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Practical Guide to Smoke and Combustion Products from Burning Polymers - Generation, Assessment and Control Sergei Levchik Marcelo Hirschler Edward Weil Smithers ismithers /Smithers - A Smithers Group Company Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.ismithers.net

C~ Preface vii 1. Smoke Obscuration/Opacity: Generation of Smoke from Polymeric Materials 1 1.1 Introduction 1 1.2 Parameters of Smoke Obscuration 1 1.2.1 Maximum Specific Optical Density of Smoke 1 1.2.2 Smoke Developed Index 1 1.2.3 Average Specific Extinction Area 2 1.2.4 Rate of Smoke Release 2 1.2.5 Total Smoke Released 2 1.2.6 Smoke Factor 3 1.3 Visible Smoke (Soot) Formation 3 1.4 Polycyclic Aromatic Hydrocarbons 5 1.5 Chemical Structure of Polymers in Relation to Smoke 6 1.6 Effects of Metals on Soot Formation 11 1.7 Effects of Flame Retardants 12 References 16 2. Generation of Combustion Products from Polymeric Materials (Smoke Toxicity) 19 2.1 Introduction 19 2.2 Common Smoke Toxicants 20 2.3 Calculation of Smoke Toxicity in Small Fires 21 2.4 Asphyxiants, 22 2.4.1 Carbon Monoxide 22 2.4.2 Hydrogen Cyanide 23 i

Practical Guide to Smoke and Combustion Products from Burning Polymers 2.5 Irritants 24 2.5.1 Organic Irritants, Acrolein 24 2.5.2 Inorganic Irritants 24 2.6 Overview of Smoke Toxicants - Is There Evidence for 'Supertoxic' Components? 28 2.7 Oxygen Depletion 28 2.8 Effect of Flame Retardants on Smoke Toxicity 28 2.8.1 Halogen Flame Retardants 28 2.8.2 Phosphorus Flame Retardants 30 2.8.3 Miscellaneous Flame Retardants 32 2.9 Autopsies of Fire Victims and Real-fire Monitoring 32 2.10 Post Flashover Fires, Mass-loss Model 33 2.11 Meaning of Smoke Toxicity Tests 35 2.12 Long-term Effects of Smoke Toxicity 36 2.13 Conclusions 40 References 40 3. Smoke Corrosivity... 49 3.1 Introduction 49 3.2 Corrosivity of Construction Materials 49 3.3 Smoke Corrosivity of Electrical and Electronic Equipment 53 3.4 Measurements of Smoke Corrosivity 54 References 58 4. Transport and Decay of Combustion Products 61 4.1 Introduction 61 4.2 Early Small-Scale Experiments 62 4.3 Large-Scale Experiments 67 4.3.1 Room-plenum Scenario 67 4.3.2 Room-corridor Scenario... 71 4.3.3 Room-corridor-room Scenario 72 4.3.4 Heating, Ventilation and Air Conditioning Scenario 73 4.4 Later Small-scale Experiments 75 ii

Contents 4.5 Modelling 77 4.5.1 Model Description 78 4.5.2 Assessment of the Hydrogen Chloride Decay Model in Hazard I 78 4.5.3 Update on Modelling 81 4.6 Other Gases 81 4.7 Conclusions 82 4.8 Appendix 85 4.8.1 Mathematical Formulation 85 References 89 5 Fire Tests to Assess Smoke and Combustion-Product Generation 93 5.1 Introduction 93 5.2 Static Small-scale Obscuration Tests on Materials 95 5.3 Dynamic Small-scale Smoke Obscuration Tests on Materials 98 5.4 Traditional Full-scale Smoke Obscuration Tests on Products 100 5.5 Full-scale Tests Measuring Heat Release and Smoke Release 105 5.6 Specialised Full-scale Tests Measuring Heat and Smoke Release on Specific Products 107 5.7 Small-scale Tests Measuring Heat and Smoke Release 109 5.8 Smoke Toxicity Tests 114 5.9 Smoke Corrosivity Tests 116 References 117 6 Methods for Reducing Visible Smoke in Specific Polymer Systems 125 6.1 General Comments 125 6.2 Smoke and Decomposition/Combustion Products from Polyvinyl Chloride 126 6.2.1 Antimony Oxide and Related Products: Effect on Smoke in Halogen-containing Polymers 127 6.2.2 The Effect of Chlorinated Paraffins and Related Chlorine Additives on Smoke 128 6.2.3 Use of Alumina Trihydrate for Reducing Smoke in Polyvinyl Chloride 129 iii

