Thermal degradation of epoxy resin/carbon fiber composites: Influence of carbon fiber fraction on the fire reaction properties and on the gaseous species release

The thermal degradation of epoxy resin/carbon fiber composites has been performed in ISO 5660 standard cone calorimeter using a piloted ignition. Two kinds of composites that differ by their volume fractions in carbon fiber (56 and 59 vol.%) were tested in this study. The cone calorimeter irradiance level was increased up to 75 kW m^?2 to characterize the carbon fiber volume fraction influence on the composite thermal degradation. Thus, main flammability and combustibility parameters were determined and calculated such as mass loss, mass loss rate, ignition time, thermal response parameter, ignition temperature, thermal inertia, and heat of gasification. As a result, all the characteristic parameters for the thermal resistance of composites were decreased when the carbon fiber volume fraction increased. Moreover, the main gaseous products (such as NO, CO, CO₂, HCN, H₂O, and lightweight hydrocarbons) emitted as well as the oxygen consumption during the composite thermal decomposition were also quantified simultaneously with a portable gas analyzer and a Fourier transform infrared spectrometer. The main species emission yields calculated from the gas analysis results increased slightly when the carbon fiber volume fraction was increased in the initial sample. The epoxy composite was represented as a sooty material with a significant production of soot particles during the combustion process. Furthermore, heat release rate, total heat release, and effective heat of combustion were calculated by using the oxygen consumption calorimetry technique. The results obtained showed that a small increasing of composite carbon fiber amount induced a sharp decrease of heat release rate and total heat release. Copyright © 2014 John Wiley & Sons, Ltd.     

Combustibility of cyanate ester resins

Flaming and non‐flaming combustion studies were conducted on a series of polycyanurates to examine the effect of chemical composition and physical properties on the fire behavior of these crosslinked, char forming, thermoset polymers. Heats of complete combustion of the polymer and fuel gases were determined by oxygen bomb calorimetry and pyrolysis‐combustion flow calorimetry, respectively. Fire calorimetry experiments were conducted to measure the total heat released, the rate of heat release and the smoke generation in flaming combustion. Fire response parameters derived from the data include the thermal inertia, heat of gasification, effective heat of combustion and combustion efficiency. Halogen‐containing polycyanurates exhibited extremely low heat release rate in flaming combustion compared with the hydrocarbon resins yet produced significantly less smoke and comparable levels of carbon monoxide and soot. Published in 2005 by John Wiley & Sons, Ltd.     

A guide to characterizing heat release rate measurement uncertainty for full‐scale fire tests

Accurate heat release rate measurements provide essential information to defining the fire safety characteristics of products. The size, complexity, and cost of full‐scale fire tests make achieving accurate and quantitative results a serious challenge. A detailed uncertainty analysis of a large‐scale heat release rate measurement facility is presented as a guide to the process of estimating the uncertainty of similar facilities. Quantitative heat release rate measurements of full‐scale fires up to 2.7 MW were conducted using the principle of oxygen consumption calorimetry. Uncertainty estimates were also computed for the heat input measurements from a well‐controlled natural gas burner. The measurements of heat input and heat release rate were performed independently, and the discrepancy between the two was well within the uncertainty limits. The propagation of uncertainty was performed at the level of voltage and temperature measurements, which avoided using mutually dependent measurement parameters. Reasons for the significant contribution to the combined uncertainty from the oxygen concentration and exhaust flow measurements are demonstrated. Also presented is a first‐order effort to account for the uncertainty due to factors in full‐scale fire tests such as operator error and environmental influences that are not modeled by the heat release rate equation. Published in 2008 by John Wiley & Sons, Ltd.     

Calibration of flow rate in cone calorimeter tests

The cone calorimeter is one of the major fire tests. The measurement method is based on the evaluation of mass flow and oxygen concentration of fire effluents to calculate heat release rate. Different studies highlighted that the governing parameter for uncertainty at important values of heat release rate was the characteristic constant of an orifice plate used to measure mass flow (C‐factor). This parameter is usually determined each testing day by oxygen consumption calorimetry with a reference methane burner. This publication presents a calibration method for volumetric flow rate without using orifice plate and then an extension to C‐factor determination without methane burner and calorimetry. The uncertainty calculation applied to a real example highlights the fact that the method is suitable to respect tolerance of standardized test conditions for both parameters. Copyright © 2013 John Wiley & Sons, Ltd.     

