Polymer flammability. II

The responses of a polymer flame to changes of specimen diameter, ignition position, and stability of the burning surface were determined. These extrinsic flame parameters restricted the transport of oxygen from the environment to the burning surface. With increasing restriction the oxygen demand from the environment for self-sustained combustion increased from a minimum oxygen demand at maximum access of environmental oxygen to the burning surface. This increase in oxygen demand was measured and correlated with surface oxygen concentrations estimated from the diffusion data of Part I. The minimum oxygen demand was demonstrated as characteristic for a given polymer and intrinsic in its chemical structure. This minimum oxygen demand, termed intrinsic combustibility, has been correlated with a polymer's thermooxidative stability, measured by thermogravimetric analysis at specific conditions. An intrinsic combustibility scale for polymers is given. In contrast, polymer flammability, as commonly measured in air, is interpreted as a variable property that depends on the extent of the interaction between extrinsic parameters, which are set by the testing configuration, with intrinsic combustibility.     

Oxygen and hydrogen atom concentration profiles in the premixed propane/oxygen flame

The oxygen and hydrogen free radical (atom) concentration profiles in the premixed propane/oxygen flame at 92.5% oxygen were determined using electron spin resonance (ESR) spectroscopy techniques. The ESR instrument was specially modified so that the flame can be probed for determining the oxygen and hydrogen atom population densities during the actual combustion process of propane burning in oxygen. The technique used for propane is similar to that suggested by Fristrom and Westenberg to measure the free radical concentration profiles in CC hydro- carbon/oxygen combustion.     

Polymer combustion

Experimental conditions have been defined for the steady-state combustion of vertically positioned polymer rods burning at the top surface. Temperature and composition profiles through solid and gas phases of the system, polymer consumption rate, and flame height were measured, and the response of these parameters to changes of the oxygen concentration in the environment were determined. Measurements showed that unreacted oxygen diffused from the environment to the burning surface and was absorbed into the polymer, forming a well defined oxygen-rich layer. Concentration of chemically bound oxygen at the surface of this layer were high, e.g., with polypropylene ca. 26 wt-%, and identical with the stoichiometry of the gases leaving the surface and serving as fuel for the flame. The composition of the gas phase at the surface indicated the conversion of 11.4% of the hydrocarbon fuel to CO, CO₂, and H₂O. An energy balance for the system confirmed that fuel production in this surface layer takes place via simultaneous oxidative and pyrolytic degradation of the polymer, with exothermic processes supplying the energy for endothermic processes. Conductive and radiative contributions from the gas phase were found to play a minor role in maintaining fuel formation. The rate of degradation of a polymer to fuel, normalized to the area of the burning surface, was found to be independent of polymer supply rate and to increase with the oxygen concentration in the environment. The degradation process was successfully modeled in TGA experiments at temperatures and oxygen concentrations representative of the burning surface. The existence of an oxidative surface layer was confirmed and the TGA degradation rate related to the surface-to-volume ratio of the polymer sample. Compositional analysis of a methane diffusion flame of a geometry identical to that of the polymer flame, revealed the presence of unreacted oxygen throughout the preheating zone and at the surface of the burner. Conversion of fuel to final combustion products at the surface was 6.3%. Temperature and composition changes as a function of oxygen concentration in the environment were determined and compared with the polymer diffusion flame. It was concluded that a polymer flame, because of its autogenerative fuel production, possesses only one degree of freedom, viz., the oxygen concentration in the environment, in contrast to the conventionally fueled diffusion flame for which fuel supply rate is an additional independent parameter. Due to this single degree of freedom, the sensitivity of the polymer flame to environmental influences is increased. Effects caused by these extrinsic factors will be the subject of a separate report.     

