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.     

Combustion behaviour of polyurethane flexible foams under Cone Calorimetry test conditions

The first part of this study focuses on the effect of cone calorimeter test variables on polyurethane flexible foam properties such as ignitability, heat release rate, effective heat of combustion and mass loss. Three of the main commercial foam types were used, i.e. conventional slabstock foams, high-resilience slabstock foams and all-MDI (methylene diphenyldiisocyanate) moulded foams. A decrease in heat flux (down to 40%) with increasing distance from the conical heater was measured. As a consequence, results were found to depend to a large extent on the thickness and the melting behaviour of the foam samples. To achieve a sufficiently constant and uniform heat flux exposure, sample thickness had to be limited to 25 mm. In addition, repeatability was found to be good under various conditions, with percentage standard deviations for effective heat of combustion, peak rate of heat release and mass loss below 10%. Levels of radiant flux above 25 kW m^?2 were found to be very severe to test flexible polyurethane foams. Under such conditions, foams that show large differences in combustion performance in small-scale flammability tests performed almost identically in the cone calorimeter. In the second part of this study the effects of foam variables, such as foam type, density and melamine content, are defined. These effects were clearly pronounced at radiant flux levels of 15–25 kWm^?2. Density was found to be the key variable in controlling ignition resistance. In addition, high-resilience slabstock foams and all-MDI moulded foams performed better than conventional slabstock foams of the same density. Melamine addition resulted in a delay of ignition for all three foam types and an incomplete combustion, decreased heat release and effective heat of combustion in HR-slabstock and all MDI moulded foams. However, melamine is not effective as a heat sink in conventional slabstock foams. The different performance of the foam types under study can be explained by a different melting behaviour.     

Gasification of silicone fluids under external thermal radiation. Part I. Gasification rate and global heat of gasification

Transient gasification rates and fluid temperatures were measured for polydimethylsiloxane fluids ranging in viscosity from 0.65 cS to 60 000 cS in a nitrogen atmosphere at external radiant fluxes from 20 kW/m² to 70 kW/m². A detailed energy balance for each fluid sample was conducted to determine its global heat of vaporization. Two major energy loss corrections were identified and quantified. The absorption of incident radiation by the volatile products from short chain oligomers was measured and found to substantially reduce the incident flux to the sample surface; the energy loss due to re-radiation was determined to be a substantial factor in reducing the net heat flux to the sample for long chain length fluids. Other energy losses, e.g. heat loss to the substrate, were observed but were less significant. The average gasification rate for each fluid increased linearly with increasing external radiant flux. The global heat of gasification increases with an increase in the chain length (molecular weight) for the siloxane oligomers. These agreed well with calculated values. The global heat of gasification for 50 cS fluid is about 1200 kJ/kg and its value remains nearly constant for all higher molecular weight dimethylsiloxanes. Pyrolysis rates for siloxane fluids are very sensitive to trace catalysts. Measurements of the global heat of gasification for ultra-clean polymers resulted in significantly higher values (3000 kJ/kg). The gasification of siloxanes occurs via two modes or combinations thereof: (1) volatilization of molecular species native to the polymer, and (2) volatilization of thermal degradation products. The former process dominates for low molecular weight siloxanes (η<10 cS) and the latter process dominates for high molecular weight siloxanes (η>1000 cS). For the intermediate molecular weight siloxanes, both volatilization and degradation processes occur. © 1998 John Wiley & Sons, Ltd.     

Controlled-atmosphere cone calorimeter studies of silicones

A controlled-atmosphere cone calorimeter was used to investigate the burning of a silicone fluid and two silicone elastomers. The silicone materials were tested at 50 kW/m² incident heat flux in environments containing 15–30% oxygen. The test results were compared with a high molecular weight hydrocarbon fluid and an ethylene propylene rubber in terms of time to ignition, peak heat release rate and total heat released, carbon monoxide yield and carbon monoxide production rate, and smoke production and smoke production rate. The data from this study show that when materials burn in oxygen-enriched, normal, and vitiated atmospheres, silicone-based materials have a comparatively low peak heat release rate, total heat released, average CO production rate, and average smoke production rate as compared with organic-based materials. The smoke production and smoke production rate of silicone elastomers can be significantly reduced by adding appropriate smoke suppressants and additives. © 1997 John Wiley & Sons, Ltd.     