Combustion characteristics of crude oils

Small‐scale free‐burning pool fire tests were conducted in a cone calorimeter to obtain the combustion characteristics of 14 different crude oils. Measurements included the heat release rate based on oxygen consumption calorimetry, mass loss rate, radiative heat flux from the flame to a nearby target, liquid fuel temperature, extinction coefficient and CO₂ and CO concentrations in the exhaust duct. The effective heat of combustion, radiative heat loss fraction and smoke yield were calculated on the basis of the measured data. It was found that the heat release rate, mass loss rate, flame radiation and smoke yield were a function of the type of crude oil. The effective heat of combustion, extinction coefficient and radiative heat loss fraction were nearly constant for the range of crude oils evaluated in this programme. The heat release rate, mass loss rate, flame radiation and smoke yield appeared to correlate well with the crude oil density. Copyright © 2001 John Wiley & Sons, Ltd.     

Estimation of rate of heat release by means of oxygen consumption measurements

Measurement of the rate of oxygen consumption provides a simple, versatile and powerful tool for estimating the rate of heat release in fire experiments and fire tests. The method is based on the generalization that the heats of combustion per unit of oxygen consumed are approximately the same for most fuels commonly encountered in fires. A measurement of the rate of oxygen consumption can then be converted to a measure of rate of heat release. Data on heats of combustion are presented to support this generalization. The applicability of the technique to combustion under fire conditions is examined, possible sources of error in the measurements are discussed, and applications of the method are reviewed. It is concluded that the accuracy of oxygen consumption based rate of heat release measurements should compare favorably with those derived from conventional calorimetric measurements.     

Heat release rate in evaluation of conveyor belts in full-scale fire tests

The theoretical bases for calculation of heat release rate during burning of conveyor belts in the fire-testing gallery has been presented. Taking as an example the results of measurements of oxygen, carbon dioxide and monoxide content in the products of combustion of conveyor belts during the testing of their flammability in the full-scale fire gallery, the possibility has been demonstrated for using the calculations of heat release rate in an assessment of conveyor belt flammability. The total quantity of heat released during the belt fire in the experimental gallery can provide the basis to develop a new method of testing as well as the criteria for assessment of fire resistance of the conveyor belts using oxygen consumption calorimetry. © 1997 John Wiley & Sons, Ltd.     

Heats of combustion of high temperature polymers

The heats of combustion for 49 commercial and developmental polymers of known chemical structure were determined using an oxygen bomb calorimeter according to standard methods. The experimental results were compared with thermochemical calculations of the net heat of combustion from oxygen consumption and the gross heat of combustion from group additivity of the heats of formation of products and reactants. The polymers examined were thermally stable, char forming thermoplastics and thermoset resins containing a significant degree of aromaticity and heteroatoms including — nitrogen, sulphur, phosphorus, silicon, and oxygen in linear and heterocyclic structures. The gross and net heats of combustion calculated from polymer enthalpies of formation and oxygen consumption thermochemistry were within 5% of the experimental values from oxygen bomb calorimetry. The heat released by combustion per gram of diatomic oxygen consumed in the present study was E=13.10±0.78 kJ/gO₂ for polymers tested (n=48). This value is indistinguishable from the universal value E13.1 kJ/gO₂ used in oxygen consumption combustion calorimetry. Published in 2000 by John Wiley & Sons Ltd.     

