The effect of temperature and ventilation condition on the toxic product yields from burning polymers

A major cause of death or permanent injury in fires is inhalation of toxic gases. Moreover, every fire is unique, and the range of products, highly dependant on fire conditions, produces a wide variety of toxic and irritant species responsible for the most fire fatalities. Therefore, to fully understand each contribution to the toxicity it is necessary to quantify the decomposition products of the material under the test. Fires can be divided into a number of stages from smouldering combustion to early well‐ventilated flaming through to fully developed under‐ventilated flaming. These stages can be replicated by certain bench‐scale physical fire models using different fuel‐to‐oxygen ratios, controlled by the primary air flow, and expressed in terms of the equivalence ratio (the actual fuel/air ratio divided by the stoichiometric fuel/air ratio). This work presents combustion product yields generated using a small‐scale fire model. The Purser Furnace apparatus (BS7990 and ISO TS 19700) enables different fire stages to be created. Identification and quantification of combustion gases and particularly their toxic components from different fire scenarios were undertaken by continuous Fourier transform infrared spectroscopy. The relationship between type of the fire particularly the temperature and ventilation conditions and the toxic product yields for four bulk polymers, low‐density polyethylene, polystyrene (PS), Nylon 6.6 and polyvinyl chloride (PVC) is reported. For all the polymers tested, except PVC, there is a dramatic increase in the yield of products of incomplete combustion (CO and hydrocarbons) with increase in equivalence ratio, as might be expected. For PVC there is a consistently high level of products of incomplete combustion arising both from flame inhibition by HCl and oxygen depletion. There is a low sensitivity to furnace temperature over the range 650–850°C, except that at 650°C PS shows an unexpectedly high yield of CO under well‐ventilated conditions and PVC shows a slightly higher hydrocarbon yield. This demonstrates the dependence of toxic product yields on the equivalence ratio, and the lack of dependence on furnace temperature, within this range. Copyright © 2007 John Wiley & Sons, Ltd.     

The generation of CO in bench-scale fire tests and the prediction for real-scale fires

Carbon monoxide (CO) is the single most important factor associated with deaths in fires; thus, predictions of CO developed in fires is an essential aspect of fire quantification. It is considered crucial to have correct CO prediction methods for post-flashover fire stages, since, in the United States at least, the majority of fire deaths are associated with fires which have gone to flashover. In this paper it is shown that the yiels of CO observed in real-scale fires are generally not related to either the chemical nature of the material being burned nor to the yield observed for the same material in bench-scale testing. Instead, the generation of CO in real-scale fires is determined largely according to the oxygen available for combustion, with thermal conditions of the fire plume also playing a significant role. This behavior is in sharp contrast to many other material fire properties, including yields of gases such as CO₂ and HCI, which can be predicated for real-scale fires from bench-scale results. Finally, results from various studies completed thus far indicate how effective prediction of real-scale CO yields may be accomplished. While bench-scale measurements are not necessary to predict real-scale CO, bench-scale toxic potency measurements can be in error if the CO component in them does not reflect on the real-scale CO yield. Thus, a method is developed whereby the bench-scale toxic potency measurements can be computationally corected to better approximate the toxic potencies measured in real-scale, post-flashover room fires. These techniques will, undobtedly, be further refined as additional experimental results become available.     

Toxicity of the pyrolysis and combustion products of poly(vinyl chlorides): A literature assessment

Poly(vinyl chlorides) (PVC) constitute a major class of synthetic plastics, Many surveys of the voluminous literature have been performed. This report reviews the literature published in English from 1969 through 1984 and endeavors to be more interpretive than comprehensive. PVC compounds, in general, are among the more fire resistant common organic polymers, natural or synthetic. The major products of thermal decomposition include hydrogen chloride, benzene and unsaturated hydrocarbons. In the presence of oxygen, carbon monoxide, carbon dioxide and water are included among the common combustion products. The main toxic products from PVC fires are hydrogen chloride (a sensory and pulmonary irritant) and carbon monoxide (an asphyxiant). The LC₅₀ value calculated for a series of natural and synthetic materials thermally decomposed according to the NBS toxicity test method ranged from 0.045 to 57 mg l^?1 in the flaming mode and from 0.045 to > 40 mg l^?1 in the non-flaming mode. The LC₅₀ results for a PVC resin decomposed under the same conditions were 17 mg l^?1 in the flaming mode and 20 mg l^?1 in the non-flaming mode. These results indicate that PVC decomposition products are not extremely toxic when compared with those from other common building materials. When the combustion toxicity (based on their HCI content) of PVC materials in compared with pure HCI experiments, it appears that much of the post-exposure toxicity can be explained by the HCI that is generated.     