Thermal properties of poly(styrene) containing brominated aryl phosphate additives

General purpose poly(styrene) is a large volume commodity polymer widely used in a range of applications. For many of these the presence of an additive to impart some flammability resistance is required. Most commonly, brominated aromatics are used for this purpose. As the polymer undergoes combustion these compounds decompose to generate bromine atoms and/or hydrogen bromide which escape to the gas phase and trap flame propagating radicals. While these species are effective in inhibiting flame propagation they present the opportunity for loss of halogen to the atmosphere. For this reason, the use of these compounds is being limited in some parts of the world. Phosphorus compounds, on the other had, impart a flame retarding influence by promoting char formation at the surface of the burning polymer. This prevents heat feedback to the polymer and consequent pyrolysis to generate fuel fragments. The combination of both bromine and phosphorus present in a single compound might generate a superior flame-retarding additive in that both modes of retardancy might be promoted simultaneously. Should this be the case smaller amounts of additive might be necessary to achieve a satisfactory level of flame retardancy. A series of such additives, brominated aryl phosphates, has been synthesized and fully characterized spectroscopically. Blends of these additives, at various levels, with poly(styrene) have been examined by DSC, TG and in the UL-94 flame test. The flammability of the polymer is dramatically diminished by the presence of the additive.     

Radical processes in polymer burning and its retardation. I. ESR methods for studying the thermal decomposition of polymers in the preflame and flame zones

The determination of the free radical distribution in the preflame and flame zones of a burning polymer (polypropylene) by ESR leads to the conclusion that in all phases of the burning polymer an exothermic reaction zone encloses an oxygen-free pyrolytic zone. Whereas in the molten preflame zone (250–350°C) the polymer decomposes to oligomers, dimers, monomers, and the relevant free radicals or biradicals, in the gaseous flame zone the heat transport from the hot outer surface into the surrounding pyrolytic zone leads (with an increasing temperature gradient) to a progressive formation of thermodynamically more stable decomposition products. The CH. radicals generated at 400–800°C, after rapid cooling, yield polyaromaties with delocalized free electrons and the atomized carbon and its dimers at 800–1200°C, after cooling, yield graphite sheets with localized free electrons in its defects. Free radicals and paramagnetic species are trapped (a) in the gaseous pyrolytic products of heated polymers on the surface of a rotating cryostat, (b) in burning polymer drops by quenching in liquid nitrogen, and (c) in different zones of a burning diffuse flame. The superimposed ESR signals of the paramagnetic products are then qualitatively and quantitatively analyzed.     

Combinations of titanium(IV) oxide,iron(III) oxide and molybdenum(VI) oxide as flame retardants and smoke suppressants for thermoplastic polymers

An inert metal oxide (TiO₂), a catalytic oxide (Fe₂O₃) and an oxide which forms volatile halides (MoO₃) have been incorporated into polypropylene and polystyrene on their own, in combination with one another, and in the absence and presence of a halogen compound (Cereclor 70 or decabromobiphenyl oxide). Studies of the resulting flame-retardant and smoke-suppressant effects of the additive systems have been carried out by means of triangular diagrams. None of the systems investigated has any sizeable effect on the flammability of polypropylene, the limiting oxygen indices being raised by no more than 8 units. A positive interaction between Cereclor 70 and molybdenum oxide results however both in an improvement in the degree of flame retardance of this polymer and in a decrease in its already rather low smoke-producing tendency. These additive systems have proved more effective in the case of polystyrene. The decreased flammability manifests itself as an increase of up to 12 LOI units, while the maximum smoke density resulting from the combustion of the polymer is considerably decreased. In some cases the maximum smoke density, D_s, is less than 5% of the value for the pure polymer. The most efficient flame-retardant and smoke-suppressant systems generally involve molybdenum oxide and these are, in particular, ternary systems containing also another metal oxide and decabromobiphenyl oxide. Iron(III) oxide has little effect on its own but nevertheless considerably enhances the activity of the other metal oxides.     