High-throughput approach to the catalytic combustion of diesel soot

A methodology for the evaluation of diesel soot oxidation catalysts by high-throughput (HT) screening was developed. The optimal experimental conditions (soot amount, catalyst/soot ratio, type of contact, composition and flow rate of gas reactants) ensuring a reliable and reproducible detection of light-off temperatures in a 16 parallel channels reactor were set up. The temperature profile measured in the catalyst/soot bed under TPO conditions when the exothermic combustion of soot takes place was shown to provide an accurate measurement of the ignition. Its reproducibility and relevance were checked. The results obtained with a reference noble metal free catalyst (La_0.8Cr_0.8Li_0.2O₃ perovskite) agree very well with literature data. Qualitative mechanistic features could be derived from these experiments, stressing the likely limiting step of oxygen transfer from catalyst surface to soot particulates to ignite the soot combustion. Ceria material was shown to be more appropriate than perovskite one. From an HT screening of a large diverse library (over 100 mixed oxides catalysts) under optimized conditions, about 10 new formulations were found to perform better than selected noble metal free reference materials.     

Measurement uncertainty analysis for calorimetry apparatuses

The absence of a standardized uncertainty analysis methodology for fire calorimetry apparatuses makes significant comparison of test results between fire laboratories difficult. From a testing (pass/fail) perspective, the lack of a common means to estimate the uncertainty is problematic. From a material development viewpoint, the ability to differentiate versions of material systems is uncertain which potentially results in economic penalties for the developer. Probability and statistics methodologies recommended by International Organization for Standardization and National Institute of Standards and Technology were applied to begin developing a standardized measurement uncertainty method for fire calorimetry apparatuses. The method was applied to each component instrument (intrinsic and calibration uncertainty only) and each related physics quantity measured indirectly. Results were reported at the 95% confidence level. The results were compared with various reference cases as well as those from a Monte Carlo Simulation technique modelling the experiments. The consistency verified our measurement uncertainty method. The results for heat release rate and average heat of combustion provide the user of Cone Calorimeter data with the ability to estimate potential experimental error inherent in the operation of the Cone. This information can be used to make informed decisions related to the matters cited above. Copyright © 2007 John Wiley & Sons, Ltd.     

A novel catalyst for diesel soot oxidation

In this study, cobalt and lead based mixed oxide catalysts were tested for their soot oxidation ability. In addition to a mixed oxide formerly marketed as ceramic paint, a home made set was also prepared by incipient wetness impregnation of a cobalt oxide powder with a lead acetate solution and subsequent calcination. The materials investigated in this study were shown to decrease the peak combustion temperature of home made soot from 500 to 385 °C in air. Soot oxidation tests under inert (N₂) atmospheres revealed that the oxidation took place by using the lattice oxygen of the catalyst. Reaction temperature could be further decreased when these mixed oxide catalysts were impregnated with platinum. An optimum platinum loading was determined as 0.5 wt% based on the peak combustion temperature of the soot. The role of Pt was to assist the oxygen transfer from the gas phase to the lattice. It was observed that NO₂ is a better oxidizing agent as compared to air whereas NO had hardly any activity against soot oxidation reaction. When the mixed oxide catalyst was impregnated with platinum, the peak combustion temperature was measured as 310 °C in the presence of NO_x and air. The catalyst's unique performance was in terms of the rate of soot oxidation. Under the experimental conditions studied here, the soot oxidation was so facile that the oxygen in the gas phase was completely depleted. This stream of oxygen depleted and CO enriched gas phase can be used to reduce NO_x in the presence of a downstream or a co-catalyst.     

氧气浓度对K2CO3催化无烟煤和石墨燃烧的影响

采用综合热分析仪研究不同氧气浓度下K2CO3催化无烟煤和石墨燃烧的特性,考察了氧气浓度对催化燃烧机制的影响. 结果表明,K2CO3提高了燃烧反应和氧气扩散速率,但对燃烧速率的提高幅度大于对氧气扩散速率提高幅度,延长了无烟煤燃烧过程的平台时间. 氧气浓度由21%增加到100%时, K2CO3催化无烟煤着火温度降低幅度由37.7℃增至78.1℃,催化石墨着火温度降低幅度由204.8℃增至233.6℃. 煤燃烧初期K2CO3使燃烧活化能下降,氧气浓度高于40%时,燃烧由扩散向反应控制转变;燃烧后期活化能低于40 kJ/mol,燃烧受扩散控制. 石墨在燃烧初期K2CO3使燃烧活化能下降,但氧气浓度增加并未改变燃烧控制步骤,燃烧受反应控制;燃烧后期氧气浓度由21%增加到100%时, K2CO3催化石墨燃烧活化能由39 kJ/mol增至110 kJ/mol,燃烧由扩散控制向反应控制转变.     

