Ignition and flash-fire studies of cellulosic materials

Various celloulosic materials were evaluated for ignitability and flash-fire propensity, using screening test methods developed at the University of San Francisco. Time to ignition, using radiation from a high-temperature radiant source without a pilot flame, appeared to be primarily a function of heat flux and material density, rather than of type of wood or celloulosic board. At heat flux levels from 5.8 to 10.5 W cm^?2, time to ignition was shortest for cellulose fiberboard with a density of 0.2225 g ml^?1, followed by western red cedar at 0.314 g ml^?1, eastern white pine at 0.348 g ml^?1, southern yellow pine at 0.422 g ml^?1, Douglas fir at 0.565 g ml ^?1, and longest for hardboard at 0.878 g ml^?1. For the cotton and rayon woven-pile upholstery fabrics, time to ignition appeared to increase with increasing fabric weight. For Cellulose insulation treated with boron-containing additives, flash-fire magnitude decreased with increasing additive content. Flash-fire magnitude decreased more that could be accounted for by decreasing weight loss alone, indication reduction in the combustibility of the volatiles produced. Reduction in flash-fire propensity of cotton bating by treatment with boron-containing additives was also observed.     

Fire properties of surrogate refuse‐derived fuels

This paper investigates the fundamental fire properties of surrogate refuse‐derived fuels (RDF), a class of multicomponent materials characterized by high void fraction, with particles of polydisperse sizes and significant internal porosity. A surrogate RDF was developed to improve the reproducibility of experimental measurements. This surrogate RDF reflects typical municipal solid waste collected in the city of Newcastle, in the state of New South Wales in Australia. The material consists of shredded newspaper, wood, grass and plastic bags, with small amounts of sugar and bread. About 95% of the material passes through 50 mm square screens, as required by ASTM E828 standard for RDF‐3 specification. The experiments presented in this paper were performed with the components of the RDF dried in a forced‐air oven at 103° C, except for grass which was dried under nitrogen. The material was found to be very hygroscopic, requiring special care in handling. The experiments performed in the cone calorimeter were designed to measure the heat release rate, total heat release, time to ignition, time to extinction, effective heat of combustion and formation of CO during the combustion process, as a function of sample thickness, sample density and the magnitude of the imposed radiative heat flux. The thermophysical properties of the surrogate material were either measured (solid density, void space, particle density, particle porosity) or extracted from the published data (heat capacity). The present surrogate RDF material was found to ignite easily, within a few seconds of the imposition of the incident heat flux of 40 kW m^?2, and then to reach rapidly the peak heat release rate of 110–165 kW m^?2. The deduced values of the critical heat flux, pyrolysis temperature and effective thermal conductivity are 9–10 (±2) kW m^?2, 280–310 (±30)° C, and 0.4–0.7 (±0.3) W m^?1 K^?1, respectively, depending on the material density. The effective heat of combustion of the RDF was estimated as 15.3 MJ kg^?1. The material produced 1 kg of CO per 18 kg of dried RDF, mostly during smouldering phase after the extinguishment of the flaming combustion. These results indicate that dried RDF pose significant fire risks, requiring that fire safety systems be implemented in facilities handling RDF. Copyright © 2005 John Wiley & Sons, Ltd.     

Burning plastics: Mechanisms of smoke formation

Quantitative pyrolysis gas chromatography studies have been conducted on three grades of cross-linked polyester resin formulated for improved resistance to surface spread of flame. Pyrolysis temperatures from 723 to 1273 K were used, and these values correspond to ‘surface’ temperatures of materials exposed to heat fluxed of 15–149 kW m^–2 which are typical of conditions experienced in real fires. Comparison is made with earlier macro studies on the evolution of smoke from plastics materials exposed to similar heat fluxes under an inert atmosphere. There is some correlation between the smoke obscuration data obtained in previous macro studies and the yield of volatile aromatic products evolved on pyrolysis. The presence of flame retardants increases the formation of carbon in the pyrolysis residue and decreases the yield of volatile aromatic products isolated. The results are considered in the context of mechanisms of smoke formation.     