电动汽车热泵系统中易燃制冷剂R290的燃烧特性

研究了制冷剂R290在电动汽车热泵空调系统潜在泄漏过程中的燃烧特性,通过实验得到了不同泄漏温度和体积流量下R290的燃烧特性,并与制冷剂R134a进行对比。实验表明:R290在低温下更难点燃,而在高泄漏体积流量下和高泄漏温度下会发生喷射火焰的吹灭现象,且当泄漏温度在30~60℃之间时,泄漏体积流量的增大会提高其燃烧强度。R290制冷剂气体温度越高,其火焰燃烧强度越大,燃烧火焰越细,火焰心高度越低;R290制冷剂气体的体积流量越大,火焰燃烧区域越大,火焰高度越低,热辐射通量越大。     

Ignitability of Polymers Related to Polymer Properties and Different Steady States of Combustion Theoretical Approach

A mathematical model of ignition and burning of organic polymers was used for evaluation and quantification of the tendency of polymers to ignition. The model permits investigation of the influence of one parameter of the polymer on the others. It was found that the model could be used for the verification of the ignitability method developed by Miller et al. [1]. Different steady states of combustion were found when using the model proposed. There is a characteristic steady state for normal flaming combustion, another for non-flaming combustion, and there are also unstable steady states that have no real physical meaning. This revised version was published online in July 2006 with corrections to the Cover Date.     

Quantitative description of low-density flames: H2 or P4 with O2

Results are surveyed on two branched-chain processes near the first ignition limit: the combustion of hydrogen and phosphorus. The causes of discrepancies between theory and experiment are considered: detailed heterogeneous factors that affect the burning rates. An explanation is given for the unusual (double) first ignition limit occurring under certain conditions when a low-density flame interacts with a surface having a complicated composition. A quantitative mechanism has been tested for such a flame for phosphorus in oxygen, which incorporates the main heterogeneous processes that influence the combustion. The origins of superdilute flames in oxygen-hydrogen mixtures have been elucidated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1273–1296, June, 1991.     

The relationship between thermal degradation and flammability

The relationship between flammability and thermal degradation is the consequence of the burning cycle needed to sustain fire. Thermal degradation behaviour of polymers is discussed in relation to generation of fuel and other products, including flame quenchers, and the production of char. The thermal degradation behaviour of the main classes of fire retardant is considered and illustrated by examples of the ways in which specific fire retardants exert their effect on a particular polymer.     

Crosslinking of Polydimethyl Siloxane Copolymers with Aromatic Dianhydrides: The Study of Thermal and Flame Retardant Properties †

Aromatic dianhydrides have been identified as potential candidates for crosslinking with biocatalytically synthesized siloxane copolymers containing a functional amino group on the isophthalate moieties. We present the synthesis, characterization, thermal and flame retardant properties of this novel class of crosslinked organo-siloxane copolymers. We also discuss the effect of the concentration of one of the crosslinkers, 1,2,4,5-benzenetetracarboxylic dianhydride (DAH), on thermal decomposition and flame retardant properties using thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC) studies. The char yields were improved in all the polymers crosslinked with the various aromatic dianhydrides. The heat release capacity of a polymer crosslinked with 20% DAH, compared to the pure polymer, was tremendously reduced from 190 J/gK to 100 J/gK. The decomposition kinetics from TGA showed that the crosslinked polymer is thermally more stable than the non-crosslinked polymer.     

Application of Plasma Fuel Reformer to an On-Board Diesel Burner

A conventional diesel burner has arisen several shortcomings, such a large supply of air for a stoichiometric combustion, and a long heat-up time to reach the light-off temperature of catalyst in a diesel after-treatment system. This study shows a promising potential of using a plasma reformer for staged diesel combustion with minimized air and fuel consumption, and increased the flame stability with low NOx emission. A working principle of a plasma fuel reformer for staged combustion is explained in detail by both visualizing the plasma-assisted flame and analyzing the gas products. The concentrations of H₂, CO, NOx and the unburned total hydrocarbons were measured by gas chromatography and a commercial gas analyzer. Considering the operating condition of diesel exhaust gas is too harsh to maintain a stable diesel flame with a conventional diesel burner, plasma fuel reformer has distinctive advantages in stable flame anchoring under the condition of low oxygen concentration and fast flow speed. The re-ignition and stable flame anchoring by entrapment of oxygen in exhaust gas is mainly attributed to the low ignition energy and high diffusion velocity of hydrogen molecule. From an economic point of view, plasma reformer is also the only technology which can use only 1/3–1/8 of the air required for the stoichiometric burning of a conventional diesel burner. A conventional burner was simulated and analyzed to consume up to 30 % more fuel compared to the plasma reformer with the staged combustion to get the same level of temperature elevation in a real diesel engine scale.     