Comparison of cone and OSU calorimetric techniques to assess the flammability behaviour of fabrics used for aircraft interiors

Two test methods for measuring the heat release rate, HRR have been compared on fabric composites used for aircraft interior materials as side‐wall panels. These methods are based on the principles of direct measurement of the convective and radiant heat by thermopiles using an Ohio State University (OSU) calorimeter, and oxygen consumption using a cone calorimeter. It has been observed when tested by standard procedures, cone results at 35 kW/m² incident heat flux do not correlate with OSU results at the same heat flux. This is because in the cone calorimeter, the sample is mounted horizontally whereas the OSU calorimetric method requires vertical sampling with exposure to a vertical radiant panel. A further difference between the two techniques is the ignition source—in the cone it is spark ignition, whereas in the OSU it is flame ignition; hence, samples in the OSU calorimeter ignite more easily compared to those in the cone under the same incident heat fluxes. However, in this paper we demonstrate that cone calorimetric exposure at 50 kW/m² heat flux gives similar peak heat release results as the 35 kW/m² heat flux of OSU calorimeter, but significantly different average and total heat release values over a 2 min period. The performance differences associated with these two techniques are also discussed. Moreover, the effects of structure, i.e. type of fibres used in warp/weft direction and design of fabric are also analysed with respect to heat release behaviour and their correlation discussed. Copyright © 2005 John Wiley & Sons, Ltd.     

Mechanical properties of fire‐damaged glass‐reinforced phenolic composites

Changes to the mechanical and physical properties of a glass‐reinforced resole phenolic composite due to intense radiant heat and fire are investigated. Fire testing was performed using a cone calorimeter, with the composite exposed to incident heat fluxes of 25, 50, 75 or 100 kW/m² for 325 s and to a constant flux of 50 kW/m² for different times up to 1800 s. The post‐fire tensile and flexural properties were determined at room temperature, and these decreased rapidly with increasing heat flux and heat exposure time due mainly to the chemical degradation of the phenolic resin matrix. The intense radiant heat did not cause any physical damage to the composite until burning began on exposure to a high heat flux. The damage consisted of cracking and combustion of the phenolic matrix at the heat‐exposed surface, but this only caused a small reduction to the mechanical properties. The implication of the findings for the use of glass‐reinforced resole phenolic composites in load‐bearing structures for marine craft and naval ships, where fire is a potential hazard, is discussed. Copyright © 2000 John Wiley & Sons, Ltd.     

Actively Cooled Calorimeter Measurements and Environment Characterization In a Large Pool Fire

Quasi-steady-state heat fluxes absorbed on the calorimeter surface in ten vertical 0.1 m high×1 m wide zones were measured by means of water calorimetry. The calorimeter surface also included an array of intrinsic thermocouples to measure surface temperatures, and an array of Schmidt – Boelter radiometers for a second, more responsive, method of heat flux measurement. The pool fire environment characterization was done with measurements from velocity probes, directional flame thermometers (DFTs), and thermocouples. The initial measurements with a 1 m×1 m water cooled vertical flat plate calorimeter located 0.8 m above and inside a 6 m×6 m JP-4 pool fire are described. Water calorimetry measured absorbed surface heat fluxes of about 65–70 kW m⁻² with a gradual decrease with increasing height above the pool. Intrinsic thermocouple measurements recorded typical calorimeter surface temperatures of about 500°C, with spatial variations of ±150°C. Gas velocities across the calorimeter face averaged 3.4 m s⁻¹ with a predominant upward component, but with an off-vertical skew. Analysis of data collected in the fire environment in the vicinity of the calorimeter was performed to characterize the fire environment and to determine the input parameters required to calibrate analytical models. For this test, the emissive power distribution near the plate was essentially linear. Flux measurement in the fire environment ranged from 75 kW m⁻² to 175 kW m⁻². With temperature and heat flux data, effective absorption coefficients were determined by using a two-flux method to solve the inverse problem. The results show that the optical thickness increases with increasing distance from the calorimeter surface. The effective absorption coefficient is approximately 0.8 m⁻¹ in the vicinity (0 – 1.85 m) of the calorimeter and is approximately 2 m⁻¹ in the vicinity (1.85 – 2.8 m) of the plume centerline. The observed decrease in heat flux on the calorimeter surface with increasing vertical height is consistent with analytical fire models derived for constant temperature surfaces. Results from several diagnostics also indicated trends and provided additional insight into events that occurred during the fire. Some events are correlated, and possible explanations are discussed.     