Update on smoke toxicity of vinyl compounds

All organic materials burn and give off toxic products. These always include water, carbon dioxide, and the single gas causing the greatest hazard in fires—carbon monoxide (CO). The intrinsic toxicity of the smoke of all combustible materials, including PVC, is very similar in terms of lethality, with very few exceptions. Toxicity of vinyl compounds is due to two major gases: CO and hydrogen chloride (HCI). Since natural combustible materials are not chlorinated, speculation has arisen about the toxicity of HCl and of PVC smoke. Recent studies have shown that it takes similar doses of HCl and CO to kill rats. Furthermore, rats and baboons will tolerate the same levels of HCl. However, mice are much more sensitive than either rats or baboons towards HCl. Baboons are a very good model for humans; therefore, mice will be killed by exposure to much lower HCl levels than those required to kill humans. HCl concentrations in real fires are quite low: HCl decays rapidly by reacting with wall materials such as gypsum, cement, or ceiling tile. It does not, however, react rapidly with plastic or glass walls, which is where toxicity tests are carried out. Therefore PVC smoke is less hazardous in reality than it appears to be from toxicity test results. Since most products have similar intrinsic toxicities, as regards lethality, the real toxicity in a fire is a consequence of the rate of generation of gases. PVC is a difficult polymer to ignite and burns very slowly, so that it will give off less toxic products per unit time than many other common materials and cause lower fire hazard.     

Theory of fire and fire processes

There are two major fire processes, an understanding of which is essential for effective fire safety design: (1) the conditions under which a combustible material may become involved in flaming combustion, and (2) the rate at which such a material, once involved, will provide an output of heat, smoke, toxic gases, etc., which can endanger people and property. The first process may be regarded as covering both ignition and spread of fire on materials; its complement is the way in which fire may become extinguished. It is necessary for such processes to bring in a characteristic of the basic combustion reaction which, directly or indirectly, expresses the reactivity of the combustion process. Thus pilot ignition is usually associated with an approximate surface fuel temperature. More basically, it is associated with a critical flow rate of volatiles and a critical heat loss from the flame, the latter being influenced by ambient oxygen and temperatures conditions as well as heat lost and gained by the fuel itself. The most important factor governing the production of dangerous product is the rate at which volatiles first (fuel controlled fires) and later air (air controlled fires) are fed into the flames. The reactivity is of less importance, although it may be one of the factors which control combustion efficiency. In general, the more efficient is the combustion the more heat is produced, but the less smoke and toxic gases are produced. Some of the main advances in the above areas are reviewed in this paper.     

The corrosiveness of fluoride-containing fire gases on selected steels

Combustion gases were produced from several cable-insulation materials in separate experiments conducted in a model fire chamber. These gases were then allowed to interact with stressed metal specimens, consisting for the most part of various stainless and hardened steels as well as of carbon steel and stainless steel sheet. Thereafter the samples as exposed were stored in a humid atmosphere. As expected, PVC combustion gases caused the cracking of spring steel and also extensive pitting corrosion of stainless steel. These results confirmed that test conditions conformed to real-life fires as observed in practice. The combustion gases deriving from fluorinated polymers were much less corrosive on stainless steel and provoked only slight pitting in isolated cases. The rate of corrosion damage on carbon steel was lower by more than an order of magnitude than in the case of PVC. However, stress corrosion of sensitized 18/8 stainless steel and spring steel was found to occur. Tests on the thermal degradation of the dluorinated polymer ‘Teflon’ FEP and ‘Tefzel’ confirmed their high stability. If one compares the behaviour of these fluoroplastics with that of PVC it can generally be concluded that, although the use of fluorinated insulation materials on cables might not altogether eliminate corrosion problems in the event of fire, it does constitute a realistic contribution to fire protection and to the reeducation of fire-related damage.     