A review on thermal decomposition and combustion of thermoplastic polyesters

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.     

Cone calorimeter analysis of flame retardant poly (methyl methacrylate)-silica nanocomposites

Nanocomposite is a promising method to reduce fire hazards of polymers. Specifically due to increased interfacial area between polymer and nanofillers, polymer nanocomposites have an advantage in reducing fire hazards efficiently even when the flame retardant additives are at a concentration of 5 mass% or less. In theory, crosslinking between the polymer chains can create a carbon-dense structure to enhance char formation, which can further promote the flame retardancy. However, little research has been done to explore the flammability of crosslinking polymer nanocomposites with a low concentration of nanosilica particles. In this study, crosslinked and non-crosslinked poly (methyl methacrylate) (PMMA) nanocomposites of a low concentration of nanosilica particles have been prepared via an in situ method. Their fire properties were tested by using the cone calorimeter at the heat flux of 50 kW m^?2. Although silica-containing flame retardants tend to negatively affect the ignitability and soot production especially at a high concentration, through the condensed phase mechanism, the samples of high loading rate of nanosilica particles show better fire retardancy performance in the aspect of flammability, including decreased heat release rate, mass loss rate, and total heat release. Additionally, crosslinking indeed attributes to the less intensive combustion of crosslinked PMMA samples, especially at a low concentration of nanosilica. The combination of nanosilica particles with the modification of the internal structure of the polymer nanocomposites might be a good strategy to improve fire retardancy.     

添加氢气对LPG/空气预混火焰结构的影响

针对氢气添加的LPG(液化石油气)+空气预混火焰结构进行了数值研究, 详细计算了在含氢比a为0%到45%、稀释引子D为21%到16%条件下的自由蔓延火焰, 得到了不同燃烧条件(φ=0.7-1.4)下的绝热燃烧速率变化规律. 由于LPG中的主要成分为丙烷和丁烷, 作者针对C3和C4物质提出了详细化学反应动力学系统, 并针对氢气添加的丁烷燃烧过程进行了数值计算, 得到了与实验相一致的结果, 验证了改进的详细化学机理的有效性. 此外, 进一步计算了对撞双火焰的加氢LPG火焰, 更加深入地探讨了火焰拉伸对燃烧稳定性和温度的影响, 重点研究了φ在0.5到0.7的稀薄燃烧, 验证了氢气添加可以有效提高稀薄燃烧条件下熄火拉伸率, 扩大稀薄燃烧的极限, 增加火焰的稳定性.     

(Photo)oxidative degradation and stabilization of flame retarded polymers

Flame retarded polymer formulations are mainly used in long-term applications whereas antioxidants, light stabilizers and co-additives provide the requested lifetime of plastic materials. However many flame retardants influence the oxidative and photooxidative stability of polymers often in a negative way resulting in early failure and loss in value. Moreover insufficient (photo)oxidative stability of the flame retardant itself may reduce the flame retardance performance over time. Therefore, there is a need to develop adjusted stabilizer systems considering the type of flame retardant, the polymer substrate and the intended application. Therefore, the influence of flame retardants on the (photo)oxidative stability of selected polymers is reviewed and strategies to extend the lifetime of flame retarded polymers are provided. In addition, the specific requirements of the stabilization of nanocomposites as potential flame retardant components are covered.     

Effects of Hydrogen Enhancement in LPG/Air Premixed Flame

A numerical study of hydrogen-enhanced liquefied petroleum gas (LPG) + air flames was presented. The variations of the adiabatic burning velocity in different conditions of combustion (?=0.7-1.4) were studied extensively. The hydrogen content in the fuel was varied from 0% to 45% and the dilution factor was from 21% to 16%. Since the major components of LPG are butane and propane, an appropriate chemical kinetic model must be chosen to solve the chemical reaction of C3 and C4 species. Validation of the chemical kinetic model against the fundamental combustion data was performed to insure accuracy. In addition, independent simulations were conducted in the opposed-jet, symmetric, twin-flame configuration. The effects of fluid mechanics, as manifested by the induced strain rate, were also considered. The effects of extinction strain rate on flame temperature and the flammability limits were calculated and the results showed that hydrogen-enhanced LPG/air premixed flames were more stable at high flame strain. The lean flammability limits were extended by the H₂ addition.     