Improved fire safety of composites for naval applications

This study is based on the use of integral, hybrid thermal barrier to protect the core of the composite structure. Thermal barrier treatments evaluated in this study include ceramic fabric, ceramic coating, intumescent coating, hybrid of ceramic and intumescent coating, silicone foam, and phenolic skin. The composite systems evaluated in combination with thermal barrier treatments included glass/vinyl ester, graphite/epoxy, graphite/bismaleimide, and graphite/phenolic. All configurations were tested for flammability characteristics. These included smoke density and combustion gas generation (ASTM E-662), residual flexural strength (ASTM D-790), heat release rate, and ignitability (ASTM E-1354). ASTM E-662 test method covers the determination of specific optical density of smoke generated by solid materials. ASTM D-790 test method covers the determination of flexural properties of composite materials in the form of rectangular bars. ASTM E-1354 (cone calorimeter) covers the measurement of the response of materials exposed to controlled levels of radiant heating with or without an external ignitor, and is used to determine the ignitability, heat release rates, mass loss rates, effective heat of combustion, and visible smoke development. Without any fire barrier treatments, all composite systems evaluated in this study failed to meet ignitability and peak heat release requirements of MIL-STD-2031 (SH) at radiant heat fluxes of 75 and 100 kW m^?2, respectively. Intumescent coating and a hybrid system consisting of intumescent coating over ceramic coating were the most effective fire barrier treatments for composite systems evaluated in this study. Using either of these treatments, all composite systems met the ignitability requirements of 90 and 60 at 75 and 100 kW m^?2, respectively. Except for glass/vinyl ester, all systems also met the peak and average heat release requirements of MIL-STD-2031 (SH) at radiant heat fluxes of 25, 75, and 100 kW m^?2, respectively.     

Ignitability and heat-release properties of forest products

Forest products comprising sawn boards of seven timber species, plywoods of three timber species, two hardboards and one particleboard have been tested to ASTM E 906—Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products. One plywood was also tested after fire-retardant treatment by pressure impregnation. The fire-retardant treated plywood was also tested after being overlaid with untreated face and back veneers. One sawn board product was also tested after coating with an intumescent fire retardant. The ignition times of the forest products that had not been fire-retardant treated increased with density when exposed to heat fluxes of 20 and 40 kWm^?2. The maximum rate of heat release and the cumulative heat released rose with increasing impressed heat flux over the range 20–60 kWm^?2. Heat-release properties were dependent upon the impressed heat flux. Relationships were also established between the maximum rate of heat release and the cumulative heat released for heat flux exposures of 20, 40 and 60 kWm^?2. The ignition times of plywood were increased by pressure-impregnated fire retardants. Fire-retardant treatment by pressure impregnation prevented the ignition of a plywood and reduced its heat-release properties. The heat-release properties of a sawn board product were reduced by a fire-retardant surface coating.     

Experimental study on the radiative ignition of silicones

Silicones comprise a wide variety of materials such as fluids, elastomers, resins, and foams. This paper reports the ignitability of some typical silicones under various external radiant heat fluxes. The ignitability of silicones was studied using a cone calorimeter under radiant heat flux levels of 0.5–60 kW m⁻². The time to ignition of the silicones was found to be proportional to a power of the incident heat flux that varies from −1.33 to −2.84. For silicone fluids, viscosity (or molecular size) is the key variable in controlling the ignitability. For silicone elastomers, the fillers play an important role in controlling the ignitability, especially at incident heat fluxes lower than 35 kW m⁻². The ignitability of silicone resins depends on the chemical structure of the resins: the pure trifunctional resin has the lowest ignitability. The ignitability of the silicone foams having the same density depends on the foam thickness, especially at incident heat fluxes lower than 30 kW m⁻². © 1998 John Wiley & Sons, Ltd.     

Processing of porous glass ceramics from highly crystallisable industrial wastes

This study was carried out to gain understanding about the sintering behaviour of highly crystallisable industrial waste derived silicate mixtures under direct heating and rapid cooling conditions. The materials used in this study were plasma vitrified air pollution control waste and rejected pharmaceutical borosilicate glass. Powder compacts sintered under direct heating conditions were highly porous; compacts with particle size <?38?μm reached a maximum density of 2.74 g?cm^??3 at 850°C, whereas compacts with particles of size <?100?and <?250?μm reached maximum densities of 2.69 and 2.72 g?cm^??3 at 875 and 900°C respectively. Further increase in sintering temperature resulted in a rapid decrease in density of the glass ceramics. Image analysis results were used to link the sudden drop in density to the increase in volume of microsized pores formed in the samples during sintering. In particular, compacts made from <?38 μm particles sintered at 950°C resulted in 65 vol.-% porosity with a pore size of ～20?μm. Such materials can be used for sound and thermal insulation purposes.     