Poly(vinyl chloride) and its fire properties

This work provides an up‐to‐date review of the fire properties of poly(vinyl chloride) (PVC) materials, both rigid (unplasticized) and flexible (plasticized). The fire properties addressed include ignitability, ease of extinction (oxygen index), flame spread (small scale and intermediate scale), heat release, smoke obscuration, smoke toxicity, hydrogen chloride emission and decay, and performance in real‐scale fires. This comprehensive review includes a wide selection of references and tables illustrating the properties of PVC materials in comparison with those of other polymeric materials, including, in many instances, wood materials. The work puts these fire properties in perspective, showing that the heat release rate (the key fire property) of rigid PVC (and that of properly flame‐retarded flexible PVC) are among the lower values found for combustible materials. This work also shows that the smoke toxicity and smoke obscuration resulting from burning PVC materials in real‐scale fires is in the same range as those of other materials.     

浅述几类化学危险品的基本特性、火灾预防措施及灭火方法

化学危险品是具有爆炸、易燃、毒害、感染、腐蚀、放射性等危险特性,在运输、储存、生产、经营、使用和处置中,容易造成人身伤亡、财产损毁或环境污染而需要特别防护的物品。文章介绍了易燃固体、自燃物品及遇水放出易燃气体的物质、易燃液体、危险气体、爆炸品、毒性物质和感染性物质、氧化性物质和有机过氧化物六类化学危险品的基本特性,说明了其火灾预防措施,并概述了它们在发生灾害事故时的处置措施或灭火方法。     

Decomposition products of PVC for studies of fires

Approximately seventy-five organic materials have been detected by gas chromatography in the thermal decomposition products of PVC and are shown by mass spectrometry and retention studies to consist mainly of aromatic and aliphatic hydrocarbons. Weight-loss experiments and time-resolved chromatography indicate that these products are formed mainly during dehydrochlorination. The products are modified by the presence of oxygen but no oxygenated organic species have been detected. Experiments to specifically monitor the production of phosgene from the decomposition of both a rigid PVC sheet and a PVC polymer in air are recorded. Phosgene has not been detected and direct seeding techniques have been used to investigate the detection limits of this material. PVC is known to release the toxic gases, carbon monoxide and hydrogen chloride, when involved in fires. It is shown that the minor products, including phosgene, make little or no contribution to the overall toxicity of the decomposition products.     

A cone calorimeter for controlled-atmosphere studies

Many fires occur in ambient atmospheric conditions. To investigate certain types of fires, however, it is necessary to consider combustion where the oxidizer is not 21% oxygen/79% nitrogen. The Cone Calorimeter (ASTM E 1354, ISO DIS 5660) has recently become the tool of choice for studying the fire properties of products and materials. Its standard use involves burning specimens with room air being drawn in for combustion. To facilitate studying fires involving different atmospheres, a special version of the Cone Calorimeter was designed. This unit allows controlled combustion atmospheres to be created by the use of bottled or piped gases. To make such operation feasible, a large number of design details of the standard calorimeter had to be modified. This paper describes the background for these changes and provides an explanation of how the controlled-atmospheres unit is operated.     

The fire performance of PVC

The role of PVC in fires is currently a controversial topic because of the many negative comments made about PVC on the occurrence of any major fire disaster. Critics also use many small-scale smoke and toxic gas tests to define the role of PVC in these fires. The purposes of this paper are (1) to summarize the current technical knowledge of real fire behavior, (2) use this understanding to interpret available data for PVC in large- and small-scale fire tests, and (3) help bring a sense of technical realism to the issues involved.     