Local temperature and wall radiant heat flux measurements in an industrial scale coal fired boiler

This paper reports measurements of local gas temperatures and wall incident radiant heat flux in an 80 MW_e pulverized coal corner fired boiler. Spatially resolved gas temperatures were measured using a 4 m long, triply-shielded suction pyrometer and total wall radiation was determined with an ellipsoidal radiometer. The data include detailed wall radiant heat flux measurements made around the periphery of the boiler at six different elevations. Local gas temperature profiles were measured at four axial positions in the boiler, with special attention to the near-burner region. Boiler operational data and coal proximate, ultimate and particle size analyses are also reported. Local gas temperatures in the boiler reached a maximum of nearly 1800 K near the burners and decayed to 1250 K at a position just above the boiler nose. In the burner plane gas temperatures varied from 600 K near the wall to 1800 K at the centre of the flame. Wall incident radiant heat fluxes varied between 440 kW m^{− 2} in the near-burner region to 100 kW m^{− 2} near the boiler nose. The radiation transport to the wall was observed to vary substantially around the periphery of the boiler, especially in the near-burner regions.     

Ignition and combustion of low‐density polyimide foam

The ignition, flaming and smoldering combustion of low‐density polyimide foam have been studied using a cone calorimeter. Low‐density polyimide foam exhibits a high ignition resistance. The minimum heat flux for the ignition of flaming combustion ranges from 48 to 54 kW/m². This minimum heat flux also indicates the heat flux for transition from smoldering to flaming combustion. The flaming combustion results show that the heat release rate of low‐density polyimide foam is very low even at a high incident heat flux of 75 kW/m². The smoldering combustion results show that the smoldering of low‐density polyimide foam becomes significant when the incident heat flux is greater than 30 kW/m². The smoldering combustion of low‐density polyimide foam cannot be self‐sustaining when the external heat source is removed. Copyright © 2003 John Wiley & Sons, Ltd.     

Ignition studies of cerium nitrate treated towels

This study evaluated the ignitability of cotton towel material saturated with an oxidizer solution of 0.5 N cerium nitrate in 2 N nitric acid. Four types of ignition testing were performed in this work: self‐heating oven tests, hot object ignition tests, radiative smoldering ignition tests, and piloted flaming ignition/burning rate tests. Results indicate that cerium nitrate significantly enhances the ignitability of the towels. Self‐heating properties of cerium nitrate treated towels were measured using the standard constant temperature oven method described by Bowes. Based upon these self‐heating properties, self‐heating is not a hazard for storage scenarios other than bulk storage (depths of several meters) of cerium nitrate treated towels at room temperature. Surface ignition of hot objects was observed for object temperatures as low as 250°C placed upon room temperature cerium nitrate treated towels. Ignition for hot objects buried within a pile of towels occurred for object temperatures as low as 230°C. Radiant heating tests of cerium nitrate treated towels showed initiation of smolder at heat fluxes as low as 3 kW/m² at surface temperatures as low as 175°C. This compares with ordinary cellulosic materials that require 7–8 kW/m² heat fluxes and temperatures of 250°C. All four scenarios demonstrate enhanced ignitability and burning rates of cerium nitrate treated towels. Copyright © 2005 John Wiley & Sons, Ltd.     

Thermal response characteristics of fire blanket materials

The thermal response characteristics of over 50 relatively thin (0.15–3.7 mm) fire blanket materials from four different fiber groups (aramid, fiberglass, amorphous silica, and pre‐oxidized carbon) and their composites have been investigated. A plain or coated fabric sample was subjected to a predominantly convective or radiant heat flux (up to 84 kW/m²) using a Meker burner and a cone heater, respectively. In addition to conventional thermal protective performance ratings for protective clothing, two transient thermal response times (for the fabric back‐side temperature to reach 300 °C and for the through‐the‐fabric heat flux to reach 13 kW/m²) and a steady‐state heat‐blocking efficiency (HBE) were introduced for both convective and radiant heat sources. For most woven fabrics, the HBE values were approximately 70 ± 10% for both convection and radiation and only mildly increased with the fabric thickness or the incident heat flux. Nonwoven (felt) fabrics with low thermal conductivity exhibited significantly better insulation (up to 87%) against convective heat. Highly reflective aluminized materials exhibited exceptionally high HBE values (up to 98%) for radiation, whereas carbon and charred aramid fabrics showed lower HBEs (down to 50%) because of efficient radiation absorption. A relatively thin fire blanket operating at high temperatures can efficiently block heat from a convective source by radiative emission (enhanced by its T⁴‐dependence and high surface emissivity) coupled with thermal insulation and from a radiant heat source by surface reflection while the aluminum surface layer remains. Copyright © 2013 John Wiley & Sons, Ltd.     

