Methods in Lignin Chemistry

Preface 1 Introduction: 1.1 Background 1.2 Fire reaction and fire resistive properties of composites 1.3 Composites and fire 1.4 Case studies of composites in fire 1.5 Concluding remarks References 2Thermal Decomposition of Composites in Fire: 2.1 Introduction2.2. Thermal decomposition mechanisms of organic polymers 2/3 Rate processes and characterisation of decomposition 2.4 Polymers and their decomposition processes 2.5 Fire damage to composites 2.6 Concluding remarks References 3 Fire Reaction Properties of Composites: 3.1 Introduction 3.2 Time-to-ignition 3.3 Heat release rate 3.4 Extinction flammability index & thermal stability index 3.5 Mass loss 3.6 Smoke 3.7 Smoke toxicity 3.8 Limiting oxygen index 3.9 Surface spread of flame 3.10 Fire resistance References 4. Fire Modelling of Composites: 4.1 Introduction 4.2 Thermal exposure 4.3 Modelling material fire dynamics 4.4 Structural modelling of fire response References 5 Modelling the Thermal Response of Composites in Fire: 5.1 Introduction 5.2 Response of composites to fire 5.3 Modelling heat conduction in composites 5.4 Modelling the fire response of composites 5.5 Modelling the thermal properties of composites 5.6 Concluding remarks References 6. Structural Properties of Composites in Fire: 6.1 Introduction 6.2 Laminate properties 6.3 Measurement of elastic constants 6.4 Mechanical properties as a function of temperature 6.5 Modelling of properties 6.6 Fire resistance of laminates under load 6.7 Modelling of fire resistance of laminates under load 6.8 Concluding remarks References 7. Post-Fire Properties of Composites: 7.1 Introduction 7.2 Post-fire properties of laminates 7.3 Modelling the post-fire properties of laminates 7.4 Post-fire properties of sandwich composites 7.5 Post-fire properties of fire protected composites 7.6 Concluding remarks References 8 Flame Retardant Composites: 8.1 Introduction 8.2 The combustion cycle 8.3 Flame retardants for composites 8.4 Flame retardant fillers for composite 8.5 Flame retardant organic polymers for composites 8.6 Flame retardant inorganic polymers for composites 8.7 Flame retardant fibres for composites 8.8 Fire protective surface coatings References 9 Fire Properties of Polymer Nanocomposites: 9.1 Introduction 9.2 Characterization of nanocomposite formation 9.3 Evaluation of fire retardancy 9.4 Clay modifications 9.5 Examples of fire retardancy of polymer nanocomposites 9.6 Mechanisms of fire retardancy in nanocomposites 9.7 Future trends in fire retardancy of nanocomposites References 10 Fire Safety Regulations: 10.1 Introduction 10.2 Fire safety regulations for rail 10.3 Fire safety regulations for automobiles, buses and trucks 10.4 Fire safety regulations for civil infrastructure 10.5 Fire safety regulations for civilian aircraft 10.6 Fire safety regulations for ships and submarines References 11 Fire Tests for Composites: 11.1 Introduction 11.2 Scale of fire reaction tests 11.3 Cone calorimeter 11.4 Atmosphere controlled cone calorimeter 11.5 Intermediate-scale cone calorimeter 11.6 Ohio State University calorimeter 11.7 Limiting oxygen index test 11.8 Flame spread tests 11.9 Smoke density tests 11.10 Furnace tests 11.11 Burn-through & jet-fire tests 11.12 Single burning item test 11.13 Room fire tests 11.14 Structural integrity in fire tests 11.15 Aircraft fire tests 11.16 Concluding remarks References 12 Health Hazards of Composites in Fire: 12.1 Introduction 12.2 Smoke toxicity test methods 12.3 Health hazards of combustion gases 12.4 N-gas model for smoke toxic potency 12.5 Health hazards of fibres 12.6 Personal protective wear against burning composite materials 12.7 Concluding remarks References Subject Index

Fire Properties of Polymer Composite Materials

The relationship between heat release rate and other fire reaction properties of fibre reinforced polymer composite materials is investigated. The heat release rate and fire reaction properties of thermoset matrix composites reinforced with combustible fibres (aramid, extended-chain polyethylene) or non-combustible fibres (glass, carbon) were determined over a range of heat flux levels using the oxygen consumption cone calorimeter technique. The fire reaction properties that were measured were time-to-ignition, smoke density, carbon monoxide yield, carbon dioxide yield, mass loss rate and total mass loss. It is discovered that these reaction properties (apart from ignition time) are linearly related to the heat release rate for composites containing non-combustible fibres. When the reinforcement is combustible, however, the heat release rate only appears to be related to the carbon monoxide yield, mass loss rate and (in some cases) smoke density. This study clearly shows the importance of the relationship between heat release rate with smoke density and carbon monoxide yield, the two reaction properties that influence the survival of humans in fire.