Thermophysical properties of Devonian shales

A detailed study of the thermophysical properties of Devonian shales from the central and eastern United States has been carried out. Thermal conductivity, thermal diffusivity, specific heat and dielectric constant data are presented. A Michigan shale sample with an oil yield of 28 litres per metric ton (1 t^?1) and a Kentucky shale (oil yield: 52 l t^?1) were selected. The specific heats of these shales are in the range 0.20–0.30 cal gm^?1 °C^?1, and increase with increasing temperature. The thermal conductivity (κ) of the two shale samples are comparable (ca. 1 W m^?1 °C^?1). The κ values show only a weak temperature dependance. The thermal diffusivity (α) of these shales range from 0.3–0.5 × 10^?2 cm² s^?1 and tend to decrease with increasing temperature. The dielectric constants show anomalously high values at temperatures above 200 °C. This effect is indicative of interfacial polarization mechanisms presumably arising from loss of water and onset of pyrolysis of the shale organic matter. Comparison of the trends in thermophysical behaviour of Devonian shales with data obtained previously on Green River oil shales is presented. The importance of thermophysical measurements in on-field applications in oil shale technology is highlighted.     

Critical flux determination by flux‐stepping

In membrane filtration related scientific literature, often step‐by‐step determined critical fluxes are reported. Using a dynamic microfiltration device, it is shown that critical fluxes determined from two different flux‐stepping methods are dependent upon operational parameters such as step length, step height, and flux start level. Filtrating 8 kg/m³ yeast cell suspensions by a vibrating 0.45 × 10^?6 m pore size microfiltration hollow fiber module, critical fluxes from 5.6 × 10^?6 to 1.2 × 10^?5 m/s have been measured using various step lengths from 300 to 1200 seconds. Thus, such values are more or less useless in itself as critical flux predictors, and constant flux verification experiments have to be conducted to check if the determined critical fluxes can predict sustainable flux regimes. However, it is shown that using the step‐by‐step predicted critical fluxes as start guesses, in our case, in constant flux verification experiments for 5 and 1/2 hours, a sustainable flux was identifiable. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Analysis of molar flux and current density in the electrodialytic separation of sulfuric acid from spent liquor using an anion exchange membrane

Separation of sulfuric acid from a dilute solution involved a plate and frame type electrodialysis unit using a commercial anion exchange membrane. Experiments were conducted in batch with catholyte concentrations ranging from 1 to 5 wt%. Effect of applied current density, initial catholyte concentration and initial concentration difference of catholyte and anolyte on the molar flux was studied extensively. The maximum molar flux was estimated to be 10.52×10^-8 mol cm^-2s^-1 at 4.45 wt% catholyte concentration and applied current density of 30 mA cm^-2. Current efficiencies were observed to be 75 to 85% at lower current density, which rose to more than 100% at 20 and 30mA cm^-2, at equal initial concentration of catholyte and anolyte. Diffusive flux and flux due to membrane potential contributed very less compared to total flux in presence of applied electric current. An equation was developed to predict the practical molar fluxes, which fitted satisfactorily with minor standard deviation. Pristine and used membrane specimens were characterized using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM).     

Flammability of GRP for use in ship superstructures

The burning characteristics of glass-reinforced panels with an isophthalic polyester resin, the same resin with an inorganic flame retardant, two differing vinylester resins or a resole phenolic as the matrix were tested at a range of incident heat flux values using a cone calorimeter. The phenolic composite was superior at all levels showing a longer ignition time, reduced heat output, less contribution to a low-level sustained fire (25 kWm^?2) and lower smoke yield.     