Hierarchical Cellular Poly(m-phenylene isophthalamide) with High Flame Retardancy,Mechanical Robustness,and Heat Resistance at Extreme Situation

High-performance cellular foams with superior mechanical properties and heat resistance are urgently needed to fulfill the applications in extreme environments. However, they are difficult to be prepared because of low gas diffusion rate in high-performance polymers. In this work, a facile solution-foaming strategy to prepare multifunctional foams based on poly(m-phenylene isophthalamide) (PMIA) is reported. The achieved PMIA foams show a hierarchically cellular structure containing macropores and mesopores. Due to their high porosity, the PMIA foams exhibit low thermal conductivity (0.0447–0.0498 W m⁻¹ K⁻¹) and high sound absorption coefficient at different frequency. A bimodal distribution on acoustic absorption is observed. With a bulk density range of 0.089–0.122 g cm⁻³, PMIA foams possess compressive moduli of 3.2–14.2 MPa and bending strength of 1.1–2.1 MPa, respectively. Moreover, they exhibit a recoverable deformation of 55.4% after 10 cycling 10% strain compressions and maintain a dimensional stability under harsh environment (–196 to 250 °C). Despite generated byproducts like polyurea, they still show a limiting oxygen index (25.2–26.3%) and relatively low heat release rate (178.3 kW m⁻²). This work provides a facile strategy to efficiently prepare high-performance PMIA foams for broad application prospects.     

Flame retardancy of ceramic-based rigid polyurethane foam composites

In this work, ceramic fillers zirconia and alumina powder were incorporated in the rigid polyurethane foams derived from modified castor oil and their impact on the mechanical, thermal, and fire performances of composite foams have been analyzed. It was observed that the addition of ceramic filler showed improved mechanical and thermal properties and best properties were shown by 6% zirconia with compressive strength of 6.61 MPa and flexural strength of 5.72 MPa. Zirconia also demonstrated an increase in T_5% up to 260 °C. Cone calorimetry shows a decrease in peak of heat release from 118 to 84 kW m⁻² and 94 kW m⁻² by the incorporation of alumina and zirconia powder, respectively. Furthermore, total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decrease remarkably on the incorporation of ceramic fillers. So, these fillers have a great potential as an additive to incorporate good mechanical, thermal, and fire properties in bio-based rigid PU foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48250.     

Heat transmission of proban®-treated fabrics subjected to a radiant heat source

The apparatus described in DIN 4842 was used to measure the heat transmission of a series of Nomex, polyester–cotton, Proban®-Treated cotton, untreated cotton and wool workwear fabrics subjected to a radiant heat source. Heat transmission was found to be dependent on the incident heat flux, fabric weight and fabric thickness. At the heat flux levels tested, 10 KJ m^?2s^?1 and 20 KJ m^?2s^?1, heat transmission was found to be largely independent of the fibre composition of the fabric when single layers of fabric were tested. The level of heat transmission was reduced by the use of multiplayer assemblies or a reflective aluminium coating, but the greatest reduction was obtained when air spaces were interposed between the fabrics. Conbinaitons of fabrics were developed which transmitted less than 205 KJ m^?2s^?1 during testing at incident heat flux levels of 10 KJ m^?2s^?1 and 20 KJ m^?2s^?1.     

Shielding effects of silica-ash layer on the combustion of silicones and their possible applications on the fire retardancy of organic polymers

This study demonstrates the shielding effects of a silica-ash layer on the combustion of silicones and their possible applications on the fire retardancy of organic materials. The deposited silica-ash layer, formed on the surface of silicone materials during combustion, has shielding effects on the combustion of silicones. It insulates the burning surface from the radiant heat of flame, as well as from the radiant heat produced from the burning of adjacent materials. It also restricts the diffusion of fuels into the combustion zone and the access of oxygen to the unburned fuels. The shielding effects provide some of the fundamentals for the development of silicone-based fire retardants. © 1998 John Wiley & Sons, Ltd.     