Heat release of polymer composites in fire

An overview is presented of the literature on the thermal decomposition and combustion of thermoplastic polyesters, especially commercially important poly(ethylene terephthalate) (PET) and poly(1,4-butylene terephthalate) (PBT) Although the literature is not clear as to whether heterolytic or homolytic scission of aliphatic fragments is the first step in the thermal decomposition of polyesters, in any case volatilization of light aliphatic fragments make polyesters easily ignitable polymers Despite the presence of benzene groups in the main polymer chain, thermoplastic polyesters show very limited tendency to char, but instead, aromatic-containing polymer fragments volatilize and feed the flame Fire retardant additives, although they usually facilitate decomposition of the polyesters at lower temperature, also usually promote charring and therefore suppress combustion Copyright © 2004 John Wiley & Sons, Ltd

A review on thermal decomposition and combustion of thermoplastic polyesters

The pyrolysis and fire behavior of glass-fiber reinforced poly(butylene terephthalate) (PBT/GF) with two different metal phosphinates as flame retardants in combination with and without melamine cyanurate (MC) were analyzed by means of thermogravimetry, thermogravimetry coupled with infrared spectroscopy, flammability, and cone calorimeter tests as well as scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray fluorescence spectroscopy. In PBT/GF, dosages of 13–20% of the halogen-free flame retardant aluminum phosphinate or aluminum phosphinate in combination with MC fulfill the requirements for electrical engineering and electronics applications (UL 94 = V-0; LOI > 42%), whereas the use of the same amount of zinc phosphinate or zinc phosphinate in combination with MC does not improve the fire behavior satisfactorily (UL 94 = HB; LOI = 27–28%). The performance under forced flaming conditions (cone calorimeter) is quite similar for both of the metal phosphinates. The use of aluminum and zinc salts results in similar flame inhibition predominantly due to the release of the phosphinate compounds in the gas phase. Both metal phosphinates and MC interact with the polymer changing the decomposition characteristics. However, part of the zinc phosphinate vaporizes as a complete molecule. Because of the different decomposition behavior of the metal salts, only the aluminum phosphinate results in a small amount of thermally stable carbonaceous char. In particular, the aluminum phosphinate-terephthalate formed is more stable than the zinc phosphinate-terephthalate. The small amount of char has a crucial effect on the thermal properties and mechanical stability of the residue and thus the flammability. Copyright © 2008 John Wiley & Sons, Ltd.

Flame retardancy mechanisms of metal phosphinates and metal phosphinates in combination with melamine cyanurate in glass‐fiber reinforced poly(1,4‐butylene terephthalate): the influence of metal cation

A kinetic study of the thermal decomposition of polyesters by controlled-rate thermogravimetry

(1) TGの等速昇温により高分子の熱分解挙動を解析するための測定条件として, 昇温速度1～10℃/minでは試料の初期重量は約1mgが好ましいことを見いだした. (2) 熱分解挙動の解析方法に関して次の結論を得た. (1) この条件では重量減少速度はノイズが多く. これを用いるFriedman法の解析結果はばらつきが大きい. (2) 反応速度式の積分式の数値近似式を用いる方法と一次近似式を用いる方法からは, 共に昇温速度の異なる重量変化率と絶対温度の逆数のプロットの重ね合わせが近似的に可能であると結論される. 両者は近似としては同じレベルのものである. (3) 数値近似式の係数を適切に選べば両者は同じ結果を与える. (3) 一次近似を用いて5種類のポリエステルの窒素中の熱分解反応を解析した. 熱分解反応様式はすべて主鎖のランダム開裂であり, 反応速度定数の頻度因子の対数と活性化エネルギーは直線的な相関を示した.

Thermal Decomposition Behaviors of Polymers Analyzed with Thermogravimetry.

Thermal analysis of polymer samples by a round robin method

PURPOSE: To obtain a material capable of providing optically uniform and transparent cured product having high refractive index, by using a sulfur- containing acryl oligomer composition obtained by converting an oligomer having terminal diol to an oligomer having terminal (meth)acrylic acid esters. CONSTITUTION: An oligomer having terminal diol obtained from a dihalogen compound, dimercaptane compound and hydroxyl group-containing mercaptan compound is reacted with an acylating agent to provide the aimed product expressed by the formula (R 1 is H or CH 3 ; R 2 and R 3 are 1W12C alkylene, 2W12C oxydialkylene or 6W20C aralkylene; X is Cl, Br or I; m is 0W4; n represents average oligomerization degree and is ≤10). The above-mentioned oligomer is optically uniformly cured to provide a cured product having high refractive index of ≥1.60 suitable in using as plastic lens and excellent transparency and workability. COPYRIGHT: (C)1989,JPO&Japio

Shoji Ichihara

Papers

A kinetic study of the thermal decomposition of polyesters by controlled-rate thermogravimetry

Thermal Decomposition Behaviors of Polymers Analyzed with Thermogravimetry.

Thermal analysis of polymer samples by a round robin method

Sulfur-containing acryl oligomer composition

Analysis of thermal decomposition behaviors with consecutive reactions by TG