Molar group contributions to the heat of combustion

Experimental results for the gross heat of combustion of over 140 commercial and developmental polymers and small molecules of known chemical structure were used to derive additive molar group contributions to the heat of combustion. The materials examined contained carbon, hydrogen, oxygen, nitrogen, phosphorus, sulphur, chlorine, fluorine and silicon in linear, branched and cyclic structures. Values for the molar group contributions were summed and divided by the molecular weight of the molecule or polymer repeat unit to yield the gross heat of combustion as determined by oxygen bomb calorimetry. This new method provides an accurate single step method for calculating the heat of combustion. The average relative error of the calculated gross heats of combustion is 2.8%. Published in 2002 by John Wiley & Sons, Ltd.     

O2/CO2气氛中水蒸气预混CH4燃烧特性与烟气余热梯级利用方案

对O2/CO2气氛中甲烷预混水蒸气燃烧特性及主要污染物生成进行了数值模拟研究,在加湿燃烧的基础上提出一种全新的清洁燃烧方式,即在保证甲烷流量一定时,通过改变入口处水蒸气的质量分数,研究水蒸气预混比Rf(0, 0.1, 0.2, 0.3, 0.4和0.5)对燃烧流场、燃烧组分和污染物浓度的影响。结果表明,随Rf增大,燃烧反应速率上升、燃烧效率提高且污染物排放量降低。模拟所得甲烷预混水蒸气的最优气氛为81%CH4/19%H2O,提出了一种高效节能的O2/CO2气氛下水蒸气预混CH4燃烧与烟气余热梯级利用方案。     

A novel catalyst for diesel soot oxidation

In this study, cobalt and lead based mixed oxide catalysts were tested for their soot oxidation ability. In addition to a mixed oxide formerly marketed as ceramic paint, a home made set was also prepared by incipient wetness impregnation of a cobalt oxide powder with a lead acetate solution and subsequent calcination. The materials investigated in this study were shown to decrease the peak combustion temperature of home made soot from 500 to 385 °C in air. Soot oxidation tests under inert (N₂) atmospheres revealed that the oxidation took place by using the lattice oxygen of the catalyst. Reaction temperature could be further decreased when these mixed oxide catalysts were impregnated with platinum. An optimum platinum loading was determined as 0.5 wt% based on the peak combustion temperature of the soot. The role of Pt was to assist the oxygen transfer from the gas phase to the lattice. It was observed that NO₂ is a better oxidizing agent as compared to air whereas NO had hardly any activity against soot oxidation reaction. When the mixed oxide catalyst was impregnated with platinum, the peak combustion temperature was measured as 310 °C in the presence of NO_x and air. The catalyst's unique performance was in terms of the rate of soot oxidation. Under the experimental conditions studied here, the soot oxidation was so facile that the oxygen in the gas phase was completely depleted. This stream of oxygen depleted and CO enriched gas phase can be used to reduce NO_x in the presence of a downstream or a co-catalyst.     

CO〈sub〉2〈/sub〉抑制煤氧吸附过程的实验研究

煤对CO2的吸附能力较强,CO2分子会优先吸附在煤表面,减少O2的吸附量,抑制煤氧吸附过程。通过程序升温实验,研究CO2对煤氧吸附的抑制作用,测定煤样在不同CO2浓度下产生O2、CO、CH4的浓度值,分析CO2浓度对耗氧速率、CO产生率的影响规律。结果表明,37%～50%浓度的CO2对煤体耗氧速率的抑制效果明显,对煤样的CO产生率及甲烷浓度有降低作用,说明CO2能够有效抑制煤氧吸附过程,防止煤炭氧化自燃的发生。研究结果对CO2防灭火技术的开发与应用具有指导作用。     