Properties of a novel inherently flame-retardant rigid polyurethane foam composite bearing imide and oxazolidinone

A novel inherently flame-retardant rigid polyurethane (PU) foam with imide and oxazolidinone was prepared by using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (PTDA) and 9,10-dihydro-9-oxa-(10-glycidoxypropylene)-10-phosphap-henanthrene-10-oxide (e-DOPO) as reactive flame retardants. The physical and mechanical properties of the prepared PU foams were investigated. The compressive strength was improved to 0.22 MPa, the thermal conductivity decreased, and the density hardly changed. Thermogravimetric (TG) analysis and TG analysis coupled with Fourier transform infrared spectroscopy indicated that the PTDA and e-DOPO showed a small improvement in thermal properties. The fire behaviors were evaluated based on the limited oxygen index (LOI), cone-calorimetry experiment, and smoke-density test. The LOI of the PU foam with PTDA and e-DOPO reached 22.4%. The peak of heat release rate and total heat release decreased to 227.50 kW m⁻² and 11.27 MJ m⁻² from 281.28 kW m⁻² and 14.05 MJ m⁻², respectively. The morphologies of the PU foam and residues after the cone-calorimetry test were characterized by scanning electron microscopy. X-ray photoelectron spectroscopy analysis indicated that PTDA and e-DOPO lead to an increase in graphite in the residue and the formation of a better barrier to prevent burning by the condensed-phase mechanism. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47943.     

Thermal effect on surrounding combustibles in minivan passenger car fires

In the fire safety design of parking lots and buildings, estimating the possibility of fire spreading to surrounding combustibles, such as neighboring buildings and cars, is essential. The ignition possibility to surrounding combustibles can be predicted from the heat flux from a burning car to the combustibles. In this study, we conducted 2 full‐scale car fire experiments using minivan passenger cars and measured the heat fluxes to their surroundings. The cars were ignited at the rear bumper with 80 g of alcohol gel fuel. The windows were closed. Heat flux gauges were placed around the car to measure the heat flux in various directions. Cedar boards were placed next to the gauges, and burn damage to the boards was observed. When the windows shattered in succession, combustion in the passenger compartment became larger. At a distance of 50 cm from the burning car, the heat flux was greater than 40 kW/m², and most of the cedar boards were completely burned. At a distance of 1 m, the heat flux was 10 to 20 kW/m², and some of the cedar boards were burned. We devised a method for modeling the shape and temperature of flames in the burning cars. Furthermore, we propose a method for calculating heat fluxes in the lateral direction of the burning minivan passenger car, and we compared the calculated and measured heat fluxes as a means of verifying the proposed method. The shape of flame in the burning car was approximated as a rectangular prism to calculate the heat flux. The calculation results were in good agreement with the experimental results. The proposed method is expected to be useful for fire safety engineering.     

A theoretical basis for flammability properties

Theoretical formulations are presented for the fire growth processes under external radiant heating. They included ignition, burning and energy release rate, and flame spread. The behaviour of these processes with external heating is described along with the critical conditions that limit them. These include the critical heat fluxes for ignition, flame spread and burning rate. It is shown how these processes and their critical conditions depend on a limited number of properties measurable by a number of standard test methods. The properties include heat of combustion, the heat of gasification, ignition temperature and the thermal properties of the material. Alternatively, the properties could be related to parameters easily found from data; namely: (1) the critical heat flux (CHF) for ignition; (2) the slope of the energy release rate with externally imposed flux, defined as heat release parameter (HRP); and (3) the ignition parameter, defined as thermal response parameter (TRP). It is further shown that the flame heat flux differences between small laminar flame ignition sources and larger turbulent flames can affect flame spread due to heat flux and ignition length factors. Finally, it is found that the critical energy release rates theoretically needed for ignition, sustained burning, and turbulent upward flame spread are roughly 13, 52, and 100 kW/m², respectively, and independent of material properties. Copyright © 2005 John Wiley & Sons, Ltd.     

An investigation of fire-plume impingement on a horizontal ceiling. 2—Impingement and ceiling-jet regions

A theoretical and experimental study of ceiling flows induced by both impinging fires and weak plumes on a horizontal ceiling is presented. Measurements along a ceiling radius were made of impinging diffusion flames with heat-release rates of 1.67 and 8.51 kW, resulting in convective and radiative ceiling-heat fluxes, radiant heat flux to the surroundings and profiles of mean velocity, mean temperature and mean concentrations of major species. However, only ceiling heat fluxes were obtained for weak plumes of pre-mixed flames of 0.24, 0.385 and 0.709kW. The predicted ceiling convective heat fluxes by an integral model are in good agreement with the measured values. In general, the present model also provides satisfactory predictions of flow thickness, bulk velocity, temperature and gas concentrations for both impinging fires and weak plumes.