Practical Guide to Smoke and Combustion Products from Burning Polymers 6.2.4 Magnesium Hydroxide and other Magnesium Compounds for Reducing Smoke in Polyvinyl Chloride V. 6.2.5 Molybdenum Compounds in Polyvinyl Chloride 1. 6.2.6 Copper Compounds as Smoke Suppressants in Polyvinyl Chloride 1 6.2.7 Borates as Smoke Suppressants in Polyvinyl Chloride 1 6.2.8 Zinc Stannates as Smoke Suppressants in Polyvinyl Chloride 1 6.2.9 Zinc Sulfide as a Smoke Suppressant in Polyvinyl Chloride 1 6.2.10 Calcium Carbonate as a Smoke Suppressant in Polyvinyl Chloride 1 6.2.11 Low Flammability Plasticisers: Phosphate Esters and their Smoke Effects 1 6.2.12 Low Temperature Lower-smoke Alkyl Diphenyl Phosphate Plasticisers 1 6.2.13 Smoke Considerations in Calendered Vinyls 1 6.2.14 Smoke Considerations in Plenum Wire and Cable 137 6.2.15 Coated Textile Applications 140 6.2.16 Vinyl Flooring 142 6.2.17 Polyvinyl Chloride from a Safety and Environmental Point of View - the Role of Smoke 142 6.3 The Smoke Problem with Styrenics 143 6.4 Smoke Considerations with Textiles 145 6.5 Smoke Considerations with Polyurethanes 145 6.6 Smoke Considerations with Polycarbonates 146 6.7 Smoke Considerations in Thermoplastic Polyesters 1 6.8 Smoke Considerations in Polyamides 6.9 Smoke Considerations in Polyolefins 6.10 Aluminum Trihydrates and Magnesium Hydroxides Low Smoke Formulations 6.11 Smoke Considerations in Unsaturated Polyester Resins in Elastomers: 6.11.1 Low Smoke Polyester Resins by Replacement of Styrene... 6.11.2 Low Smoke Unsaturated Acrylate Oligourethane Resins with Alumina Trihydrate 6.11.3 Char-forming Low-smoke Additive for Unsaturated Polyester Resin Systems

Contents 6.12 Inherently Low Smoke Phenolic Resins 154 6.13 Low Smoke Epoxy Resins 155 References 156 7 Regulations, Codes and Standards Associated with Smoke 167 7.1 Background: Regulations, Codes and Standards 167 7.2 Regulations 169 7.2.1 How Regulation for Fire Safety Works in the United States 169 7.2.2 Federal Regulations 170 7.2.3 State Regulations 171 7.2.4 Local Regulations 172 7.2.5 Regulations of Specific Items 172 7.2.5.1 Aircraft 173 7.2.5.2 Ships 174 7.2.5.3 Trains and Underground Rail Vehicles 177 7.2.5.4 Motor Vehicles 187 7.2.5.5 Buses and School Buses 187 7.2.5.6 Mine Conveyor Belts 187 7.2.5.7 Carpets 188 7.2.6 Comparison with International Regulations 188 7.3 Codes 199 7.3.1 International Code Council Codes 199 7.3.1.1 International Building Codes 199 7.3.1.2 International Fire Codes 201 7.3.1.3 International Residential Codes 201 7.3.1.4 International Mechanical Codes 202 7.3.1.5 International Existing Building Codes 203 7.3.1.6 Other International Code Council Codes 203 7.3.2 National Fire Protection Association Codes and Standards 203 7.3.2.1 National Electrical Codes 203 7.3.2.2 National Life Safety Code 204 7.3.2.3 Uniform Fire Code 205 7.3.2.4 National Fire Protection Association Building Code 205 v

Practical Guide to Smoke and Combustion Products from Burning Polymers 7.3.2.5 Buildings of Historic or Cultural Interest 205 7.3.2.6 Manufactured Housing 206 7.3.2.7 Air-Conditioning Standard 207 7.3.2.8 Other National Fire Protection Association Codes and Standards 207 7.3.3 International Association of Plumbing and Mechanical Officials Codes 207 7.3.3.1 Uniform Mechanical Code 208 7.4 Standards 208 7.4.1 Organisations and Committees Issuing Fire Standards or Standards with Fire Tests 208 7.4.2 Standard Test Methods for Smoke Obscuration 209 7.4.3 Standard Test Methods Associated with Smoke Toxicity 210 7.5 Conclusions 211 References 211 8 Fire Hazard and Smoke Generation 221 References 225 Abbreviations 227 vi