水蒸气纯氧条件下合成气燃烧特性

水蒸气纯氧燃烧技术因具有高效零污染物排放的特点而备受关注,对合成气在水蒸气纯氧条件下的燃烧特性进行了实验研究。在扩散燃烧实验台上测量了H₂O/O₂为2.0时,燃烧室中心气体成分和火焰温度随停留时间的变化规律,分析了过量氧气系数对合成气水蒸气纯氧燃烧过程的影响。研究结果表明:过量氧气系数为0时,H₂和CO的燃烧主要在前28 ms内,H₂的燃烧速率较快,能够快速燃尽;CO燃烧较慢,燃烧室出口含量依然很高。过量氧气系数从0增大到10%时,CO的浓度整体降低,燃烧速率提高,燃烧前期火焰温度提高。燃烧室出口CO浓度随过量氧气系数的增加逐渐降低,氧气微过量时CO浓度迅速下降,继续增大时,燃烧室出口CO的浓度下降缓慢。     

Thermal Separation of Soot Carbon

We present here a simple and versatile variant of the thermal analysis of soot carbon, and a discussion on the encountered analytical artifacts. The method is based on a two-step combustion procedure; the removal of the organic material that does not absorb visible light is optimized during a precombustion step at 340°C during 2 hours under a pure oxygen flow, and the remaining carbon is then determined by coulometric titration of the CO₂ evolved from the combustion of the samples. These analytical conditions minimize the crossover between the different components of the aerosol, but better to a clear-cut division between organics and soot carbon, the quantitative evaluation of their thermal evolution is obtained. Artifacts have been tested thoroughly with various standards and replicates of ambient air samples collected. The method gives reliable soot carbon determination at the microgram level in samples from a wide variety of environments. Combined H / C atomic ratio measurements and investigations of the problems associated with the thermal determination of soot carbon permit gaining some insight on the nature of carbonaceous aerosols. They reinforce the indication that soot carbon is not composed primarily of elemental carbon. Also, it is suggested that highly polymerized natural organic aerosols though different in nature could behave thermally and optically like soot.     

Flame retardancy of some ethylene–vinyl acetate copolymer‐based formulations

The combustion behaviour and thermal decomposition of ethylene–vinyl acetate copolymer (EVA) (26 wt% vinyl acetate content) formulations containing alumina trihydrate, ammonium polyphosphate, melamine, pentaerythritol and their co‐mixtures, were studied using cone calorimetry and thermogravimetric analysis. Formulations containing ammonium polyphosphate burned with the formation of intumescent carbonaceous chars, with EVA acting as a carbonization agent. EVA materials containing ammonium polyphosphate (20 wt%), with a sufficient amount of alumina trihydrate or melamine, were superior to the non‐intumescent alumina trihydrate and melamine containing formulations in terms of the heat release rate, mass loss rate and smoke production. Melamine showed some smoke suppressant effect and significant CO reducing properties. However, the melamine–EVA and melamine–alumina trihydrate–EVA showed a very high heat release rate. Thermogravimetric studies showed that oxygen played a favourable role in enhancing the char formation by encouraging active participation of the polymer matrix in the interaction with polyphosphoric acid. Copyright © 2000 John Wiley & Sons Ltd.     

Experimental study on heat release rate measurement in tunnel fires

Knowledge about the heat release rate (HRR) is essential for studying tunnel fires. The standard method in ISO 9705 is widely applied to calculate the HRR of combustion by measuring the consumption of oxygen in a fire. However, the studies of HRR measurement in full‐scale tunnel fires are rare because of the complication and costs of large experiments. This paper presents a system based on the principle of oxygen consumption calorimetry for the measurement of HRR and total heat release (THR) of full‐scale fires in tunnels. A total of 22 fire experiments are performed in a large‐scale ventilated testing metro tunnel with dimension of 100.0 m × 5.5 m × 5.5 m to validate the reliability and effectiveness of this system. Firstly, four oil spray fire tests are conducted with nozzle flow of 106 L/h at (1 ± 0.1) MW HRR to calibrate the instrumentation. Then, 18 full‐scale fire tests using square diesel pools at five sizes (0.5, 1.0, 2.5, and 5.0 m²) and wood cribs as fire sources are carried out for the measurement of HRR and THR. Results provided by the comparison between the measured HRR and THR values of the fire tests and the theoretically calculated ones show that our system works effectively in the HRR measurement of full‐scale fires in tunnels.