Detailed determination of smoke gas contents using a small‐scale controlled equivalence ratio tube furnace method

A series of tests including seven different materials and products have been conducted using a controlled equivalence ratio tube furnace test method. The main objective of the tests was to determine yields of fire‐generated products at defined combustion conditions. The tube furnace test method was set up and run in close agreement with that described in BS 7990:2003. At the time of experimental work the new tube furnace method was in the process of becoming an international standard. It was thus of interest to make an assessment of the capability of the method for determining production yields of important toxic fire products from different types of materials and products. The test series included solid wood, flexible polyurethane (PUR), fire‐retarded rigid PUR, a polyvinyl chloride (PVC) carpet, a high‐performance data cable with fluorine‐containing polymer matrix, a PVC‐based cable sheathing material and fire‐retarded polyethylene cable insulation material. Duplicate tests were generally conducted at both well‐ventilated and vitiated combustion conditions with these materials. The smoke gases produced from the combustion were quantified for inorganic gases by FTIR technique in all tests. A more detailed analysis of the smoke gases was conducted for some of the materials. This extended analysis contained a detailed assessment of organic compounds including, e.g. volatile organic compounds, isocyanates, aldehydes and polycyclic aromatic hydrocarbons. The analysis further included measurement of the size distribution of fire‐generated particles for some of the materials. The quantification of toxic inorganic gases produced by combustion at both well‐ventilated and vitiated conditions was successful regarding repeatability and stability. Typical yields for the two fire stages investigated were determined for a wide range of materials and products. The detailed analysis of organic compounds further corroborated that the new tube furnace method can replicate defined combustion conditions. Copyright © 2007 John Wiley & Sons, Ltd.     

Predicting toxic gas concentrations resulting from enclosure fires using local equivalence ratio concept linked to fire field models

A practical CFD method is presented in this study to predict the generation of toxic gases in enclosure fires. The model makes use of local combustion conditions to determine the yield of carbon monoxide, carbon dioxide, hydrocarbon, soot and oxygen. The local conditions used in the determination of these species are the local equivalence ratio (LER) and the local temperature. The heat released from combustion is calculated using the volumetric heat source model or the eddy dissipation model (EDM). The model is then used to simulate a range of reduced‐scale and full‐scale fire experiments. The model predictions for most of the predicted species are then shown to be in good agreement with the test results. Copyright © 2006 John Wiley & Sons, Ltd.     

Carbonyl sulphide in fire gases

The toxic gases released by combustion/pyrolysis of wool include CO, HCN and four compounds containing sulphur. Animal test data suggest that the toxicity of the sulphur compounds is significant. Wool was pyrolysed and the gases were analysed by GC-MS. SO² was the main sulphur-containing gas produced by flaming combustion in an oxygen-enriched atmosphere. In pyrolysis under various conditions COS was a major sulphur-containing product. Although it is a highly toxic gas, COS has not so far been reported by workers engaged in the toxicity of fire gases. It is suggested that analysis of COS be included in the analytical toxicology of sulphur-containing polymers.     

Fire conditions for smoke toxicity measurement

This paper identifies those fire conditions most often present when smoke toxicity is the cause of death. It begins with a review of the evidence that smoke-inhalation deaths are in the majority in fire fatalities in the United States. Next, there is an analysis of the evidence from the national fire experience showing the connection between post-flashover fires and smoke-inhalation deaths. Third is a presentation of real-scale fire test results demonstrating that post-flashover conditions are necessary to produce enough smoke to cause smoke-inhalation deaths in the cases where they actually occur. The fourth component is a sampling of results from computer simulations of fires, affirming and broadening the results from the fire tests. It is concluded that smoke-inhalation deaths occur predominantly after fires have progressed beyond flashover. This conclusion then provides a focus for smoke toxicity measurement in particular and fire hazard mitigation in general.     

Limitations of using combustion toxicity testing for product selection

During the last two decades there has been considerable concern about the combustion toxicity of synthetic materials such as PVC, and about their impact on overall fire hazard. Studies using many different methodologies have shown that the combustion toxicity of PVC is not unusual, but is comparable to many natural and synthetic materials. Because of various limitations, these tests have not been considered useful for code setting or regulatory activities. Furthermore, it has been emphasized that combustion toxicity is only one of many factors which must be evaluated in determining the fire hazard of a material. Still, the fact remains that PVC has performed favorably under many different conditions.     

