 396</p> <p>References 397</p> <p><b>9 Multicomponent Flame Retardants 413<br /></b><i>Bernhard Schartel</i></p> <p>9.1 The Need for Multicomponent Flame Retardants 413</p> <p>9.2 Concepts 419</p> <p>9.3 Combination with Fillers 424</p> <p>9.4 Adjuvants 428</p> <p>9.5 Synergists 431</p> <p>9.6 Combinations of Different Flame Retardants 435</p> <p>9.7 Combinations of Different Flame-Retardant Groups in One Flame Retardant 437</p> <p>9.8 Conclusion 439</p> <p>References 439</p> <p><b>10 Other Non-Halogenated Flame Retardants and Future Fire Protection Concepts & Needs 475<br /></b><i>Alexander B. Morgan, Paul A. Cusack and Charles A. Wilkie</i></p> <p>10.1 The Periodic Table of Flame Retardants 475</p> <p>10.2 Transition Metal Flame Retardants 478</p> <p>10.2.1 Vapor Phase Transition Metal Flame Retardants 478</p> <p>10.2.2 Condensed Phase Transition Metal Flame Retardants 479</p> <p>10.2.2.1 Metal Oxides 480</p> <p>10.2.2.2 Metal Complexes 481</p> <p>10.3 Sulfur-Based Flame Retardants 484</p> <p>10.4 Carbon-Based Flame Retardants 485</p> <p>10.4.1 Cross-Linking Compounds – Alkynes, Deoxybenzoin, Friedel-Crafts, Nitriles,</p> <p>Anhydrides 486</p> <p>10.4.1.1 Alkynes 486</p> <p>10.4.1.2 Deoxybenzoin 488</p> <p>10.4.1.3 Friedel-Crafts 488</p> <p>10.4.1.4 Nitriles 490</p> <p>10.4.1.5 Anhydrides 490</p> <p>10.4.2 Organic Carbonates 491</p> <p>10.4.3 Graft Copolymerization 492</p> <p>10.4.4 Expandable Graphite 493</p> <p>10.5 Bio-Based Materials 494</p> <p>10.6 Tin-Based Flame Retardants 496</p> <p>10.6.1 Introduction 496</p> <p>10.6.2 Zinc Stannates 497</p> <p>10.6.3 Halogen-Free Applications 498</p> <p>10.6.3.1 Polyolefins 499</p> <p>10.6.3.2 Styrenics 500</p> <p>10.6.3.3 Engineering Plastics 500</p> <p>10.6.3.4 Thermosetting Resins 503</p> <p>10.6.3.5 Elastomers 503</p> <p>10.6.3.6 Paints and Coatings 505</p> <p>10.6.3.7 Textiles 506</p> <p>10.6.4 Novel Tin Additives 506</p> <p>10.6.4.1 Coated Fillers 507</p> <p>10.6.4.2 Tin-Modified Nanoclays 509</p> <p>10.6.4.3 Mechanism of Action 510</p> <p>10.6.4.4 Summary 512</p> <p>10.7 Polymer Nanocomposites 513</p> <p>10.8 Engineering Non-Hal FR Solutions 513</p> <p>10.8.1 Barrier Fabrics 514</p> <p>10.8.2 Coatings 515</p> <p>10.8.2.1 Inorganic Coatings 515</p> <p>10.8.2.2 IR Reflective Coatings 517</p> <p>10.8.2.3 Nanoparticle Coatings 517</p> <p>10.8.2.4 Conformal/Integrated Coatings 518</p> <p>10.9 Future Directions 519</p> <p>10.9.1 Polymeric Flame Retardants and Reactive Flame Retardants 521</p> <p>10.9.2 End of Life Considerations For Flame Retardants 524</p> <p>10.9.3 New and Growing Fire Risk Scenarios 528</p> <p>10.9.4 Experimental Methodology for Flame Retardant Screening 531</p> <p>References 532</p> <p>Index 555</p>

<p><b>Alexander B. Morgan, PhD</b> has over twenty-five years of experience in the areas of materials flammability, polymeric material flame retardancy, fire science, fire testing, thermal decomposition chemistry, and fire safety engineering with an emphasis on chemical structure property relationships and fire safe material design. He has helped academic, government, and industrial customers solve their flame retardant and fire safety needs in a wide range of applications. Dr. Morgan is on the editorial review board for <i>Fire and Materials</i>, and is the Editor-in-Chief for the <i>Journal of Fire Science</i>. He is also a member of ASTM, Sigma Xi, International Association of Fire Safety Scientists, and the American Chemical Society.</p>

<p><b>The 2^nd edition of the definitive single book of information, regulations, and how to use non-halogenated flame retardant technology.</b></p> <p>This book focuses on non-halogenated flame retardants with an emphasis on practical and applied issues, and builds upon the 1st edition, but is not just a re-do/re-edit of 1st</sup> edition content. While non-halogenated flame retardants have not greatly changed since the 1^st edition was published in 2014, there have been enough advances and changes to merit a 2^nd edition. The book includes chapters on regulation and drivers for non-halogenated flame retardants, specific chapters on each of the major classes of flame retardants, as well as some newer technologies/niche non-halogenated solutions which are either starting to enter the market (coatings / bio-derived flame retardants) or are at least being studied with enough detail to bring to the attention of the reader. <p>As with the 1^st edition, the 2^nd edition still takes a practical approach to addressing the narrow subject of non-halogenated flame retardancy. It includes more emphasis on flame retardant selection for specific plastics, practical considerations in flame retardant material design, and what the strengths and limits of these various technologies are. Previous flame retardant material science books have covered non-halogenated flame retardants, but they focus more on how they work rather than how to use them. This book focuses more on the practical uses, hence the title of the book “Handbook”, which should make it of good use to industrial chemists and material scientists. <p><b>Audience</b> <p>The primary audience is material scientists, industrial chemists, fire safety engineers who have to meet flame retardant needs to sell products. It will also be useful to academics working to develop new flame retardant solutions.

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