Study of Ignition of High-Energy Materials with Boron and Aluminum and Titanium Diborides

This paper describes the ignition of high-energy materials (HEMs) on the basis of ammonium perchlorate and ammonium nitrate and an energetic binder, containing the powders of Al (base composition), B, AlB₂, AlB₁₂, and TiB₂, upon initiation of the process by a CO2 laser in the heat flux density range of 90–200 W/cm². The ignition delay time and surface temperature of the reaction layer during the heating and ignition of HEMs in air are determined. It is obtained that the complete replacement of a micron-sized aluminum powder by amorphous boron in the composition of HEMs significantly reduces the ignition delay time of the sample (by 2.2–2.8 times) with the same heat flux density, and this occurs due to the high chemical activity of and difference between the mechanisms of oxidation of boron particles. The use of aluminum diboride in HEMs reduces the ignition delay time by 1.7–2.2 times in comparison with the base composition. The ignition delay time of the HEM sample with titanium diboride decreases slightly (by 10–25%) relative to the ignition delay time of the base composition.     

Characteristics of smoke in different thermal regimes

This paper examines the smoke emission and properties of polypropylene and flame retarded polypropylene injection moulded plaques. The prepared samples were irradiated in a Stanton Redcroft NBS type smoke box with an incident radiant energy of 2.5 W/cm². Nucleating agents were also introduced to increase the particle size of the smoke produced. The conclusions reached from this work on the emission of smoke in a non-flaming mode were that as the flame retardant additive content was increased, the optical density decreased, thus extending the time for escape. The emission of smoke from these polymers subjected to other radiant sources and in a flaming and non-flaming mode is being investigated further.     

Direct preparation of porous polyethylene filters by radiation polymerization of ethylene

In order to prepare porous, macroscopically homogeneous filters without a separate packing process, ethylene was polymerized by radiation in glass tubes. The bulk density of the polyethylene is approximately proportional to ρ (? M)²I^0.9t², where ρ M is average ethylene density, ? M is average ethylene fugacity, I is radiation dose rate, and t is reaction time. The effect of the bulk density on “treatment capacity” was investigated by experiments where air samples containing 0.1 wt-% iodine vapor were filtered. Treatment capacity is difined as that amount of air per gram of polyethylene which passes through a filter until the polyethylene reaches the break point. The treatment capacity is approximately constant at 9 × 10² cm³/g over the bulk density range from 0.03 to 0.07 g/cm³, and it is lower at the outside of this range. The pressure drop due to the polyethylene filters varies with the 2.7th power of the bulk density when the bulk density is more than 0.03 g/cm³; below 0.03 g/cm³ this exponent increases with decreasing bulk density. Because of both the necessity of high Treatment capacity and that of low pressure drop, the optimum bulk density of polyethylene in the filter is about 0.03 g/cm³.     

High pyroelectric response over a broad temperature range in NBT-BZT: SiO2 composites for energy harvesting

Pyroelectric energy harvesting is considered a highly promising technology for converting low-grade waste heat into electricity, but the practical applications of pyroelectric generators is limited by the their poor energy densities and instability. In this work, we construct SiO₂ networks with low heat capacities in NBT-BZT ceramics. These networks improve the heat transfer (dT/dt) and broaden the pyroelectric temperature region of the composites by reducing heat absorption capacity, thereby leading to high pyroelectric energy density and stability. The temperature range of the NBT-BZT composite with 0.1 wt% SiO₂ for pyroelectric coefficient higher than 20 × 10^?4 C m^?2 K^?1 is increased to 20 °C, This increase results in the high thermostability of energy harvesting. In addition, the NBT-BZT: 0.1 wt% SiO₂ composites show an optimized pyroelectric energy density of 110 u J cm^-3, nearly three times that of the pure NBT-BZT ceramics. This work is beneficial for the application of high-performance pyroelectric materials for devices used in energy harvesting.     

Permeation of water vapor through cellulose triacetate membranes in hollow fiber form

A modification of the carrier gas method for measuring permeability of a hollow fiber to a vapor is described with particular application to water vapor permeation through asymmetric cellulose triacetate in hollow fiber from. Conventional methods are inadequate because the high flux of permeation vapor combined with its low pressure on the permeate side and the small diameter of the fiber lead to an excessive buildup of pressure in the permeate stream—in some cases so great as to render much of the fiber length ineffective. The method described in this paper involves the permeation from the outside to the inside of the fiber of a binary mixture consisting of the water vapor and a fairly highly permeable carrier (helium). There is a significant pressure drop along the fiber, but a theoretical treatment is presented to take this into account and to permit a determination of the vapor permeability. Experiments at 35°C over a range of water vapor pressures up to 1.7 cm Hg gave a water flux of 9 × 10^?3 cc(S.T.P.)/cm²-sec-cm Hg, with an apparent slight decrease with increasing pressure. Over the same range of water vapor pressure the helium flux decreased from 2.3 × 10^?4 to 1.85 × 10^?4 cc(S.T.P.)/cm²-sec-cm Hg.     