Furniture and furnishings in the home—some fire statistics

A statistical study of fires in the United Kingdom involving the ignition of furniture and furnishings is presented. This paper examines the data for one year (1970). The analysis shows that in fires starting in furniture and furnishings the chance of a fatality is over twice that in other domestic fires. The majority of furniture fires involve upholstery or bedding and over 90% were started by smokers' materials, electric appliances, space heating or as the result of the activities of children or suspected arsonists. Eighty-five percent of the fatalities were found in the room of origin of the fire. Eighty per cent were overcome by smoke or toxic gases. Sixty percent of the fatalities were either under 5 or over 65 years of age. Monetary values are assigned for damage, casualties and deaths in fire. These costs can be used to assess the value of fire precautions. With the values taken, the total losses in furniture fires in the home amounted to £19 million in 1970. Life loss accounted for the major part of this sum. The expected annual loss per dwelling as a result of the ignition of furniture is thus only about £1, and is only £3 for all dwelling fires. This low figure suggests an approach of either selective spending on those most at risk (the elderly and handicapped) or by government activity through publicity and education.     

An alternative method for in vitro fire smoke toxicity assessment of polymers and composites using human lung cells

An alternative method for in vitro fire smoke toxicity assessment of polymers and composites using human lung cells has been investigated. A range of building and train interiors including polyethylene (PE), polypropylene (PP), polycarbonate (PC), polymethyl methachrylate (PMMA), polyvinyl chloride (PVC), fiberglass‐reinforced polymer (FRP), and melamine‐faced plywood (MFP) were studied. The exposure of combustion toxicants to human lung cells (A549) at the air/liquid interface was acquired using a Harvard Navicyte Chamber. Cytotoxic effects on human cells were assessed based on cell viability using the MTS assay (Promega). Cytotoxicity results were expressed as no observable adverse effect concentration (NOAEC), 10% inhibitory concentration (IC₁₀), 50% inhibitory concentration (IC₅₀), and total lethal concentration (TLC) values (mg/l). Mass loss data and toxic product yield were also determined. Results suggested that PVC (IC₅₀ 1.99 mg/l) was the most toxic materials followed by PP, FRP‐16, PC, PMMA, FRP‐10, PE, and melamine plywood. Some materials revealed to be more toxic under flaming combustion (PP, PC, FRP‐16, and FRP‐10), while others (PVC, PMMA, PE, and melamine plywood) appeared more toxic under non‐flaming combustion. The method developed can be used to screen the toxicity of materials which would be important information in building and mass transport material selection. Copyright © 2010 John Wiley & Sons, Ltd.     

Highway vehicle fire data based on the experiences of US fire departments

In 2003–2007, US fire departments responded to an average of 267 600 highway vehicle fires per year. These fires caused an average of 441 civilian deaths, 1326 civilian injuries, and $1.0bn (in US dollars) in direct property damage annually. Highway vehicles include cars, trucks, and other vehicles designed for highway use; highway vehicle fires can occur anywhere, not just on a highway. While these fires and associated losses have been falling in recent years, highway vehicles fires accounted for 17% of reported US fires, 12% of US fire deaths, 8% of US civilian fire injuries, and 9% of the direct property damage from reported fires. Data from the US Fire Administration's National Fire Incident Reporting System and the National Fire Protection Association's fire department survey were used to provide details about the circumstances of highway vehicle fires. Mechanical or electrical failures caused roughly three‐quarters of the highway vehicle fires but only 11% of the deaths. Collisions and overturns were factors contributing to the ignition in only 3% of the fires, but fires resulting from these incidents caused 58% of these vehicle fire deaths. The rate of bus fires per billion miles driven was 3.5 times that for highway vehicle fires overall. Copyright © 2012 John Wiley & Sons, Ltd.     

Toxicity of the combustion and decomposition products of polyurethanes

The acute toxicity by inhalation of polyurethane combustion and decomposition products was investigated by means of animal experiments. The results demonstrated that previous regulative and normative approaches which are based on the chemical nature of the materials tested and the analytically determined concentration data for major fire gas components are inconsistent with the research findings set out in TR 9122 of ISO TC92 SC3. The animal experiments, which complied with the test and assessment criteria put forward by the experts of ISO TC92 SC3 ‘Toxic Hazards in Fire’, provided convincing evidence that the overall toxic potency of the decomposition products released by polyurethane foam and PU coatings under comparable fire conditions was the same as for wood or wool. It was found that the acute toxic hazard potential of combustion gases is determined by the concentration of toxic components in the fire effluents (which in turn depends on the quantity of material burned in unit time) and by local conditions. This means that all parameters capable of affecting the combustion process are critical.