Features of the propagation of laminar spherical flames initiated by a spark discharge in mixtures of methane,pentane, and hydrogen with air at atmospheric pressure

Using high-speed digital color cinematography, we studied the propagation of a laminar spherical flame in stoichiometric mixtures of hydrogen, methane, and pentane with air in the presence of additives at atmospheric pressure in constant-volume reactors, and derived quantitative data on the time of formation of a stable flame front. Cellular flames caused by gas-dynamic instability attributable to convective flows arising during the afterburning of gas were observed in hydrocarbon-air stoichiometric mixtures diluted with inert additives. It was found that the effect of additives of carbon dioxide and argon (>10%) and minor additives of CCl₄ on the combustion of hydrocarbons, and of propylene on the combustion of hydrogen-rich mixtures, lead to periods of delay in the development of a laminar spherical flame; in addition, additives of propylene promote the combustion of hydrogen poor mixtures.     

Progress on the synthesis and catalytic and anti‐migration properties of ferrocene‐based burning rate catalysts

Burning rate catalysts are of great importance in solid composite propellants for their unique property of accelerating combustion speed. Among various kinds of burning rate catalysts, ferrocene and its derivatives exhibit excellent catalytic effects and have become the most widely used burning rate catalysts. However, these simple ferrocenyl compounds trend to migrate in solid composite propellants during storage, which causes great damage to the propellants, equipment and environment and can even affect personal safety. The exploration of novel anti‐migratory ferrocene‐based compounds has become an advanced research hotspot in the field of burning rate catalysis. This review focuses on recent progress on the synthesis and catalytic properties of ferrocene‐based polymers and ferrocene derivatives as burning rate catalysts. Two main aspects of anti‐migratory exploration, i.e. synthesis of ferrocene‐based polymers and modification of the side groups of ferrocene, are summarized. Ferrocene‐based polymers can be obtained via condensation polymerization, addition polymerization, ring‐opening polymerization, polymer reactions, etc. Ferrocenyl compounds with active groups and ferrocene‐based metal coordination compounds were developed instead of the methods of lengthening the carbon chain of side groups and improving molecular polarity. Also, possible mechanisms of burning rate catalytic activity and migration are discussed and analyzed. Finally, the key points of the development of ferrocene‐based burning rate catalysts and solid composite propellants are proposed. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal degradation and flame retardance in copolymers of methyl methacrylate with diethyl(methacryloyloxymethyl)phosphonate

Methyl methacrylate (MMA) has been free radically copolymerized, both in bulk and in solution, with diethyl(methacryloyloxymethyl)phosphonate (DEMMP), to give polymers which are significantly flame retarded when compared with PMMA, as indicated by the results of limiting oxygen index (LOI) measurements, UL 94 tests, and the results of cone calorimetric experiments. The physical and mechanical properties of the copolymers are similar to those of PMMA, except that the bulk copolymers are slightly crosslinked, and are better than those of PMMA flame retarded to a similar extent by some phosphate and phosphonate additives. Examination of the some of the gaseous products of pyrolysis and combustion, and of chars produced on burning, show that flame retardation occurs in the copolymers by both a condensed-phase and a vapour-phase mechanism. The condensed-phase mechanism is shown to involve generation of phosphorus acid species followed by reaction of these with MMA units giving rise to methacrylic acid units. The methacrylic acid units subsequently form anhydride links, which probably impede depolymerization of the remaining MMA sequences, resulting in evolution of less MMA (the major fuel when MMA-based polymers burn). By undergoing decarboxylation, leading to interchain cyclisation and, eventually, to aromaticisation, the anhydride units are probably also the principal precursors to char.