Burning rate of solid wood measured in a heat release rate calorimeter

Burning rate is a key factor in modeling fire growth and fire endurance of wood structures. This study investigated the burning rate of selected wood materials as determined by heat release, mass, loss and charring rates. Thick samples of redwood, southern pine, red oak and basswood were tested in a heat release rate calorimeter. Results on ignitability and average heat release, mass loss and charring rates are reported for a heat flux range between 15 and 55 kw m^?2. In this range, burning rate increased linearly with heat flux. Burning rate was very species dependent. Heat release rate was related to mass loss by effective heat of combustion, which also increased with heat flux. Charring rate was related to mass loss rate and original wood density. Important char property data such as yield, density and contraction are reported. A simplified calculation method is proposed for calculating mass loss rate and charring rate based on heat release rate.     

Effect of curprous oxide in combination with molybdenum trioxide on smoke suppression in rigid poly(vinyl chloride)

Further investigation of the synergistic effect of smoke suppression between cuprous oxide and molybdenum trioxide in rigid poly(vinyl chloride) (PVC) was carried out by using a cone calorimeter (cone) at a high incident heat flux of 50 kW m^?2. Experimental data derived from the cone calorimeter indicated that binary mixtures of Cu₂O and MoO₃ clearly showed the synergistic effect in reducing smoke by decreasing total smoke production (TSP), average specific extinction area (av‐SEA), and smoke production rate (SPR). This result is in good agreement with that obtained from the NBS smoke chamber. However, the combustion process of rigid PVC could clearly be seen from the heat release rate (HRR), curve, SPR, and fire degradation obtained from the cone test, which could not be determined from the NBS smoke chamber. It was also found that the binary mixture showed the synergistic effect by increasing was also found that the binary mixture showed the synergistic effect by increasing char residue and reducing the fire degradation of the PVC backbone at a high incident heat flux of 50 kW.m^?2. All experimental data well supported the early cross‐linking mechanism of the PVC backbone mentioned in the literature and were consistent with the fire degradation behavior obtained from the cone calorimeter.     

Radiant flash pyrolysis of biomass using a xenon flashtube

Biomass materials, including lignin, redwood, corn cob, Calotropis Procera, Leucaena wood, Kraft paper, newsprint, cow manure, D -glucose, and D -cellobiose, were pyrolyzed in vacuum by the visible radiant flux emitted from a Xenon flashtube. The flux density exceeded 8 kW/cm² during the 1 ms flash. Sirup yields were low (avg 25%), while the gas yield was high (avg 32%). The gaseous products were composed primarily of CO and CO₂. The high relative yields of CO establish the existence of a high temperature fragmentation pathway active during the flash pyrolysis of all biomass materials.     

Radiative Ignition of Fine‐Ammonium Perchlorate Composite Propellants

Radiative ignition of quasi‐homogeneous mixtures of ammonium perchlorate (AP) and hydroxyterminated polybutadiene (HTPB) binder has been investigated experimentally. Solid propellants consisting of fine AP (2 μm) and HTPB binder (~ 76/24% by mass) were ignited by CO₂ laser radiation. The lower boundary of a go/no‐go ignition map (minimum ignition time vs. heat flux) was obtained. Opacity was varied by adding carbon black up to 1% by mass. Ignition times ranged from 0.78 s to 0.076 s for incident fluxes ranging from 60 W/cm² to 400 W/cm². It was found that AP and HTPB are sufficiently strongly absorbing of 10.6 μm CO₂ laser radiation (absorption coefficient ≈250 cm⁻¹) so that the addition of carbon black in amounts typical of catalysts or opacitymodifying agents (up to 1%) would have only a small influence on radiative ignition times at 10.6 μm. A simple theoretical analysis indicated that the ignition time‐flux data are consistent with in‐depth absorption effects. Furthermore, this analysis showed that the assumption of surface absorption is not appropriate, even for this relatively opaque system. For broadband visible/near‐infrared radiation, such as from burning metal/oxide particle systems, the effects of in‐depth absorption would probably be even stronger.